Natural Gas Conversion V, Proceedings ofthe 5th International Natural Gas Conversion Symposium,

606 Pages·1998·17.24 MB·English

by  A, A. Parmaliana, D. Sanfilippo, F. Frusteri, Vaccari and F, Arena (Eds.)

P R E F A C E
Many words have been used to give the more appropriate idea of the scientific, economic
and technological impact of the Natural Gas Conversion on energy production, chemical and
petrochemical industry as well as on the economy of the countries possessing large reserves. NG
Conversion has been considered a challenging topic for the modem catalysis, now, at the eve of the
third millennium, it is one of the greatest and proven scientific achievement of the last decade
which will imply significant change in the current technology related to fuel, gasoline ,
intermediates and chemicals production. A rapid look at the volumes collecting the papers presented
at the NG Conversion Symposia allows to experience the growing interest devoted to the NG
Conversion along the years as well the consolidated trend to lessen the attention towards topics
which in spite of their potential importance are quite far from the industrial exploitation and to
focus all the efforts towards research subjects which deserve a greater technological interest being
then economically rewarding.
Along the years the number of papers aimed to present technological issues and economical
evaluation of the gas to liquid (GTL) processes is growing, the Fischer-Tropsch chemistry, catalysis
and technology is currently revisited, new approaches for syngas production are currently pursued.
However, even if such topics constitute the driving forces for attracting more and more interest
towards the NG Conversion we must consider that innovative research approaches for the NG
Conversion involving the use of membrane reactor and/or electrochemical devices original methods
for the direct conversion of natural gas to formaldehyde and methanol as well oxygenates of higher
added value obtained trough two-step or cross-coupling reaction systems are presently pursued by
many academic and industrial research groups worldwide. On other hand, such a great scientific
and technological interest posed in the NG Conversion, apart the reasons above outlined, arises
from the fact that on January 1988 the ascertained and economically accessible reserves of NG
amounted worldwide to over 144,000 billion cubic meters, corresponding to 124 billion tons of oil
equivalents (comparable with the liquid oil reserves estimated to 138 billion TOE). It is
hypothesized that the volume of NG reserve will continue to grow at the same rate of the last
decade. Forecasts on production indicate a potential increase from about 2,000 billion cubic meters
of 1990 to not more than 3,300 billion cubic meters in 2010, even in a high economic development
scenario. NG consumption represents only one half of oil one: 1.9 billion TOE/y as compared with
3.5 of oil. As a consequence in the future gas will exceed oil as carbon atom source.
All these aspects indicate that in the future the potential for getting energetic vectors or
petrochemicals from NG will continue to grow.
vi
The first need is to transport NG from production sites to the consumption markets. Current
technologies for marking available this "remote gas" are basically as CNG via pipelines (on-shore -
off-shore) or LNG via ocean shipping in dedicated tankers. The delivered cost is relevant to the
distance and over 1 ,000- 2,000 kilometers LNG becomes competitive with CNG. The value at
which this remote gas is made available in the developed markets represents the break-even price or
the economic baseline for any alternative uses.
The presence of light paraffins (C2-C4) in the NG can be a key factor in promoting further
exploitation of the NG conversion.
Indeed, light NG paraffins, apart from their use in steam cracking, have had some additional
exploitation: maleic anhydride from butane and the selective production of olefins (propylene and
isobutylene, butadiene) via dehydrogenation are the most significant examples. On this account, the
changing scenario of the chemical commodities producer countries due to the increasing tendency
of developing countries to better exploit their internal resources, and not only for captive utilization,
have led to the development of technologies aimed at transforming NG components into more
valuable or transportable products.
During the last twenty years, a network of new and old technologies aimed at making
available wider possibilities of economically attractive transformation of natural gas to higher
valued chemicals or liquid fuels has been growing in a more or less co-ordinated effort of
technological innovation taking into consideration the presence of C2-C4 hydrocarbons together
with methane.
In the last 3-4 years information on the NG conversion has overcome the limit of the
scientific or technological literature and has entered the financial news world, meaning that the
attention of market operators is addressed to this opportunity.
It is in this context that we present this volume collecting the Proceedings of the Fifth
Natural Gas Conversion Symposium which will be held in Giardini Naxos-Taormina the 20-25
September 1998. The Symposium continues the tradition set by four previous meetings held in
Auckland (New Zealand, 1987), Oslo (Norway, 1990), Sydney (Australia, 1993) and Kruger
National Park (South Africa,1995).
The scientific programme consists of invited plenary and key-note lectures, oral and poster
contributions. The papers cover the following area topics:
Catalytic combustion, Integrated production of Chemicals and Energy from Natural Gas,
Fischer-Tropsch Synthesis of Hydrocarbons; Innovative Approaches for the Catalytic
Conversion of Natural Gas and Novel Aspects of Oxidative Coupling, Natural Gas
Conversion via Membrane based Catalytic Systems; Synthesis of Oxygenates from Syngas,
vii
Partial Oxidation of Methane and Light Paraffins to Oxygenates," Catalytic Conversion of
light Paraffins; Production of Syngas ( Oxyreforming, Steam Reforming and Dry
Reforming); Natural Gas Conversion-Industrial Processes and Economics.
