281 Pages
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En vue de l'obtention du


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281 Pages


Niveau: Supérieur, Doctorat, Bac+8
THÈSE En vue de l'obtention du DOCTORAT DE L'UNIVERSITÉ DE TOULOUSE Délivré par l'Institut National Polytechnique de Toulouse Discipline ou spécialité : Génie des Procédés Présentée et soutenue par Amit SHARMA Le 20/07/2009 TITRE Catalytic Reaction Engineering using Ionic liquids: Hydroformylation of 1-Octene JURY Prof. Raghunath V. Chaudhari Rapporteur Prof. Claude De Bellefon Rapporteur Prof. Michel Prevost Membre Dr. François Malbosc Membre Dr. Carine Julcour Membre Prof. Henri Delmas Directeur de thèse Ecole doctorale : Mécanique Energétique Génie Civil Procédés (MEGeP) Unité de recherche : Laboratoire de Génie Chimique (LGC) Directeur(s) de Thèse : Prof. Henri DELMAS N° d'ordre :

  • cobalt-based catalyst

  • génie des procédés

  • very friendly research

  • process

  • perplexing problems has

  • catalysis

  • hydroformylation reaction



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Published 01 July 2009
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N° d’or dr e :
En v u e d e l' ob t e n t ion d u
D é liv r é p a rPoly t echnique Nat ional de Toulousel’I nst it ut D iscip lin e ou sp é cia lit é :océdésGénie des Pr
Pr é se n t é e e t sou t e n u e p a r Am it SH ARM A Le 2 0 / 0 7 / 2 0 0 9 TI TRE Ca t a ly t ic Re a ct ion En g in e e r in g u sin g I o n ic liq u id s: H y d r of or m y la t ion of 1 - Oct e n e
JU RY Pr of. Raghunat h V. Chaudhar i Rappor t eur Pr of. Claude De Bellefon Rappor t eur Pr of. Michel Pr ev ost Mem br e Dr . Fr ançois Malbosc Mem br e Dr . Car ine Julcour Mem br e Pr of. Henr i Delm as Dir ect eur de t hèse Ecole d oct or a le :Mécanique Ener gét ique Génie Civ il Pr océdés ( MEGeP) U n it é d e r e ch e r ch e :Labor at oir e ique ( de Génie Chim LGC)D ir e ct e u r ( s) d e Th è se :Henr i DELMASPr of.
Firstly i would like to express by gratefulness and thanks to ProfessorHenri DELMAS, who gave me the opportunity to join his group under the project of CEFIPRA, and directed me with his valuable guidance through my thesis work. I take this opportunity to express my gratitude and obeisance to Mdm.Carine JULCOUR-LEBIGUE, her naturally gifted power to understand and ability to simplify the most perplexing problems has made a permanent mark in me. Without her support and open mind for new concepts, without the freedom to explore new ideas, and eventually without the patience she had with me, this work would not have been as fruitful as it was.
I would like to acknowledge Prof. R.V. Chaudhari and Prof. Claude de Bellefon for accepting to be the Rapporteur of my thesis and. Prof. Michel Prevost and Dr. François Malbosc to be a part of the jury member. I’m grateful for their valuable suggestions on the thesis work. During my PhD research project, I have also worked for a short span at the “National Chemical Laboratory”, Pune, India. I owe my special thanks to Dr. R.M. Deshpande and Dr. A.A. kelkar for giving me the opportunity to work in their group at the High Pressure Lab., NCL. It was a pleasure working in NCL under their supportive guidance and very friendly research group. I also would like to express my gratitude towards all the faculty and staff members of LGC for their invaluable help. Special thanks to Jean-Louis LABAT, Ignace COGHE, Lahcen FARHI, Jean-Louis NADALIN, Alec MAUNOURY and Lucien POLLINI for their great expertise in the Autoclave reactor set-up and troubleshooting and also for their friendship. I wish to thank Christine REY ROUCH for her great help in conducting experiments with TGA, Martine AURIOL for helping me with Gas-chromatography, Marie Line DE SOLAN and Serge MOUYSSET for conducting SEM and ICP analysis
and Marie-Line PERN for helping me with the viscosity experiments. I also owe my gratitude to Marie MORERE for her help in the operation of Head space Gas Chromatography. Also thanks to Luce Bernard for her help and cooperation during the HSGC experiments. I also express my special thanks to my colleagues Frederic, Carmen, Cathy, Isa, Rana, Harold, Joaquim, Elham, Marianne, Gaelle, Hicham, Abdullai for their kindness and a very nice time during my whole PhD tenure. I want to acknowledge your geneorisity for having such a wonderful time in Europe. I always look forward to spending time with you. I cannot complete this acknowledgement without mention of my beloved family members Mumma, papa, Bhaiya and Richa who have put in their efforts and prayers for me to attain success in life. I am falling short of words to express my feelings towards them. Their blessings and encouragement were beyond comparison. Words are forgotten…..
