Table Of ContentSustainable Strategies for the
Upgrading of Natural Gas:
Fundamentals, Challenges,
and Opportunities
NATO Science Series
A Series presenting the results of scientific meetings supported under the NATO Science
Programme.
The Series is published by IOS Press, Amsterdam, and Springer (formerly Kluwer Academic
Publishers) in conjunction with the NATO Public Diplomacy Division.
Sub-Series
I. Life and Behavioural Sciences IOS Press
II. Mathematics,Physics and Chemistry Springer (formerly Kluwer Academic Publishers)
III.Computer and Systems Science IOS Press
IV.Earth and Environmental Sciences Springer (formerly Kluwer Academic Publishers)
The NATO Science Series continues the series of books published formerly as the NATO ASI Series.
The NATO Science Programme offers support for collaboration in civil science between scientists of
countries of the Euro-Atlantic Partnership Council.The types of scientific meeting generally supported
are “Advanced Study Institutes”and “Advanced Research Workshops”, and the NATO Science Series
collects together the results of these meetings.The meetings are co-organized by scientists from
,
NATO countries and scientists from NATOs Partner countries – countries of the CIS and Central and
Eastern Europe.
Advanced Study Institutesare high-level tutorial courses offering in-depth study of latest advances
in a field.
Advanced Research Workshops are expert meetings aimed at critical assessment of a field, and
identification of directions for future action.
As a consequence of the restructuring of the NATO Science Programme in 1999, the NATO Science
Series was re-organized to the four sub-series noted above. Please consult the following web sites for
information on previous volumes published in the Series.
http://www.nato.int/science
http://www.springeronline.com
http://www.iospress.nl
Series II:Mathematics,Physics and Chemistry – Vol.191
Sustainable Strategies for the
Upgrading of Natural Gas:
Fundamentals, Challenges,
and Opportunities
edited by
Eric G.Derouane
Universidade do Algarve,
Faro,Portugal
Valentin Parmon
Boreskov Institute of Catalysis,
Novosibirsk, Russia
Francisco Lemos
Instituto Superior Técnico,
Universidade TTTécnica de Lisboa,
Portugal
and
Fernando Ramôa Ribeiro
Instituto Superior Técnico,
Universidade TTTécnica de Lisboa,
Portugal
Published in cooperation with NATO Public Diplomacy Division
Proceedings of the NATO Advanced Study Institute on
Sustainable Strategies for the Upgrading of Natural Gas:
Fundamentals, Challenges, and Opportunities
Vilamoura, Portugal
6–18 July 2003
A C.I.P.Catalogue record for this book is available from the Library of Congress.
ISBN-10 1-4020-3309-5 (PB) Springer Dordrecht, Berlin, Heidelberg, New York
ISBN-13 978-1-4020-3309-4 (PB) Springer Dordrecht, Berlin, Heidelberg, New York
ISBN-10 1-4020-3308-7 (HB) Springer Dordrecht, Berlin, Heidelberg, New York
ISBN-10 1-4020-3310-9 (e-book) Springer Dordrecht, Berlin, Heidelberg, New York
ISBN-13 978-1-4020-3308-7 (HB) Springer Dordrecht, Berlin, Heidelberg, New York
ISBN-13 978-1-4020-3310-0 (e-book) Springer Dordrecht, Berlin, Heidelberg, New York
Published by Springer,
P.O.Box 17, 3300 AADordrecht, The Netherlands.
Printed on acid-free paper
All Rights Reserved
© 2005 Springer
No part of this work 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, with the exception of any
material supplied specifically for the purpose of being entered and executed on a
computer system, for exclusive use by the purchaser of the work.
Printed in the Netherlands.
