Table Of ContentMethane and Alkane
Conversion Chemistry
Methane and Alkane
Conversion Chemistry
Edited by
Madan M. Bhasin
Union Carbide Corporation
South Charleston, West Virginia
and
D. W. Slocum
Western Kentucky University
Bowling Green, Kentucky
Springer Science+Business Media, LLC
Library of Congress Cataloging in Publication Data
Methane and alkane conversion chemistry / edited by Madan M. Bhasin and D. W Slocum,
p. cm.
"Proceedings of American Chemical Society Symposium on Methane and Alkane
Conversion Chemistry, held March 13-17, 1994, in San Diego, California"—T.p. verso.
Includes bibliographical references and index.
ISBN 978-1-4613-5730-8 ISBN 978-1-4615-1807-5 (eBook)
DOI 10.1007/978-1-4615-1807-5
1. Synthetic fuels—Congresses 2. Methane—Congresses. 3. Alkanes—Congresses. 4.
Qtidation—Congresses. I. Bhasin, Madan M. II. Slocum, D. W (Donald Warren), 1933-
III. American Chemical Society Symposium on Methane and Alkane Conversion Chemistry
(1994: San Diego, Calif.)
TP360.M465 1996 95-51190
661.8' 14-4c20 CIP
Proceedings of American Chemical Society Symposium on Methane and Alkane Conversion Chemistry,
held March 13-17, 1994, in San Diego, California
ISBN 978-1-4613-5730-8
© 1995 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1995
Softcover reprint of the hardcover 1st edition
All rights reserved
10 98765432 1
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
PREFACE
Natural gas, an abundant natural energy and chemical resource, is underutilized. Its inherent
high energy content is compromised by its volatility. Storage and transportation problems
abound for liquified natural gas. Several of the drawbacks of the utilization of natural gas,
particularly its high volatility, could be offset by development of an economical and efficient
process for coupling and/or further homologation of its principal component, methane.
Alternatively, other conversion strategies such as partial oxidation to methanol and syngas, to
oxygenates or conversion to such products via the intermediacy of chlorides should also be
considered.
Given the energy-intensive regimes necessary for the likely activation of methane, it
was inevitable that researchers would tum to the use of heterogeneous catalysts.
Heterogeneous catalysis is now a relatively mature discipline with numerous and diverse
reactions being explored alongside informative studies on surface characterization,
mechanism, and theory. Relationships to important related areas such as homogeneous
catalysis, organometallic chemistry, and inorganic chemistry have become firmly established
within this discipline.
The field of methane and alkane activation is now over ten years old. The first
decade of investigation produced results plagued by low yields and low-moderate
conversions with well-articulated mechanistic limitations. As we begin the second decade of
inquiry, novel strategies have brought increasing yields and conversions to such products as
ethane, ethylene, methanol, and formaldehyde. These new approaches utilize separation of
products via membranes or adsorbents. Moreover, additional mechanistic insight has been
forthcoming from theoretical and computational examination as well as experimental
investigation.
Catalysis itself is a strategic resource whose importance and remarkable capabilities
have been often demonstrated yet whose potential cannot be overestimated. As we progress
toward a chemical industry where process improvements for both bulk, commodity, and
specialty chemicals will increasingly be in demand, new and less expensive sources of raw
material must be sought. Natural gas is an obvious candidate source. Therefore, methods are
needed to activate methane for conversion to higher hydrocarbons, particularly to useful
olefins, the most important chemical industry building blocks, and to fuels.
The symposium from which this book originates was developed to further these
aspirations and concerns. Organization of the symposium was under the auspices of the
Catalysis and Surface Science Secretariat of the American Chemical Society, such
organization constituting one of the major undertakings of the Secretariat. The symposium
took place during the 207th National Meeting of the American Chemical Society which was
held in San Diego, March 13-17, 1994. Two ACS Divisions, Petroleum Chemistry and
Industrial and Engineering Chemistry, co-sponsored the four-day affair.
Investigations of methane and alkane activation are taking place throughout the
v
world. International representatives from Japan, China, Australia, India, Russia, and several
European countries made this symposium even more interesting and valuable to all
participants. Contributions by overseas researchers received financial support from the
Petroleum Research Fund, Norton Chemical Process Products Corporation, and Union
Carbide Corporation. Thus, the observations described in this monograph represent the
progress of a broad cross-section of the research going on throughout the world.
We, the editors, are most appreciative of the support that we received. We also would
like to express our sincerest thanks to our co-organizers, Professor Jack H. Lunsford (Texas
A&M University) and Dr. Jon G. McCarty (SRI International).