Memories are remembered……..
Introduction CHAPTER 1: Bibliography 1.1 Introduction 1.2 Catalysis 1.3 Hydroformylation reaction and industrial applications 1.3.1 Cobalt-based catalyst Exxon process Shell process BASF process
1.3.2 Rhodium-based processes UCC process Ruhrchemie/Rhône-Poulenc process 1.4 Novel developments and research areas in hydroformylation 1.4.1 Supercritical carbon dioxide (scCO2) 1.4.2 New solvents for biphasic catalysis 1.4.3 Interfacial catalysis 1.4.4 Supported Liquid Phase Catalysis (SLPC) 1.5 Ionic Liquids  1.5.1 History 1.5.2 Properties of Ionic Liquids
1.5.3 Applications of Ionic Liquids
4 7 12 14 14 15 15 15 16 17 18 19 20 2122 24 24 26 27
1.5.4 Ionic Liquids for transition-metal catalysis 29 1.6 Literature survey on hydroformylation in ILs 30  1.6.1 Solubility of syngas in Ionic Liquids 30  1.6.2 Solubility of reactants and products in Ionic Liquids 36  1.6.3 Hydroformylation reaction using Ionic Liquids 41 Monophasic systems 41 Biphasic approach 43 Alternative reaction systems 51 1.7 Objectives and organization of the thesis 55 CHAPTER 2: Physicochemical properties of the reaction system 2.1 Introduction: hydroformylation of 1-octene in [Bmim][PF6] /decane biphasic system 57 2.2 Physical properties of [Bmim][PF6] 58  2.2.1 Purity 59  2.2.2 Physical properties 60 2.3 Diffusivity of H2and CO in [Bmim][PF6] 61 2.4 H2and CO solubility in [Bmim][PF6] 63  2.4.1 Measurement technique 63  2.4.2 Henry’s constants 66  2.4.3 Comparison with literature data 69 2.5 Solubility and partition coefficient of 1-octene and n-nonanal in [Bmim][PF6] 72  2.5.1 Measurement techniques 73  2.5.2 Solubility results 82 2.5.3 Partition coefficients of 1-octene and n-nonanal ([Bmim][PF6] / decane system) 83  2.5.4 Comparison with literature data 84 2.6 Conclusions 84
CHAPTER 3: Gas-liquid mass transfer in (biphasic) ionic liquid systems 3.1 Introduction 86 3.2 Measurement of gas-liquid mass transfer coefficients 89 3.2.1 Reactor set-up 89 3.2.2 Measurement technique 90
3.3 Gas-liquid mass transfer coefficients of H2and CO in [Bmim][PF6] 91 3.3.1 Critical stirrer speed and gas induction 91 3.3.2 Experimental values of kLa 93 3.3.3 Gas-liquid mass transfer correlations 95 3.4 Gas-liquid mass transfer coefficients of H2and CO in [Bmim][PF6]/decane emulsions 101 3.5 Conclusions 104 CHAPTER 4: Biphasic hydroformylation of 1-octene using ionic liquid 4.1 Introduction 105 4.2 Experimental Procedure 106 4.2.1 Materials 106 4.2.2 Reaction procedure 107 4.2.3 Analytical method 108 4.2.4 Ballast pressure measurement 109 4.2.5 Reaction characteristics: reaction rate, TurnOver Frequency, yield and selectivity 109 4.3 Kinetic study in chemical regime 112 4.3.1 Verification of chemical regime: theoretical considerations and effect of stirrer speed 112 4.3.2 Typical concentration-time profiles 115 4.3.3 Range of operating conditions 116 4.3.4 Effect of catalyst concentration 117
4.3.5 Effect of the initial concentration of 1-octene
4.3.6 Effect of H2and CO partial pressures
4.3.7 Effect of temperature 4.3.8 Ligand effect (sulfoxantphos vs. TPPTS) 4.4 Modelling of initial reaction rates 4.4.1 Investigated models
4.4.2 Optimization strategy
4.4.3 Final optimization results
4.5 Modelling of concentration-time profiles
4.5.1 Predictions for main hydroformylation reaction
4.5.2 Predictions when accounting for isomerisation
4.6 Recycling of catalyst
4.7 Reaction rate in mass transfer limiting regime
4.8 Effect of ultrasounds on reaction rate
4.9 Conclusion
119 122 127 129
131 131 132 134 137 137 139 143 144 149 154
CHAPTER 5: Hydroformylation of 1-octene using supported ionic liquid phase catalyst 5.1 Introduction 156 5.2 Experimental 158 5.2.1 Materials 158 5.2.2 Preparation and characterization of supported ionic liquid phase catalyst 158 Preparation of SILP catalyst 159 Characterization of the catalyst 160 5.2.3 Experimental set-up and procedure 166 Reactor set-up 166 Reaction procedure 167 Analytical method 168 5.3 Effect of operating parameters 169
5.3.1 Catalyst loading
5.3.2 Initial concentration of 1-octene
5.3.3 H2and CO pressures
5.3.4 Temperature
5.4 Recycle study 5.5 Conclusion Conclusion and Perspectives Nomenclature
References Annexes
172 174 176 180 182 183
194 215