TABLE OF CONTENTS
Preface ix
Lectures 1
Natural Gas: Fuel or Feedstock? 3
Jens R. Rostrup-Nielsen
Molecular Chemistry of Alkane Activation 25
Frigyes Solymosi
Economics of Alkane Conversion 51
Jean-Paul Lange
Theoretical Basis of the Activation of Light Alkanes 85
M. Witko, R. Tokarz-Sobieraj, R. Grybo(cid:286)
Surface Organometallic Chemistry of Tantalum: Application to the
Metathesis of Alkanes Catalyzed by a Tantalum Hydride
Supported on Silica 107
J. Thivolle-Cazat, C. Coperet, S. Soignier, M. Taoufik, J.M.
Basset
The Challenges in Converting Remote Natural Gas to Valuable
Products 125
David Trimm
Alternative Routes to Synfuel from Natural Gas 137
David Trimm
New Technologies for Light Alkane Upgrading 149
Jorge Gascon, Carlos Tellez, Javier Herguido, Miguel
Menendez
Fundamentals of the Fischer-Tropsch Synthesis 173
A.L. Lapidus
Reactor Technology for Syngas and Hydrogen 185
E. H. Stitt
Engineering Alkanes to Olefins and Higher Value Chemicals 217
Domenico Sanfilippo, Ivano Miracca, Marco Di Girolamo
Membrane Reactors for the Fischer-Tropsch Synthesis 249
Alexander A. Khassin
Sources of Methane for Sustainable Development 273
V.N. Parmon
Communications 285
CO Separation by Membranes in Natural Gas Processing 287
2
G. Clarizia, E. Drioli
vi
Structural and Textural Properties of MCM-41 Mesoporous
Molecular Sieves Containing Nb, V, Mo – Alternative Catalysts
for Hydrocarbons Oxidation 293
I. Nowak, B. Kilos, M. Ziolek, J.C. Volta
Acidic and Catalytic Properties of Dealuminated BEA Zeolites 301
J. P. Marques, I. Gener, P. Ayrault, J.C. Bordado, J.M. Lopes,
F. Ramôa Ribeiro, M. Guisnet
Influence of the H-Ferrierite Sample on the Selectivity of Skeletal
n-Butene Isomerization 305
B. De Menorval, N. S. Gnep, M. Guisnet
Study on the Lattice Defects in the Mixed Oxides of Neodymium
and Alkaline Earth Elements and their Role on the Oxidative
Coupling of Methane 309
D. Filkova, R. Edreva-Kardjieva, N. Dragan, D. Crisan, L.
Petrov
Molecular Mechanism of the Methane Dissociation on the
Vanadium Oxides Clusters. DFT Calculations 317
Witold Piskorz, Ewa Broclawik
Acidity, Activity and Micro-Kinetics Studies in an H-ZSM5 321
P. Borges, R. Ramos Pinto, M.A.N.D.A. Lemos, J. Védrine,
E.G. Derouane, F. Lemos, F. Ramôa Ribeiro
Microkinetic Model for Propane Activation over H-ZSM5 327
X. Wang, H. Carabineiro, M.A.N.D.A. Lemos, F. Lemos, F.
Ramôa Ribeiro
13C MAS NMR Mechanistic Study of the Initial Stages of Propane
Activation over Zn/H-MFI Catalyst 333
Yu.G. Kolyagin, J. Quartararo, E.G. Derouane, F. Fajula, I.I.
Ivanova
Dehydrogenation of Propane over Chromium-Based Catalysts 339
P. Michorczyk, J. Ogonowski, D. Ralowicz
Catalytıc Oxıdatıon of Methanol to Formaldehyde 345
A. H. Yılmaz, F. S. Atalay, S. Atalay
Conversion of Gas Condensate over Metal-Containing MFI
Catalysts 351
A.G. Popov, A.V. Smirnov, J. Krysciak, M. Derewinski, O.V.
Barsukov, E.G. Derouane, F. Lemos, F. Fajula, I.I. Ivanova
Coke Formation on Alumina and Alumina Supported Platinum
Catalysts 359
Zenon Sarbak
Activation Studies of the Cs-Doped Cu/ZnO Catalyst for the
Higher Alcohol Synthesis 365
L. Nowicki, T. Olewski, T. Bedyk, S. Ledakowicz
vii
Development of High Temperature Catalytic Reactors for
OxidativeConversion of Natural Gas 377
S. Cimino, F. Donsì, R. Pirone, G. Russo
The Effect of Process Conditions on Product Formation in Fischer-
Tropsch Synthesis 383
Sh. S. Itkulova
Mathematical Modeling of Steam Reforming Tubes with Shaped
Particles 389
A.P. Kagyrmanova, I.A. Zolotarskii, N.V. Vernikovskaya, E.I.
Smirnov, V.A. Kuzmin
Application of NMR Microimaging for the Investigation of the
Heterogeneous Catalytic Reactions inside Catalyst Pellets and
Fixed Catalyst Bed 395
A.A. Lysova, I.V. Koptyug, A.V. Kulikov, V.A. Kirillov,
R.Z. Sagdeev, V.N. Parmon
Conclusions 401
Natural Gas as Feedstock 403
Jacques C. Védrine
Sustainable Strategies for the Upgrading of Natural Gas 413
Eric G. Derouane
Participants 421
Subject Index 435
Author Index 441
PREFACE
Energy and feedstock materials for the chemical industry are in
increasing demand and, with constraints related to the availability and use of
oil, the energy and chemical industry is undergoing considerable changes.