The topics of the Symposium witness the large global R&D effort to look for new and
economic ways of NG exploitation, ranging from the direct conversion of methane and light
paraffins to the indirect conversion through synthesis gas to fuels and chemicals. Particularly
underlined and visible will be the technologies already commercially viable.
The 5 th NGCS is therefore a way of showing the increasing role of NG a source of value
creation for companies and as a perspective clean raw material for answering to the environmental
societal concerns.
The interest raised by the Symposium has been overwhelming as accounted by the large
number of papers presented and delegates. The countries participating in the congress and
contributing to the Proceedings reported here are:
o:. Algeria o:. Korea
~ Argentina ~ Malaysia
~176A ustralia ~ Mexico
o~o Canada ~ Norway
o~~ China ~ Poland
~176D enmark ~176P ortugal
~176E ngland o:~ Russia
o:. Finland o~~ SaudiArabia
o:. France o:. Slovakia
~176G ermany ~176S outh Africa
�~9~ Greece ~ Spain
~176H ungary ~176T he Netherlands
~ Ireland ~176U .S.A.
~ Italy o:~ Venezuela
~ Japan
The Organising Committee is grateful to the International Scientific Committee for having
given to the Italian Chemical Community the chance and the honour to handle the organisation of
viii
such international scientific event as well for the scientific co-operation in the choice of the
congress topics and paper selection.
The 5t h Natural Gas Conversion Symposium is supported by the Division of the Industrial
Chemistry and Catalysis Group of the Italian Chemical Society, the Institute CNR-TAE and the
University of Messina.
The Italian Catalysis Community is particularly keen to gather in Italy all the Scientists
active in this strategic area. We feel that this event marks also the active role played by the Italian
Scientific Community in developing original and viable routes for the NG Conversion.
We are confident and the content of this volume proves this view, that mature and
technologically feasible processes for the natural gas conversion are already available and that new
and improved catalytic approaches are currently developing and we hope that their validity and
feasibility are soon documented. This is an exciting area of the modem catalysis which certainly
will open novel and rewarding perspectives for the chemical, energy and petrochemical industries.
With this optimism we address the Symposium to all the participants, to all the scientists active in
the area.
It is a pleasure to acknowledge the generous support given by the Sponsors which have
greatly contributed the success of the event, the assistance of the members of the International
Scientific Committee, the hard work of the Organising Committee and the many student assistants
and all who have contributed to the success of the Symposium through presentation, discussion,
chairing of Sessions and refereeing of manuscripts.
Messina 25 June 1998
Adolfo Parmaliana
Domenico Sanfilippo
Francesco Frusteri
Angelo Vaccari
Francesco Arena
ix
ORGANIZERS
The symposium has been organized by:
�9 Division of Industrial Chemistry and Catalysis Group of the Italian Chemical
Society
�9 Institute CNR-TAE (Messina)
�9 University of Messina
ORGANIZING COMMITTEE
A. Parmaliana University of Messina Italy
D. Sanfilippo Snamprogetfi SpA, Milano Italy
F. Frusteri Istituto CNR-TAE, Messina Italy
F. Arena University of Messina Italy
G. Cacciola Istituto CNR-TAE Italy
G. Deganello University of Palermo Italy
P. Garibaldi Euron SpA, Milano Italy
R. Maggiore University of Catania Italy
G. Petrini Enichem SpA, Milano Italy
A. Vaccari University of Bologna Italy
SCIENTIFIC COMMITTEE
C. Apesteguia Argentina J. Lunsford USA
M. Baerns Germany I. Maxwell The Netherlands
T.H. Fleisch USA C. Mirodatos France
A. Holmen Norway J. Ross Ireland
G. Hutchings UK J. Rostrup-Nielsen Denmark
E. Iglesia USA D. Sanfilippo Italy
B. Jager South Africa L.D. Schmidt USA
E. Kikuchi Japan D. Trimm Australia
W. Li China
xi
5 th Natural Gas Conversion Symposium, 20-25 September 1998, Giardini Naxos - Taormina
FINANCIAL SUPPORT
The organising committee would like to thank the following Organisations for the
financial support sponsorship:
LIST of SPONSORS
�:9o Azienda Autonoma per I ' lncremento
Turistico della Provincia di Messina
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o:oAKZO NOBEL CHEMICALS S.p.A.
*:*AMOCO Corp.
o:oBANCO di SICILIA
o:oENGELHARD
o:oE NI S.p.A. ! ~ i ! ....
o:oE NITECNOLOGIE S.p.A.
o:oEURO SUPPORT MANUFACTURING B.V.
o:oE URON S.p.A.
o:oHALDOR TOPSOE A.S.
.:. K.T.I.S.p.A.
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NATURAL GAS CONVERSION V
Studies in Surface Science and Catalysis, Vol. 119
A. Parmaliana et al. (Editors)
�9 1998 Elsevier Science B.V. All rights reserved.
