Catalytic Conversions of Synthesis Gas and Alcohols to Chemicals

468 Pages·1984·14.13 MB·English

by  Richard G. Herman (auth.)

Catalytic
Conversions of
Synthesis Gas and
Alcohols to Chemicals
Catalytic
Conversions of
Synthesis Gas and
Alcohols to Chemicals
Edited by
Richard G. Herman
Lehigh University
Bethlehem, Pennsylvania
Plenum Press. New York and London
Library of Congress Cataloging in Publication Data
Symposium on Catalytic Conversions of Synthesis Gas and Alcohols to Chemicals (1983:
White Haven, Pa.)
Catalytic conversions of synthesis gas and alcohols to chemicals.
"Proceedings of a Symposium on Catalytic Conversions of Synthesis Gas and Alcohols
to Chemicals, held April 6-8, 1983, at the Middle Atlantic Regional Meeting of the
American Chemical Society at Pocono Hershey Resort, White Haven,
Pennsylvania"-CIP verso t.p.
Includes bibliographical references and index.
1. Catalysis-Congresses. 2. Synthesis gas-Congresses. 3. Alcohols-Congresses. 4.
Chemicals-Congresses. I. Herman, Richard G. II. American Chemical Society. Middle
Atlantic Regional Meeting (17th: 1983: White Haven, Pa.) Ill. Title.
TP156.C35S96 1983 661'.805 83-26884
ISBN-13: 978-1-4612-9696-6 e-ISBN-13: 978-1-4613-2737-0
DOl: 10.1007/978-1-4613-2737-0
Proceedings of a Symposium on Catalytic Conversions of Synthesis
Gas and Alcohols to Chemicals, held April 6-8, 1983, at the Middle
Atlantic Regional meeting of the American Chemical Society, in the
Pocono Hershey Resort, White Haven, Pennsylvania
© 1984 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1984
A Division of Plenum Publishing Corporation
233 Spring Street, New York, N.Y. 10013
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted,
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recording, or otherwise, without written permission from the Publisher
DEDICATION BY THE EDITOR
Dedicated to my scientific mentors, Abraham Clearfield, Sten
Ahrland, Jack H. Lunsford, and Kamil Klier, who, with patience, per
severance, and example, provide continual encouragement, to my in
spirational academic great-grandfather, Linus Pauling, to an inspi
rational great-grandfather of catalysis, Paul H. Emmett, and to the
past and present faculty, especially of the Chemistry Department, at
Fredonia State University College, who teach the heart and mind that,
with study, effort, and optimism, nearly all goals are attainable.
PREFACE
Most of the papers contained in this volume are based on pres
entations made at the symposium on Catalytic Conversions of Synthesis
Gas and Alcohols to Chemicals, which was held at the 17th Middle At
lantic Regional Meeting of the American Chemical Society, April 6-8,
1983, in the setting of the Pocono Hershey Resort, White Haven, PA.
I thank Dr. Ned D. Heindel, General Chairman, and Dr. Natalie Foster,
Program Chairman, both of Lehigh University, for the invitation to
organize the symposium. Financial support was received from Air
Products and Chemicals, Inc. for the organization of the symposium,
and acknowledgement is made to Air Products and Chemicals, Inc. and
to the Donors of the Petroleum Research Fund, administered by the
American Chemical Society, for partial support of the conduct of the
symposium.
The theme of this volume is the recent progress made in devel
oping and understanding viable catalytic syntheses of chemicals di
rectly from synthesis gas (CO + H2) or indirectly via alcohols. An
aim of the symposium and of this volume is to provide a meaningful
blend of applied and basic science and of the chemistry and engineer
ing of processes that are, or hold promise to be, economically and
industrially feasible. The topics demonstrate the increasing impor
tance of synthesis gas as a versatile feedstock and emphasize the
central role that alcohols, such as methanol, can playas chemical
intermediates. Although recent developments in, and new perspectives
of, established processes are presented, the emphasis is to provide
insights into processes that are still in the research, development,
and scale-up stages.
