Heterogeneous Catalysis and Fine Chemicals, Proceedings of an International Symposium PDF
Preview Heterogeneous Catalysis and Fine Chemicals, Proceedings of an International Symposium
Studiesin Surface Science and Catalysis AdvisoryEditors:B.DelmonandJ.T. Yates Vol. 41 HETEROGENEOUS CATALYSIS AND FINE CHEMICALS Proceedingsofan International Symposium, Poitiers, March 15-17, 1988 Editors M. Guisnet,J. Barrault, C. Bouchoule, D. Duprez, C. Montassierand G. Perot LaboratoiredeCatalyse enChimieOrganique (VA CNRS350), Universite de Poitiers, 40AvenueduRecteurPineau,86022Poitiers, France ELSEVIER Amsterdam - Oxford- NewYork- Tokyo 1988 ELSEVIERSCIENCEPUBLISHERSB.V. SaraBurgerhartstraat25 P.O.Box211, 1000AEAmsterdam, The Netherlands DistributorsfortheUnitedStatesandCanada: ELSEVIERSCIENCEPUBLISHINGCOMPANYINC. 52, VanderbiltAvenue New York, NY 10017,U.S.A. ISBN0-444-43000-8(Vol.41) ISBN0-444-41801-6(Series) ©ElsevierScience Publishers B.V., 1988 All rights reserved. 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Althoughalladvertisingmaterial isexpectedtoconformto ethical (medical) standards,inclusionin this publication does not constitute aguarantee or endorsement of the quality or value of such productorofthe claims madeof itby its manufacturer. Printed inTheNetherlands XI FOREWORD The first International Symposium on Heterogeneous Catalysis and Fine Chem- icals was held in Poitiers, France, March 15-17, 1988. It was organized by the Laboratory of Catalysis in Organic Chemistry of the University of Poitiers with- in the framework of the International Symposia of the "Centre National de la Recherche Scientifique" (CNRS). It has to be admitted that heterogeneous catalysis and fine chemicals are not the most likely subjects one would expect to find paired at an international symposium. Indeed, heterogeneous catalysis evokes an image of huge refineries and petrochemical plants, whilst fine organic chemistry suggests the synthesis, on a small scale of course, of complex and expensive products. Until quite re- cently, the activity of laboratories in the area of heterogeneous catalysis was mainly devoted to the study of reactions and catalysts for the refining and petrochemical industries. However, because of the recession in the traditional heavy industries along with the development of advanced technologies in all the industrial countries, the impact of heterogeneous catalysis in the synthesis of fine chemicals is becoming more and more noticeable. The first International Symposium is to be seen in this perspective. Two panels of industrial and academ- ic researchers, one on selective hydrogenation, the other on selective synthesis of substituted aromatics, showed moreover that heterogeneous catalysis already plays a significant role in fine organic chemistry. It was also shown how neces- sary it is to have available fundamental research of a high standard to bring to- gether experienced researchers in catalysis and organic chemistry. Indeed, the highly advanced knowledge we have of the catalysis of hydrocarbon reactions cannot always be applied directly to the reactions of functional compounds. The chemis- try of functional compounds often requires non-noble rather than noble metal cat- alysts, a liquid rather than a gas phase in the presence of solvents .••..... Moreover new problems arise: the catalysts are often required to selectively and totally transform a functional group into another in a medium which because of the heteroatoms present may easily degrade or poison the catalysts themselves. About 60 papers were submitted from which the Scientific Committee selected the 35 communications (oral or by poster) which fitted most closely the theme of the symposium. The main topics were introduced in 6 plenary lectures and 3 in- vited communications, maintaining in the process a balance between the industrial and the academic points of view. XII This international symposium, in which over 220 researchers participated (almost 40% of them from industry), provided an opportunity for contact between academic researchers and manufacturers, users -or potential users- of solid cat- alysts for fine chemical synthesis. There is no doubt that this will contribute to developing better cooperation between them which is absolutely vital if real progress is to be made. The Organizing Committee would like to thank all the participants and par- ticularly those who obligingly took part in the panels. We would also like to thank all the members of the Laboratory of Catalysis in Organic Chemistry and of ATLAS (Association of postgraduate students and doc- tors of this laboratory) for their enthusiastic help. Special thanks are due to the members of the Scientific Committee who accom- plished the difficult task of selecting the communications. The Editors are particularly grateful to the referees for their efforts in revising the manuscripts submitted and so ensured the high scientific level of the papers. M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, C. Montassier, G. P~rot XIII PREFACE Le premier Symposium International "Catalyse Heterogene et Chimie Fine" s'est tenu Ii Poitiers du 15 au 17 mars 1988. Ce Colloque etait organise par le Laboratoire de Catalyse en Chimie Organique de l'Universite de Poitiers dans le cadre des Colloques Internationaux du Centre National de la Recherche Scientifique (CNRS). 