M. M. Bhasin
D. W. Slocum
vi
CONTENTS
GAS CONVERSION: METHANE AND ALKANE ACTIVATION CHEMISTRY
Oxidative Coupling of Methane-A Progress Report ............................................................ 3
M.M. Bhasin and K.D. Campbell
Methane and Light Alkane (C2-C4) Conversion over Metal Fluoride-Metal Oxide
Catalyst System in Presence of Oxygen ................................................................... 19
X.P. Zhou, S.Q. Zhou, W.D. Zhang, Z.S. Chao, W.Z. Weng, R.Q. Long,
D.L. Tang, H.Y. Wang, SJ. Wang, lX. Cai, H.L. Wan, and K.R. Tsai
Oxidative Coupling of Methane over Sulfated SrOILa203 Catalysts .................................. 31
Janos Sarkany, Qun Sun, Juana Isabel Di Cosimo, Richard G. Herman,
and Kamil Klier
The Oxidative Coupling of Methane over Zr02, Doped LiIMgO Catalysts ........................ 39
G.C. Hoogendam, K. Seshan, J.G. van Ommen, and lR.H. Ross
Evidence for the Production of Methyl Radicals on the Na2 W04/Si02 Catalyst upon
Interaction with Methane ......................................................................................... 45
Zhi-Cheng Jiang, Liang-Be Feng, Hua Gong, and Hong-Li Wang
Two-Step, Oxygen-Free Route to Higher Hydrocarbons from Methane over Ruthenium
Catalysts ................................................................................................................... 49
Manoj M. Koranne and D. Wayne Goodman
Homologation Reactions of Alkanes on Transition-Metal Surfaces .................................... 59
R.H. Cunningham, R.A. van Santen, A.V.G. Mangnus, and lH.BJ. Hoebink
A Comparative Study of Catalytic Behaviours of Sr-Ti, Sr-Zr, Sr-Sn Perovskites and
Corresponding Layered Perovskites for the Oxidative Coupling of Methane ......... 71
x.c.
W.M. Yang, QJ. Yan, and Fu
Promotion by Dichloromethane of the Oxidative Coupling of Methane on LiMnlMgO
Catalysts ................................................................................................................... 79
R. Mariscal, M.A. Pena, and lL.G. Fierro
Kinetics of Reaction of Oxygen with Lithium Nickel Oxide, and the Role of Surface
Oxygen in Oxidative Coupling of Methane ............................................................. 85
Y.-K. Sun, IT. Lewandowski, G.R. Myers, AJ. Jacobson, and R.B. Hall
vii
Conversion of Methane to Higher Hydrocarbons over Supported Transition Metal
Oxide Catalysts ........................................................................................................ 95
Liwu Lin, Laiyuan Chen, Zhusheng Xu, and Tao Zhang
MECHANISM AND MODELING OF METHANE-RICH OXIDATION
Effect of Diffusion Limitations of Surface Produced Radicals on the C2 Selectivity in the
Oxidative Coupling of Methane ............................................................................. 113
P.M. Couwenberg, Q. Chen, and G.B. Marin
Effects of Product Separation on the Kinetics and Selectivity of Oxidative Coupling ...... 123
R.B. Hall and G.R. Myers
Reactive vs. Adsorbed Oxygen in the Heterogeneous Oxidation of Methane
over Li/MgO ........................................................................................................... 131
AJ. Colussi and V.T. Amorebieta
The Role of Free Methyl Radicals in the Selective Oxidation of Methane over Silica-
Supported Molybdena .............................................................. ". ............................ 137
Roy S. Mauti and Charles A. Mims
Transient Studies of Methane Oxidative Coupling over Li Promoted LaNi03
Catalysts ................................................................................................................. 143
Zbigniew Kalenik and Eduardo E. Wolf
Synthesis of C2+ Hydrocarbons and Syngas by Gas Phase Methane Oxidation under
Pressure .................................................................................................................. 157
K. Fujimoto, K. Ornata, T. Nozaki, and K. Asami
Infrared Spectroscopic Studies of Adsorbed Methane on Oxide Surfaces at
Low Temperatures .................................................................................................. 163
Can Li, Guoqiang Li, Weihong Yan, and Qin Xin
Computer-Aided Elucidation of Reaction Mechanisms: Partial Oxidation of Methane .... 171
Raul E. Valdes-Perez
METHANE TO OXYGENATES AND CHEMICALS
Selective Photo-Oxidation of Methane to Formaldehyde Using Supported Group VB
and VIB Metal Oxide Catalysts ............................................................................. 179
Kenji Wada and Yoshihisa Watanabe
A Study of the lroniSodalite Catalyst for the Partial Oxidation of Methane
