Philippe Kalck - Academia.edu (original) (raw)
Papers by Philippe Kalck
CRC Press eBooks, Dec 12, 2002
Schéma de procédés pour § 2-2.2. 2 2 Arbre-produits pour § 2.3-2.3. 6.2 3 Schéma de procédés pour... more Schéma de procédés pour § 2-2.2. 2 2 Arbre-produits pour § 2.3-2.3. 6.2 3 Schéma de procédés pour § 3-3.3. 2 4 Schéma de procédés pour § 3.3. 3.-3.4 5 Arbre-produits du chapitre 4 6 Schéma de procédés et arbre-produits du chapitre 5 7 Arbre-produits du ...
Applied Catalysis A-general, Apr 1, 2003
This study shows that the air oxidation treatment of an activated carbon originates drastic chang... more This study shows that the air oxidation treatment of an activated carbon originates drastic changes in its chemical surface composition leading to the formation of a less acidic surface with thermally stable oxygenated groups, mainly hydroxyl and carbonyl groups. The oxidation treatment also induces changes in the textural properties, although less pronounced than the extent of the chemical changes. The
... 405(!· 123 POrio. I'onllgal 2. U !{t!\lAI' l:quIP:." des l .... l all."l;... more ... 405(!· 123 POrio. I'onllgal 2. U !{t!\lAI' l:quIP:." des l .... l all."l; :III .'I: c (lHJut:cs Mjlll.:I,."': ENSCT. IIR Ric Ill: Nmhllnnc, 31 0 77 T(l lllnll ~t.: CI\ 3. Laho ral(1 in~ de Cl(al y~c. Ch inli..: FUI!.! cl PtIIYlIll"n:s. ENSCT. 11:;; Ric eh: N;u'hunnc. 31 077 Tilulntl:>c C.1x ...
Topics in Organometallic Chemistry, 2016
The use of general descriptive names, registered names, trademarks, service marks, etc. in this p... more The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.
Selective catalytic hydrogenation of α,β-unsaturated aldehydes represents today an important rout... more Selective catalytic hydrogenation of α,β-unsaturated aldehydes represents today an important route in the industrial preparation of fine chemicals. Heterogeneous catalysts are normally less selective than the homogeneous, but easier to handle. Therefore, there is still room for improvement especially regarding catalyst selectivity to the unsaturated alcohol. Our work shows that the surface chemistry also plays an important role on selectivity. We describe an activation procedure for platinum and iridium metal catalysts supported on carbon nanotubes, which improves significantly both selectivity and activity. In the case of platinum, selectivity towards the unsaturated alcohol increased 8 times to a maximum of 66% at 79% conversion.
HAL (Le Centre pour la Communication Scientifique Directe), 2016
A dirhodium hydrido-carbonyl catalyst system based on a binuclating tetraphosphine ligand is disc... more A dirhodium hydrido-carbonyl catalyst system based on a binuclating tetraphosphine ligand is discussed. Spectroscopic and DFT computational studies support the formulation of the key catalyst complex in acetone solvent as [Rh2(μH)2(CO)2(rac-P4)] , which is highly active and regioselective for producing linear aldehydes under mild conditions. This dicationic catalyst suffers from facile fragmentation reactions in acetone that lead to inactive monometallic and bimetallic complexes. The addition of water to the acetone solvent leads to deprotonation from the dicationic catalyst to form monocationic dirhodium catalyst species that are far less susceptible to deactivation. Spectroscopic and DFT computational studies indicate that the key monocationic catalyst is [Rh2(μ-H)(CO)3(rac-P4)]. Although the monocationic bimetallic catalyst is less active on a per molecule basis relative to the dicationic catalyst, there is a higher concentration present producing better overall catalyst rates and selectivity.