11 n'est pas habituel d'associer Catalyse Heterogene et Chimie Fine. En effet, la Catalyse Heterogene fait souvent penser aux tres grandes unites du raffinage ou de la petrochimie, la Chimie Organique Fine suggerant quant Ii elle 1a synthase en petite quantite de produits complexes et tres chers. Jusqu'li ces dernieres annees 1'activite des laboratoires de Catalyse Heterogene etait d'ailleurs consacree pour 1'essentiel Ii 1'etude des reactions et des catalyseurs de la chimie lourde. Toutefois le declin des activites lourdes traditionnelles et le developpement des technologies avancees que connaissent tous les pays developpes ont recemment favorise l'eclosion de recherches en Chimie Fine. Ce premier Symposium International s'inscrit dans cette evolution. De nombreuses communications et les deux tables rondes organisees avec la participation de chercheurs de l'Industrie et de l Universite, la premiere sur l'hydrogenation selective, la seconde t sur la synthese selective d'aromatiques substitues ont d'ailleurs montre que 1a Catalyse Heterogene jouait dejIi un role important en Chimie Organique Fine. Toutefois, une augmentation de ce role necessite une recherche fondamentale d'un haut niveau associ ant des chercheurs experimentes en Catalyse et en Chimie Organique. En effet la connaissance trss approfondie de la catalyse des reactions d'hydrocarbures n'est pas directement utilisable dans les reactions des composes fonctionnels. Les catalyseurs et les milieux reactionnels sont souvent differents : metaux non nobles au lieu de metaux nobles, phase liquide avec des solvants au lieu de phase gaz... et des problemes nouveaux apparaissent les catalyseurs doivent souvent transformer selectivement et totalement un groupe fonctionnel en un autre et ceci dans un milieu qui peut aisement les degrader ou les empoisonner. Environ 60 papiers ont ete soumis parmi lesquels le Comite Scientifique a choisi les 35 communications (oreles ou par affiches) qui correspondaient le mieux aux themes du Symposium. Les aspects fondamentaux et industriels de ces themes furent introduits par 6 conferences plenieres et 3 communications invitees. XIV Ce Symposium International auquel participerent plus de 220 chercheurs, dont environ 40 du secteur industriel a ete 1'occasion d'echanges entre les chercheurs universitaires, les fabricants et les utilisateurs de catalyseurs solides pour 1a Chimie Organique Fine. Ces echanges devraient contribuer au developpement de la cooperation entre les divers partenaires, cooperation sans laquelle aucun progres reel n'est possible. Le Comite d'Organisation remercie tous les participants et plus parti- culierement ceux qui ont bien voulu animer les deux tables rondes. Nos remerciements vont aussi a tous les membres du Laboratoire de Catalyse en Chimie Organique et d'Atlas (Association des Chercheurs et Anciens Chercheurs de ce Laboratoire) qui ont participe avec enthousiasme a 1'organisation de ce Symposium. Des remereiements particu1iers sont dOs aux membres du Comite Scientifique, qui ont eu la tache delicate de choisir les communications, ainsi qu'aux rapporteurs, qui par leurs suggestions et leurs critiques, ont largement contribue au haut niveau scientifique des papiers. M. Guisnet, J. Barrault, C. Bouchoule, D. Duprez, C. Montassier, G. Perot XV SCIENTIFIC COMMITTEE A. BAlKER, Institute of Technology R. MAUREL, Institut de Recherche Zurich, Switzerland sur la Catalyse, Villeurbanne, J. BARBIER, Universite de Poitiers, France France J.C. MENOELSOHN, Societe Nationale M. BLANCHARD, Ministere de la Recherche Elf-Aquitaine, France et de l'Enseignement Superieur, D. OLLIVIER, Departement Chimie, France CNRS, France J.P. BONNELLE, Universite de Lille, Y. ONO, Institute of Technology, France Tokyo, Japan P. CANESSON, Universite de Poitiers, I. PASQUON, University of Milano, France Italy B. DELMON, Universite Catholique de J. PERICHON, Universite Paris- Louvain, Belgium Val de Marne, France S. DELAVARENNE, CdF Chimie, France J.J. ROONEY, Queen's University, P.C. GRAVELLE, Division Catalyse SFC Belfast, United Kingdom