The practical orientation of this volume is directed towards
professional chemists and engineers. However, the papers are written
in an instructional fashion so that this volume can be used as a com
plementary reference book in advanced undergraduate or graduate
courses in catalysis.
I wish to thank Dr. Henry Leidheiser, Jr., Director of the Canter
for Surface and Coatings Research at Lehigh University from 1968 to
1983, for his continuous encouragement and support. Appreciation is
vii
viii PREFACE
extended to all of the authors for their pleasant and timely cooper
ation and for their efforts in producing quality papers. I espe
cially appreciate and thank my wife, Helen Lynn, for.her assistance
in the formatting of this volume and for typing the final copy.
Richard G. Herman
September 1, 1983
CONTENTS
INTRODUCTORY ORIENTATION
Perspectives on the United States Feedstocks for the
Production of Energy and Chemicals • • 3
Richard G. Herman
The Production of Synthesis Gas from Methane, Coal
and Biomass . • • • . • . • . . • • . . 37
Michael S. Graboski
DIRECT CONVERSION OF SYNTHESIS GAS TO CHEMICALS
Effects of Cobalt on Synthesis Gas Reactions over
Copper-based Catalysts • • • • • • 53
F. N. Lin and F. Pennella
Thorium-Copper Intermetallic Catalysts for the
Synthesis of Methanol 65
G. B. Atkinson, E. G. Baglin, L. J. Nicks, and
D. J. Bauer
Alcohol/Ester Fuels from Synthesis Gas • • • • • 81
John F. Knifton, Robert A. Grigsby, Jr., and
Sheldon Herbstman
Untangling the Water Gas Shift from Fischer-Tropsch:
A Gordian Knot? •••••••••••• 97
Cheryl K. Rofer-DePoorter
Some Aspects of the Slurry Phase Fischer-Tropsch Process 129
J. V. Bauer, B. W. Brian, S. A. Butter, P. N. Dyer,
R. L. Parsons, and R. Pierantozzi
ix
x CONTENTS
Metal-Zeolite Catalysts for the Conversion of Synthesis
Gas to Selected Hydrocarbon Products • • • • • • • 151
v.
U. S. Rao, R. J. Gormley, R. R. Schehl, K. H. Rhee,
R. D. H. Chi, and G. Pantages
Conversion of Synthesis Gas to Olefins over Physical
Mixtures of High Si02/A1203 ZSM-5 and Fe(K) •••••• 167
F. G. Dwyer and W. E. Garwood
Catalyst Support Effects on Selectivity in the
Fischer-Tropsch Synthesis 179
J. G. Goodwin, Jr., Y. W. Chen, and S. C. Chuang
REACTIONS WITH SYNTHESIS GAS TO FORM CHEMICALS
The Use of Perfluoroalkanesulfonic Acids in the
Palladium-Catalyzed Carbomethoxylation of Olefins 193
F. J. Waller
Phosphine Modified Cobalt Carbonyl Catalysts for the
Hydroformylation of Dicyclopentadiene 203
Clayton D. Wood and Philip E. Garrou
Ethylene Glycol from Methanol and Synthesis Gas via
Glycolic Acid • • • • • • • • • • • • • 221
S. Suzuki, J. B. Wilkes, R. G. Wall, and S. J. Lapporte
SYfithesis Gas to Formic Acid via Methanol Carbonylation 249
Alan Peltzman
Recent Advances in Alcohol Homologation: The Effect of
Promoters 261
W. R. Pretzer and M. M. Habib
UTILIZATION OF ALCOHOLS TO PRODUCE CHEMICALS
Polyethers and Organorhodiums: A Study of Oxidative
Addition and Transfer Hydrogenation • • • • • 287
M. L. Deem
Synthesis of High Octane Ethers from Methanol and
Iso-Olefins • • • • • • • • • • • • • 307
Jack D. Chase
Conversion of Methanol to Low Molecular Weight Olefins
with Heterogeneous Catalysts • • • • • • • • • • • 323
Lujia Liu, Ricardo Garza Tobias, Kenneth McLaughlin,
and Rayford G. Anthony
CONTENTS xi
Catalytic Conversion of Alcohols to Olefins 361
Oemer M. Kut, Robert D. Tanner, J. E. Prenosil, and
Kenneth Kamholz
Conversion of Methanol to Hydrocarbons on Heteropoly
Compounds • • • • 395
J. B. Moffat and H. Hayashi
Formaldehyde from Methanol • • • • • • • • • • • • • 413
C. J. Machiels, U. Chowdhry, R. H. Staley, F. Ohuchi,
and A. W. Sleight
Catalytic Conversions of Methanol to Chloromethanes 419
S. Akiyama, T. Hisamoto, T. Takada, and S. Mochizuki
Alkylation of N- and O-Heteroatom Compounds with Alcohols,
with Special Reference to the Synthesis of Alkylamines. 433
Richard G. Herman
APPENDICES
1. U. S. Energy Conversion Factors 4~
2. Chemical Nomenclature 465
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
INDEX 469
INTRODUCTORY ORIENTATION