HAL (Le Centre pour la Communication Scientifique Directe), 2017
HAL (Le Centre pour la Communication Scientifique Directe), 2015
For over a decade now, the industrial world has been moving towards a greener, safer, cleaner ind... more For over a decade now, the industrial world has been moving towards a greener, safer, cleaner industry that is more environmentally friendly. This movement has been principally driven by an increasing awareness of environmental issues by the society worldwide, initially stimulated by the concept of sustainable development. Indeed in 1980, the International Union for Conservation of Nature (IUCN) introduced the term sustainable development for the fi rst time. It was employed again in 1987 in Mrs. Brundtland's report (entitled 'Our Common Future') when she was Prime Minister of Norway and Chair of the United Nations World Commission on Environment and Development (WCED). She defi ned the concept of sustainable development as "development that meets the needs of the present without compromising the ability of future generations to meet their own needs." Since then, the concept of sustainable development has been adopted worldwide. Although this approach towards sustainability was initiated in the process industries in the 1990s, the increasing environmental, health and safety regulations, and REACH in particular, have more recently triggered profound changes in industry, which are linked to an increased social awareness and attitude, as well as the integration of risks. Reconciling the industrial and economic progress, whilst preserving and respecting the natural balance of the planet has indeed become a challenge. In this area, chemical engineering is involved at the utmost level. There is an urgent need for methods and chemical engineering routes that respect the environment and this has been one of the objectives in chemical engineering in recent years. This trend is named "Green Process Engineering" and implies a change in the traditional concepts of process effi ciency, which in addition to conventional reaction performance, takes into account the economic value of wastes (by reusing and recycling), the elimination of wastes at the source and the non-use of toxic or hazardous substances. In this context, the principles of "green chemistry" support the prevention of pollution instead of waste disposal. The key to the development of acceptable processing methods, in terms of environmental protection, lays in the extensive substitution of old technologies and processes by the use of innovative reaction media and new activation techniques for reactions whereby catalysis is of prime importance. The emergence of new tools for chemical synthesis is of course accompanied by the evolution of chemical processes vi Green Process Engineering but also the implementation of innovative processing equipment and how they are operated. It is therefore essential to educate and to inform engineers and technicians of the tools available to promote the use of sustainable processes in their professional career. By including Green Process Engineering in education, students will receive and spread their knowledge around them, which will naturally cause industry to evolve. These reasons led us to publish this book, which is the fi rst such work written in English. It was originally published in French in 2010 (Dunod) and awarded the Roberval Prize in France in 2011. This book is addressed to researchers and academic staff, students, engineers and technicians. It can also be used as a support for training courses. Written by researchers and academic staff who work in close partnership with industry, this book provides the keys for the successful implementation of green processes in the process industries. Three different but complementary approaches are described in the three parts of this book. They appear in increasing order of process complexity, starting from the improvement of the existing methods and processes, then by considering a change of technology, and fi nally to the implementation of new synthesis routes. Jean-Claude Charpentier, who is a worldwide expert in the fi eld of chemical engineering, has honorably written the introduction and through this, he has given his global vision on modern chemical engineering today. The fi rst part of this book, which is entitled "Tools for green process engineering", includes three chapters dealing with the available tools and methods for implementing green processes. They focus on how to: i) better integrate social and environmental criteria, in addition to technical and economic criteria, in the design and development of processes; ii) optimize the processes; iii) model processes with computer-aided process engineering tools that offer higher fl exibility to incorporate new technological devices. This is an overall approach at the level of the production chain. In the second part of the book "Technologies and innovative methods for intensifi cation", the technical aspects of process intensifi cation are introduced. Chapters on Miniaturization and Multifunctional reactors describe i) the miniaturized systems that offer improvements in production quality by the signifi cant decrease in the size/capacity ratio, low energy consumption and a decrease in the amount of waste products, and ii) multifunctional reactors, which are an effi cient equipment due to the synergetic integration of multiple functions, respectively. The following chapters are then devoted to the intensifi cation of the chemical reaction itself and of transport phenomena. They cover the implementation of ultrasounds and microwaves to improve the performance and/or selectivity of reactions and specifi c operations such as extraction, as well as the use of formulation-based approaches, in particular by implementing microemulsions as novel reaction media. The third part of the book focuses on "a new generation of processes", although some of them are not really recent. In the latter, conventional operations are substantially modifi ed with the prime objective of creating sustainable processes. The fi rst three chapters in this section deal with new media: supercritical fl uids used as a solvent or as a reaction medium, ionic liquids, as well as water and solvent-free reactions. These chapters are signifi cantly chemistry-oriented, one of the basedisciplines of the chemical engineer. They present the latest scientifi c advances on the development of new generation processes. Most conventional branches of chemical engineering, such as electrochemistry, catalysis, photocatalysis, biocatalysis and biotechnology are based core disciplines and that have been redirected towards new applications to take into account current environmental needs. In each of these chapters, the reader will fi nd theoretical concepts and many examples of applications. It is hoped that amongst the different independent chapters of this book, the reader will fi nd concepts, insights and ideas ... for the design and development of the production processes of tomorrow. Green and sustainable process engineering is an emerging and evolving discipline. It offers solutions that meet the economic, societal and environmental needs of the planet.