PIRSEM, France J.R.H. ROSS, University of Twente, J.C. JACQUESY, Universite de Poitiers, The Netherlands France M. THIERS, Rh6ne-Poulenc, France G. MARTINO, Institut Fran~ais du I. TKATCHENKO, Laboratoire de Petrole, Rueil-Malmaison, France Chimie de Coordination, Toulouse, France ORGANIZING COMMITTEE M. GUISNET Chairman J. BARRAULT and D. DUPREZ Secretaries C. BOUCHOULE, C. MONTASSIER and G. PEROT Members Atlas 86 (Association of students of the Catalysis Group of Poitiersl XV SCIENTIFIC COMMITTEE A. BAlKER, Institute of Technology R. MAUREL, Institut de Recherche Zurich, Switzerland sur la Catalyse, Villeurbanne, J. BARBIER, Universite de Poitiers, France France J.C. MENOELSOHN, Societe Nationale M. BLANCHARD, Ministere de la Recherche Elf-Aquitaine, France et de l'Enseignement Superieur, D. OLLIVIER, Departement Chimie, France CNRS, France J.P. BONNELLE, Universite de Lille, Y. ONO, Institute of Technology, France Tokyo, Japan P. CANESSON, Universite de Poitiers, I. PASQUON, University of Milano, France Italy B. DELMON, Universite Catholique de J. PERICHON, Universite Paris- Louvain, Belgium Val de Marne, France S. DELAVARENNE, CdF Chimie, France J.J. ROONEY, Queen's University, P.C. GRAVELLE, Division Catalyse SFC Belfast, United Kingdom PIRSEM, France J.R.H. ROSS, University of Twente, J.C. JACQUESY, Universite de Poitiers, The Netherlands France M. THIERS, Rh6ne-Poulenc, France G. MARTINO, Institut Fran~ais du I. TKATCHENKO, Laboratoire de Petrole, Rueil-Malmaison, France Chimie de Coordination, Toulouse, France ORGANIZING COMMITTEE M. GUISNET Chairman J. BARRAULT and D. DUPREZ Secretaries C. BOUCHOULE, C. MONTASSIER and G. PEROT Members Atlas 86 (Association of students of the Catalysis Group of Poitiersl XVI FINANCIAL SUPPORT The organizers are grateful to their generous sponsors - Centre National de la Recherche Scientifique (CNRS) and Programme Interdisciplinaire de Recherche Energie et Matieres Premieres (PIRSEM) - Universite de Poitiers and U.F.R. Sciences Fondamentales et Appliquees - Division Catalyse de la Societe Fran~aise de Chimie - Atochem - CDF Chimie - Derives Resiniques et Terpeniques - Institut Fran~ais du Petrole - Rh6ne-Poulenc - Societe Nationale Elf Aquitaine M. Guisnet etsl,(Editors), HeterogeneousCstslvsisandFineChemicals 1988Elsevier SciencePublishersBV., Amsterdam~ PrintedinThe Netherlands MECHANISTIC RELATIONSHIPS BETWEEN HOMOGENEOUS AND HETEROGENEOUS CATALYSIS: SOME CONCEPTS ARISING FROM SURFACE ORGANOMETALLIC CHEMISTRY. J.M. BASSET, J.P. CANDY, A. CHOPLIN, P. DUFOUR, P. LOUESSARD, C. SANTINI Institut de Recherches sur la Catalyse, 2 avenue A. Einstein, 69626 VILLEURBANNE CEDEX (France) The knowledge of the mechanisms of action of many homogeneous catalysts has been growing rather quickly in the last decades. This fact is mainly due to a fast development of molecular chemistry especially organometallic chemistry which has been at the origin of the proposal of a variety of elementary steps. In contrast, progresses in the knowledge of the mechan1sffis of action of most solid catalysts still remain more limited. In many cases. rhe nature of the catalvst-reactant interaction remains uncertain and the elementarv steps ace not precisely well known. In a few cases, detailed mechanisms can be advanced but those examples are modest in comparison with structural and mechanistic details that have been developed in molecular chemistrv. One of the difficulties encountered in heterogeneous catalys1s 1S that the surfaces of solid catalysts are extremely complicated. The number of the so-called "active sites" can be very small with regards to the overall surface and consequently their structure is almost unknown at an atomic level. It is probably such complexity which has been at the origin of the new development of surface organometallic chemistry: one may hope that the develoDment of this area will favor the understanding of heterogeneous catalysis in the same way as organometallic chemistry has been at the or1gin of a better understanding of the mechanism of action of homogeneous catalysts. One of the reason for such development of surface organometallic chemistry is probably related with the organometallic character of a working site in surface catalysis. In a first approximation, one can consider that during a catalytic cvcle, the molecule(s) which interactCs) with the surface has (have), at least during one elementary step, one or many chemical bonds with one or several surface atoms. Therefore the so-called "active site", during the catalytic process, is a kind of supramolecule which includes both the molecule(s) and one or a few atoms from the surface. If the substrate is an
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