to Methanol ............................................................................................................ 187
Steven Betteridge, C. Richard A. Catlow, Robin W. Grimes, Justin SJ. Hargreaves,
Graham J. Hutchings, Richard W. Joyner, Christopher J. Kiely, Darren F. Lee,
Quentin A. Pankhurst, Stuart H. Taylor, and David Whittle
Partial Oxidation of Methane to Formaldehyde over Vanadia Catalysts:
Reaction Mechanism .............................................................................................. 195
B. Kartheuser, B.K. Hodnett, H. Zanthoff, and M. Baems
viii
Comparison of the Conversion of Methane and Ethane on Metal-Oxygen Cluster
Compounds ............................................................................................................. 207
S. Hong, S. Kasztelan, E. Payen, and lB. Moffat
Partial Oxidation of Methane by Molecular Oxygen over Supported V20S Catalysts:
A Catalytic and in Situ Raman Spectroscopy Study .............................................. 219
Qun Sun, Jih-Mim Jehng, Hangchun Hu, Richard G. Herman, Israel E. Wachs,
and Kamil Klier
Partial Oxidation and Cracking of Alkanes over Noble Metal Coated Monoliths ............. 227
M. Huff and L.D. Schmidt
Structural Features of Silica-Supported Vanadia Catalysts and Their Relevance in the
Selective Oxidation of Methane to Formaldehyde ................................................. 241
Marisol Faraldos, Miguel A. Bat'iares, James A. Anderson, and Jose Luis G. Fierro
Methane Conversion in AC Electric Discharges at Ambient Conditions ........................... 249
Rajat Bhatnagar and Richard G. Mallinson
Catalytic Studies of Methane Partial Oxidation ................................................................. 265
G. Stewart Walker and Jacek A. Lapszewicz
Some Characteristics of the Partial Oxidation ofCH4 to CH30H at High Pressures ........ 27 1
Hyman D. Gesser, Norman R. Hunter, and Albert N. Shigapov
Some Features of High Pressure Methane Oxidation to Methanol and Formaldehyde ...... 287
V.S. Arutyunov, V.Ya. Basevich, and V.1. Vedeneev
Strategies in Methane Conversion ...................................................................................... 291
Rameshwar D. Srivastava, Sai V. Gollakota, Gary J. Stiegel, and Arun C. Bose
Direct Oxidation of Methane with Organometallic Reactions ........................................... 297
Charles E. Taylor, Richard R. Anderson, Curt M. White, and Richard P. Noceti
Coupling of Catalytic Partial Oxidation and Steam Reforming of Methane to Syngas ..... 305
V.R. Choudhary, A.M. Rajput, and B. Prabhakar
Acetaldehyde from Chloromethane and Carbon Monoxide ............................................... 315
Y. Soong, R.R. Schehl, and R.P. Noceti
Para-Selective Gas Phase 02 Oxidation ofXylenes over FelMolBorosilicate Molecular
Sieve, CVD Fe/Mo/DBH ....................................................................................... 321
Jin S. Yoo, Chin Choi-Feng, and Gerry W. Zajac
Methanol Oxidation over Oxide Catalysts .......................................................................... 339
Stuart H. Taylor, Justin SJ. Hargreaves, Graham J. Hutchings, and
Richard W. Joyner
Index ................................................................................................................................... 347
ix
GAS CONVERSION: METHANE AND ALKANE
ACTIVATION CHEMISTRY
OXIDATIVE COUPLING OF METHANE - A PROGRESS REPORT
M.M. Bhasin and K.D. Campbell
Union Carbide Corporation
Industrial Chemicals Division, Research and Development
South Charleston, West Virginia 25303 (USA)
INTRODUCTION
A number of different schemes have been proposed to directly convert methane
(from abundant natural gas) into useful products, i.e., ethylene, propylene, as the
chemical industry building blocks, and liquid fuels for transportation since the
publication of early Union Carbide Corporation (UCC) work in 1982 [1]. At the heart
of these schemes lies the ability to convert methane in high selectivity to ethylene and
ethane. Though homogeneous catalysts, biological as well as biomimetic, and
heterogeneous catalyst systems have been extensively studied in recent years, this paper
will focus entirely on the heterogeneous catalytic route. Heterogeneous catalysis is
200
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Figure 1. Number of pUblications/year in the area of heterogeneous oxidative coupling
of methane. Number represents those published in English.
l'v/ethane and Alkane Conversion Chemistry
Edited by M. M. Bhasin and D. W. Slocum. Plenum Press. New York. 1995