![Research paper thumbnail of A Mechanistic Investigation of Oxidative Addition of Methyl Iodide to [Tp*Rh(CO)(L)]](https://attachments.academia-assets.com/115128348/thumbnails/1.jpg)
](Inorganic Chemistry, May 18, 2002
A parametric study investigating the impact of temperature, run duration, total pressure, and com... more A parametric study investigating the impact of temperature, run duration, total pressure, and composition of the gaseous phase on the catalytic growth of multi-walled carbon nanotubes (MWNT) has been performed. MWNT have been produced very selectively on the multi gram scale by catalytic chemical vapor deposition from ethylene in a fluidized bed reactor. The kinetics of MWNT growth is fast and, with the catalyst used, no induction period has been observed. The kinetic law is positive order in ethylene concentration and the process is limited by internal diffusion in the porosity of the catalyst. The formation of MWNT in the macroporosity of the catalyst induces an explosion of the catalyst grains. Such a process, thanks to the absence of temperature gradient and to the efficient mixing of the grains allows a uniform and selective treatment of the catalyst powder leading to very high selectivity towards MWNT formation. High purity MWNT have been obtained after catalyst dissolution. Depending on the temperature of production, the specific surface area of this material ranged between 95 and 455 m 2 /g.
Georg Thieme Verlag eBooks, 2018
Chemischer Informationsdienst, Aug 23, 1977
ChemInform Abstract Die Zugabe eines tertiären Phosphins oder Phosphits zu einer Toluollösung der... more ChemInform Abstract Die Zugabe eines tertiären Phosphins oder Phosphits zu einer Toluollösung der nach bekannter Methode erhaltenen Verbindung (Ia),die quadratisch-planar koordinierte; Metall mit Liganden in cis-oder trans-Stellung und geneigter Konfiguration enthält. führt durch Substitution desÄthylens zu den Komplexen (Ib), für die nach IR-und NMR-Daten eineähnliche Struktur vorgeschlagen wird. Die für (Ib) angewendete Darstellungsmethode liefert ausgehend von Verbindungen des Typs (II) bzw. (III) analoge Verbindungen mit Triphenylphosphin oder Phosphitliganden statt des Olelin: Wird dimeres Chloro-cyclooctadien-(l,5)-rhodium mit Phosphin oder Phosphit bzw. dimerem Chlorodicarbonyl-Rh umgesetzt, so erhält man die Verbindung (IV) bzw. (V). Die Reaktion von (Ia) mit der dimeren Chlorodicarbonyl-Rh-Verbindung in Gc genwart von Triphenylphosphin führt zu dem Derivat (VI).
CRC Press eBooks, Dec 12, 2002
Schéma de procédés pour § 2-2.2. 2 2 Arbre-produits pour § 2.3-2.3. 6.2 3 Schéma de procédés pour... more Schéma de procédés pour § 2-2.2. 2 2 Arbre-produits pour § 2.3-2.3. 6.2 3 Schéma de procédés pour § 3-3.3. 2 4 Schéma de procédés pour § 3.3. 3.-3.4 5 Arbre-produits du chapitre 4 6 Schéma de procédés et arbre-produits du chapitre 5 7 Arbre-produits du ...
Applied Catalysis A-general, Apr 1, 2003
This study shows that the air oxidation treatment of an activated carbon originates drastic chang... more This study shows that the air oxidation treatment of an activated carbon originates drastic changes in its chemical surface composition leading to the formation of a less acidic surface with thermally stable oxygenated groups, mainly hydroxyl and carbonyl groups. The oxidation treatment also induces changes in the textural properties, although less pronounced than the extent of the chemical changes. The
... 405(!· 123 POrio. I'onllgal 2. U !{t!\lAI' l:quIP:." des l .... l all."l;... more ... 405(!· 123 POrio. I'onllgal 2. U !{t!\lAI' l:quIP:." des l .... l all."l; :III .'I: c (lHJut:cs Mjlll.:I,."': ENSCT. IIR Ric Ill: Nmhllnnc, 31 0 77 T(l lllnll ~t.: CI\ 3. Laho ral(1 in~ de Cl(al y~c. Ch inli..: FUI!.! cl PtIIYlIll"n:s. ENSCT. 11:;; Ric eh: N;u'hunnc. 31 077 Tilulntl:>c C.1x ...
Topics in Organometallic Chemistry, 2016
The use of general descriptive names, registered names, trademarks, service marks, etc. in this p... more The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.