In the recent years, major restructuring has occurred in the oil,
petrochemical, and chemical industry, with increasing attention devoted to
the use of natural gas, methane in particular, as a chemical feedstock rather
than just as a fuel. The conversion of remote natural gas into liquid fuels or
other transportable chemicals is a challenge to industrial catalysis. Few
processes exist so far with the major ones involving the conversion of
natural gas to synthesis gas by steam reforming, CO reforming, or partial
2
oxidation, followed by the syntheses of methanol, hydrocarbons (Fischer-
Tropsch synthesis), or ammonia. IThe development of new processes for the
conversion of natural gas has suffered from the price differential between
the product and natural gas being to small. However, this situation is now
changing: (i) as synthetic fuels have a premium value because they are
sulphur-free and may also have high cetane and octane numbers and (ii) as
new routes appear to synthesize higher value products.
The need for the use of cheaper and widely available feedstocks, and the
development of sustainable and environmentally friendly chemical
processes is rapidly growing under both economical and public pressures.
Obviously, adding value to light (C -C ) hydrocarbons, i.e., the use of
1 4
natural gas whose major component is methane, as a chemical feedstock, has
become of increasing importance as natural gas reserves appear to exceed oil
reserves. However, the upgrading and functionalization of natural gas
components will only be a reality if it is demonstrated that there is a
fundamental basis and a tangible advantage into making selectively C-C
bonds (from light hydrocarbons) and high value oxygenates, rather than
breaking C-C- bonds (cracking of oil) or generating carbon oxides.
Promising new uses of methane which exclude the production of synthesis
gas and its utilization, and the oxidative coupling of methane, are the high
temperature pyrolysis of C -C alkanes with short residence time in a hot
1 3
zone leading to polycyclic aromatics, the conversion of methane to aromatic
compounds using molybdenum-modified zeolites as catalysts, the direct and
selective conversion of methane to methanol or formaldehyde (homogenous
gas phase process or homogeneous and heterogeneous catalytic processes),
the oxidative methylation of hydrocarbons with methane, and the
carbonylation of methane by CO to acetic acid. Other interesting reactions
are the direct conversion of ethane to ethanol or acetic acid, and that of
ix
x
propane to isopropanol, acrolein, and acrylic acid. Heterogeneous catalysis
should not be viewed as the preferred choice for such conversions, and
either homogeneous catalysis or biomimetic alkane activation should also be
considered.
Advances in the development of new sustainable routes for the
conversion of natural gas will be strongly promoted by increasing
integration of efforts and expertise comprising all the areas of knowledge
involved. Catalysts and processes cannot be addressed separately. They must
be developed continuously and interactively by academic and industrial
teams. Academic programs often study reactions and catalysts under
conditions that are convenient, but not necessarily relevant to potential
application, while industrial laboratories devote much less effort to
mechanistic studies that are often central to understanding and progress. To
counter this splitting of effortsthat may hinder progress in this area, research
programmes aimed at addressing future research targets in this field should
involve multidisciplinary teams comprising chemists from the
heterogeneous and homogeneous catalysis communities, materials scientists,
theoretical scientists and (reaction and reactor) chemical engineers. In
addition, it is essential that strong collaborations should bet established
between the industrial and academic communities. These collaborations
should be established at the project design stage to ensure that both viable
targets and timescales are agreed and achieved.
The aim of the ASI that took place in Portugal in July 2003 was to gather
a multidisciplinary group of people involved in the field, experts,
practitioners, and students, in the discussion of this important issue for the
energy and chemical industry. One of the outcomes of this ASI is the present
book which comprises all the written contributions that were presented,
either as lectures by the invited speakers or by communications from other
participants, as well as the discussions that took place during the lectures,
the workshops and the poster sessions. The book is divided into three
sections. The first one contains the lectures presented at the meeting, the
second one comprises the communications contributed during the discussion
periods, and the third one covers the conclusions of the NATO ASI.
The editors wish to thank all attendees of the meeting, , in particular the
lecturers who promoted the discussions by their lively and superb
presentations as well as the other active and dedicated participants . Special
thanks are due to the people involved in the organisation of the ASI, in
particular to the local organising committee, Hugo Carabineiro, Ricardo
Ramos Pinto, Pedro Borges, Maria Amélia Lemos, Filipe Freire, José
Manuel Lopes, Carla Pinheiro, Isabel Fonseca, and to Pat Gibbs for her
efficient secretarial help. Sponsorship of the meeting by the NATO Science
Programme, the Technical University of Lisbon, Finibanco, Fundação para a
Ciência e Tecnologia, Taguspark Society, BP, Total, the British Council, the
xi
French Embassy in Portugal and Sociedade do Ar Líquido is also
acknowleged.
Eric Derouane
Valentin Parmon
Francisco Lemos
Fernando Ramôa Ribeiro