N a t u r a l Gas as r a w ma te r i a l for c l ean fuels and c h e m i c a l s
in the nex t d e c a d e s
by M. Col i t t i
E n i C h e m , Mi l an , I ta ly
Modern industry originates in a change of feedstock, the result of a never-ending quest
for a better, cheaper raw material. In the origin, there was coal, a source of both energy
and industrial feedstock, the so-called synthesis gas. Then, coal was replaced by liquid
hydrocarbons, coming from a refinery or from wells of crude oil and gas. The passage
from solid to liquids was part and parcel of a structural change which has produced an
extraordinary acceleration of economic growth. We might hope that the same will
happen when natural gas will comes in to displace the liquids.
New feedstocks do not come in without a fight. It is not only a matter of price, but also
of technology, and of the natural tendency of industries to protect their own investments
in plants which are all of a sudden made to look old. Rather than repeat for the nth time
the list of technologies which can turn natural gas into a basic feedstock for oil and
petrochemical industries, I will try to discuss how will companies decide upon this
matter. What are the main elements of such a decision? Predictably, its main element is
a comparison between costs and prices. However, this is not a simple matter, to be
decided on a back-of-an-envelope calculation: it is, rather, a differential decision, based
on a comparison between the situation in which we are now, and a future one, by itself
uncertain.
The first element is the price of the new feedstock per ton of the product we want, which
is deeply influenced by the cost of new technological processes and therefore requires a
technological assessment of the variable as well as the fixed costs, and of the direct
costs as well as the amortisation of the capital invested. These costs will be compared
with the price of the products we want, which, as history will teach us, might change
together with the feedstock. Let' s try to deal with these elements, briefly but, if possible,
clearly, although in a purely descriptive way.
Who makes the price of gas? Methane is in great demand as fuel and it is said that it
will fully displace oil in such uses. Therefore, its value in any area of the world tends
to be what can be netted back from sales to Europe. In the rich markets of the Old
Continent, gas is sold as fuel in competition with delivered light gasoil, at prices which
leave to the seller a good part of its competitive advantage (with the exception, of
course, of the ecological improvement, which is collective). It is therefore too highly
priced for it to become a raw material. A large industrial conversion plant could not
conceivably pay the same price that can be extracted from a household consumer for
gas delivered inside his house.
This means that gas is available at industrial prices only if produced in areas which are
too far from Europe, and do not have a great fuel demand themselves. In these areas the
industrial transformation of gas into liquids should take full advantage of the lower cost
of transporting a liquid.
The other big factor in defining the long term gas price is the large reserves of natural
gas in the world, which should tend to keep its price down, at least in certain areas, but
this is by no means certain: gas sources which cannot enter the rich markets do not seem
to influence the price at all.
The second element, technology, determines the capital to be invested to obtain a ton of
the product we desire from the new feedstock. This number should be quite certain,
based on rock-bottom certainty of the engineers' calculations. However, first generation
plants do require more capital per ton of product than second or third generation ones.
Not only the scale of the plant increases with experience; also, technological change
starts with high-pressure high-temperature plants and moves into low-pressure, low-
temperature ones, which cost much less to build and maintain. So the comparison, to be
honest, has to be done taking into account future things like the experience curve, the
acceleration of reactions produced by accumulated know how, in short, the overall
technological trends.
Let's talk of the third element, the price of the products that can be obtained. The
tendency to manufacture the most valuable product possible has to be balanced by the
fact that highly-priced products are often small-volumes specialities. To combine the
high volumes which come from world-scale plants with high-price products, a
sometimes impossible operation, could perhaps be performed by aiming at the market
for ecological components, that is, products so fine that they can be used to upgrade
low-cost base products. This case is however partly clouded by the uncertainty on the
future trends of the environmental legislation, which seems already bound to swallow
every product in an ever lengthening list of baddies. Alternatively, one can imagine
plants which combine productions, for example, of liquids (methanol) with that of
electricity. Trouble is, the areas which do not offer a great market for gas are not hungry
for other energy sources either, and to sell there large volumes of electricity might be as
difficult, if not more, than to transport that gas to the nearest high-price market.
The choice is therefore complex, and the qualitative elements we have just briefly listed
do become figures only after assumptions which do not always reduce the uncertainty,
but sometimes increase it. Different companies will react differently to this challenge,
the majority of them falling into one or the other of the following categories.
The innovator~ who runs the risk of investing in new technologies or in old ones
revisited and adapted to new productions. He may be motivated by the lure of large
innovation profits to be obtained either by producing more cheaply something already in
the market, or by marketing a new product. Paradoxically, this decision may be justified
in two opposite ways: by saying either that you have more investment capital that
investment opportunities in proven technologies; or that, having invested and found gas,
you cannot allow that sunk capital simply to lie fallow, not producing anything.
The follower, who tends to avoid risk, and therefore leaves to the innovators not only the
capital risk, but also the job to improve the technology and to develop the know-how.