Selective catalytic hydrogenation of α,β-unsaturated aldehydes represents today an important rout... more Selective catalytic hydrogenation of α,β-unsaturated aldehydes represents today an important route in the industrial preparation of fine chemicals. Heterogeneous catalysts are normally less selective than the homogeneous, but easier to handle. Therefore, there is still room for improvement especially regarding catalyst selectivity to the unsaturated alcohol. Our work shows that the surface chemistry also plays an important role on selectivity. We describe an activation procedure for platinum and iridium metal catalysts supported on carbon nanotubes, which improves significantly both selectivity and activity. In the case of platinum, selectivity towards the unsaturated alcohol increased 8 times to a maximum of 66% at 79% conversion.
HAL (Le Centre pour la Communication Scientifique Directe), 2016
A dirhodium hydrido-carbonyl catalyst system based on a binuclating tetraphosphine ligand is disc... more A dirhodium hydrido-carbonyl catalyst system based on a binuclating tetraphosphine ligand is discussed. Spectroscopic and DFT computational studies support the formulation of the key catalyst complex in acetone solvent as [Rh2(μH)2(CO)2(rac-P4)] , which is highly active and regioselective for producing linear aldehydes under mild conditions. This dicationic catalyst suffers from facile fragmentation reactions in acetone that lead to inactive monometallic and bimetallic complexes. The addition of water to the acetone solvent leads to deprotonation from the dicationic catalyst to form monocationic dirhodium catalyst species that are far less susceptible to deactivation. Spectroscopic and DFT computational studies indicate that the key monocationic catalyst is [Rh2(μ-H)(CO)3(rac-P4)]. Although the monocationic bimetallic catalyst is less active on a per molecule basis relative to the dicationic catalyst, there is a higher concentration present producing better overall catalyst rates and selectivity.
HAL (Le Centre pour la Communication Scientifique Directe), 2017
HAL (Le Centre pour la Communication Scientifique Directe), 2015
For over a decade now, the industrial world has been moving towards a greener, safer, cleaner ind... more For over a decade now, the industrial world has been moving towards a greener, safer, cleaner industry that is more environmentally friendly. This movement has been principally driven by an increasing awareness of environmental issues by the society worldwide, initially stimulated by the concept of sustainable development. Indeed in 1980, the International Union for Conservation of Nature (IUCN) introduced the term sustainable development for the fi rst time. It was employed again in 1987 in Mrs. Brundtland's report (entitled 'Our Common Future') when she was Prime Minister of Norway and Chair of the United Nations World Commission on Environment and Development (WCED). She defi ned the concept of sustainable development as "development that meets the needs of the present without compromising the ability of future generations to meet their own needs." Since then, the concept of sustainable development has been adopted worldwide. Although this approach towards sustainability was initiated in the process industries in the 1990s, the increasing environmental, health and safety regulations, and REACH in particular, have more recently triggered profound changes in industry, which are linked to an increased social awareness and attitude, as well as the integration of risks. Reconciling the industrial and economic progress, whilst preserving and respecting the natural balance of the planet has indeed become a challenge. In this area, chemical engineering is involved at the utmost level. There is an urgent need for methods and chemical engineering routes that respect the environment and this has been one of the objectives in chemical engineering in recent years. This trend is named "Green Process Engineering" and implies a change in the traditional concepts of process effi ciency, which in addition to conventional reaction performance, takes into account the economic value of wastes (by reusing and recycling), the elimination of wastes at the source and the non-use of toxic or hazardous substances. In this context, the principles of "green chemistry" support the prevention of pollution instead of waste disposal. The key to the development of acceptable processing methods, in terms of environmental protection, lays in the extensive substitution of old technologies and processes by the use of innovative reaction media and new activation techniques for reactions whereby catalysis is of prime importance. The emergence of new tools for chemical synthesis is of course accompanied by the evolution of chemical processes vi Green Process Engineering but also the implementation of innovative processing equipment and how they are operated. It is therefore essential to educate and to inform engineers and technicians of the tools available to promote the use of sustainable processes in their professional career. By including Green Process Engineering in education, students will receive and spread their knowledge around them, which will naturally cause industry to evolve. These reasons led us to publish this book, which is the fi rst such work written in English. It was originally published in French in 2010 (Dunod) and awarded the Roberval Prize in France in 2011. This book is addressed to researchers and academic staff, students, engineers and technicians. It can also be used as a support for training courses. Written by researchers and academic staff who work in close partnership with industry, this book provides the keys for the successful implementation of green processes in the process industries. Three different but complementary approaches are described in the three parts of this book. They appear in increasing order of process complexity, starting from the improvement of the existing methods and processes, then by considering a change of technology, and fi nally to the implementation of new synthesis routes. Jean-Claude Charpentier, who is a worldwide expert in the fi eld of chemical engineering, has honorably written the introduction and through this, he has given his global vision on modern chemical engineering today. The fi rst part of this book, which is entitled "Tools for green process engineering", includes three chapters dealing with the available tools and methods for implementing green processes. They focus on how to: i) better integrate social and environmental criteria, in addition to technical and economic criteria, in the design and development of processes; ii) optimize the processes; iii) model processes with computer-aided process engineering tools that offer higher fl exibility to incorporate new technological devices. This is an overall approach at the level of the production chain. In the second part of the book "Technologies and innovative methods for intensifi cation", the technical aspects of process intensifi cation are introduced. Chapters on Miniaturization and Multifunctional reactors describe i) the miniaturized systems that offer improvements in production quality by the signifi cant decrease in the size/capacity ratio, low energy consumption and a decrease in the amount of waste products, and ii) multifunctional reactors, which are an effi cient equipment due to the synergetic integration of multiple functions, respectively. The following chapters are then devoted to the intensifi cation of the chemical reaction itself and of transport phenomena. They cover the implementation of ultrasounds and microwaves to improve the performance and/or selectivity of reactions and specifi c operations such as extraction, as well as the use of formulation-based approaches, in particular by implementing microemulsions as novel reaction media. The third part of the book focuses on "a new generation of processes", although some of them are not really recent. In the latter, conventional operations are substantially modifi ed with the prime objective of creating sustainable processes. The fi rst three chapters in this section deal with new media: supercritical fl uids used as a solvent or as a reaction medium, ionic liquids, as well as water and solvent-free reactions. These chapters are signifi cantly chemistry-oriented, one of the basedisciplines of the chemical engineer. They present the latest scientifi c advances on the development of new generation processes. Most conventional branches of chemical engineering, such as electrochemistry, catalysis, photocatalysis, biocatalysis and biotechnology are based core disciplines and that have been redirected towards new applications to take into account current environmental needs. In each of these chapters, the reader will fi nd theoretical concepts and many examples of applications. It is hoped that amongst the different independent chapters of this book, the reader will fi nd concepts, insights and ideas ... for the design and development of the production processes of tomorrow. Green and sustainable process engineering is an emerging and evolving discipline. It offers solutions that meet the economic, societal and environmental needs of the planet.
Inorganic Chemistry, May 18, 2002
A parametric study investigating the impact of temperature, run duration, total pressure, and com... more A parametric study investigating the impact of temperature, run duration, total pressure, and composition of the gaseous phase on the catalytic growth of multi-walled carbon nanotubes (MWNT) has been performed. MWNT have been produced very selectively on the multi gram scale by catalytic chemical vapor deposition from ethylene in a fluidized bed reactor. The kinetics of MWNT growth is fast and, with the catalyst used, no induction period has been observed. The kinetic law is positive order in ethylene concentration and the process is limited by internal diffusion in the porosity of the catalyst. The formation of MWNT in the macroporosity of the catalyst induces an explosion of the catalyst grains. Such a process, thanks to the absence of temperature gradient and to the efficient mixing of the grains allows a uniform and selective treatment of the catalyst powder leading to very high selectivity towards MWNT formation. High purity MWNT have been obtained after catalyst dissolution. Depending on the temperature of production, the specific surface area of this material ranged between 95 and 455 m 2 /g.
Georg Thieme Verlag eBooks, 2018
Chemischer Informationsdienst, Aug 23, 1977
ChemInform Abstract Die Zugabe eines tertiären Phosphins oder Phosphits zu einer Toluollösung der... more ChemInform Abstract Die Zugabe eines tertiären Phosphins oder Phosphits zu einer Toluollösung der nach bekannter Methode erhaltenen Verbindung (Ia),die quadratisch-planar koordinierte; Metall mit Liganden in cis-oder trans-Stellung und geneigter Konfiguration enthält. führt durch Substitution desÄthylens zu den Komplexen (Ib), für die nach IR-und NMR-Daten eineähnliche Struktur vorgeschlagen wird. Die für (Ib) angewendete Darstellungsmethode liefert ausgehend von Verbindungen des Typs (II) bzw. (III) analoge Verbindungen mit Triphenylphosphin oder Phosphitliganden statt des Olelin: Wird dimeres Chloro-cyclooctadien-(l,5)-rhodium mit Phosphin oder Phosphit bzw. dimerem Chlorodicarbonyl-Rh umgesetzt, so erhält man die Verbindung (IV) bzw. (V). Die Reaktion von (Ia) mit der dimeren Chlorodicarbonyl-Rh-Verbindung in Gc genwart von Triphenylphosphin führt zu dem Derivat (VI).