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INSTITUT FRANÇAIS DU PÉTROLE

INSTITUT FRANÇAIS DU PÉTROLE. "Ionic liquids in catalysis: some examples of developments" Merck Ionic Liquids Workshop 11th October, 2005 Lyon, France Christophe VALLÉE , Hélène OLIVIER-BOURBIGOU Department of Molecular Catalysis IFP-Lyon. The solvent in catalytic reactions.

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INSTITUT FRANÇAIS DU PÉTROLE

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  1. INSTITUT FRANÇAIS DU PÉTROLE • "Ionic liquids in catalysis: • some examples of developments" Merck Ionic Liquids Workshop 11th October, 2005 Lyon, France Christophe VALLÉE, Hélène OLIVIER-BOURBIGOU Department of Molecular Catalysis IFP-Lyon

  2. The solvent in catalytic reactions • From an industrial point of view, the best solvent is NO solvent • solvent separation and recycling : energy demanding • possible contamination of the the reaction products • pressure for cleaner technologies.... • Why a solvent ? • solubilization and stabilization of the active species • enhancement of reaction rates and selectivities • recycling of the catalyst • biphasic reaction or • monophasic reaction and two-phase separation • Which solvents ?

  3. Ionic liquids in catalysis : advantages • Ionic liquids do not evaporate ! • Containment is much easier than for volatile organic solvents. • Large set of physico-chemical properties • adjustable miscibility with organic substrates (multiphasic catalysis) • tuneable solvation properties • Liquid and suitable support for homogeneous catalysts • homogeneous catalyst immobilisation and recovery • Ionic liquids can interact with solutes and catalytic intermediates • new solvent effect (IL=solvent): new or improved selectivity • promoter for the reaction (IL=“co”-catalyst) : higher activity • stabilization of active species (IL=ligand source) : longer catalyst lifetime • Improvement of chemical processes • More efficient use of chemicals and catalysts; less waste. • Energy saving.

  4. Some examples of recent developments in homogeneous catalysis • Ni-catalyzed butene dimerisation • Selective propene dimerisation • Ni-catalyzed butadiene hydrocyanation • Co olefin hydroformylation

  5. Ni-catalyzed Olefin Dimerization

  6. The Industrial Dimersol IFP Process First industrial application in 1980 (Japan)...

  7. The Industrial Dimersol IFP Process First industrial application in 1980 (Japan)... • Advantages: • mild reaction conditions (40-45°C) • process flexibility • Limitations: • Olefin conversion dependent on its concentration • Dimer selectivity dependent on monomer conversion • Catalyst is neutralised at the output of the reactor although still active • use of the catalyst is not optimum • continuous catalyst carry over and waste production

  8. homogeneous catalyst : how to get rid of its limitations ? ionic active species generated in-situ by reaction of Ni(II) salt + alkylaluminium derivative Liquid-liquid biphasic catalysis Which solvent ? The Homogeneous Industrial Dimersol Process

  9. Cl-/Al (molar) >1 Cl-/Al (molar) <1 Basic Ionic Liquid Acidic Ionic Liquid Cl- EtAlCl3- EtAlCl2 EtAlCl3- Et2Al2Cl5- Et3Al3Cl7- NiCl2 • ACTIVITY for olefin dimerization in presence of NiX2 • NON-ACTIVE Formation of NiCl42- The choice of the ionic liquid : the organochloroaluminates 1-Butyl-3-Methylimidazolium chloride + EtAlCl2

  10. butene gaz pressure reducer liquid butene ionic liquid + Ni reaction start-up with stirring Olefin dimerisation in ionic liquid Laboratory test Y. Chauvin, B. Gilbert, I. Guibard, J. Chem. Soc. Chem. Commun. 1715 (1990) Y. Chauvin, S. Einloft, H. Olivier, Ind. Eng. Chem. Res. 34 (4), 1149 (1995)

  11. reaction evolution : formation of a liquid phase not miscible in the IL Olefin dimerisation in ionic liquid Laboratory test magnetic stirring

  12. Olefin dimerisation in ionic liquid Laboratory test decantation of the two phases

  13. Olefin dimerisation in ionic liquid Laboratory test separation of the product phase

  14. Olefin dimerisation in ionic liquid Laboratory test separation of the product phase

  15. T°C reaction starts again with the same ionic liquid containing Ni-catalyst Olefin dimerisation in ionic liquid Laboratory test

  16. extrait dans la phase organique Dimerization of propene with Ni(II) : lab results rapid deactivation BMIC + EtAlCl2 (1:1,2) Y. Chauvin, B. Gilbert, I. Guibard, J. Chem. Soc. Chem. Commun. 1715 (1990) Y. Chauvin, S. Einloft, H. Olivier, Ind. Eng. Chem. Res. 34 (4), 1149 (1995)

  17. Dimerization of propene with Ni(II) BMIC + AlCl3 + EtAlCl2 BMIC + EtAlCl2

  18. Products Products Reactant Ni Active phase containing catalyst Butenes Continuous Flow Pilot Plant Demonstration - representative butene feedstock, no fresh IL added - run was deliberately stopped after more than 5 months operation - IL lifetime and long term stability was demonstrated F. Favre,A. Forestière, F. Hugues, H. Olivier-Bourbigou, J.A. Chodorge, Oil Gaz European Magazine, 83,2/2005

  19. Feed : 75% butenes, isobutene<2% Difasol (pilot results) Dimersol (3 reactors) industrial results Benefits of biphasic dimerization Octene selectivity

  20. Benefits of biphasic dimerization butenes octenes organic phase [Ni] butenes octenes ionic liquid : very low octene solubility C4 dodecenes C12 consecutive side-reactions are minimized

  21. Benefits of biphasic dimerization Feed : C4 Raffinate-2, 75% butenes, 20 tons per hour • decrease catalyst consumption • decrease reactor volume

  22. Synthesis of Dimethylbutenes

  23. Dimethylbutenes : key intermediates for fine chemicals insecticide Danitol TM (by Sumitomo) musk perfume Tonalid TM

  24. > 70% with PR3 ligand : regioselectivity The simplest way of DMB synthesis : Selective propene dimerization [Ni] • Industrial production by Sumitomo (1983) • Ni homogeneous catalyst • high 2,3-DMB selectivity (>70%/total hexenes) • elaborate catalyst formula with basic PR3 • toluene as solvent • solvent separation needs an efficient distillation column • no catalyst recycling (destruction with NaOH)

  25. Propene dimerization in chloroaluminates Phosphine effect • Solvent : Acidic chloroaluminate (BMIC : AlCl3 : EtAlCl2) * after 1 hour reaction time; P(Cy)3 = tricyclohexylphosphine • Same Phosphine effect is observed in chloroaluminate as in homogeneous system.

  26. Competition for the phosphine between «soft » Ni and « hard » AlCl3 • [PR3.NiR]+A- + Al2Cl7-[NiR]+A- + AlCl3.PR3 + AlCl4- • regioselective non regioselective Propene dimerization in chloroaluminates

  27. Stabilisation of DMB selectivity by addition of small amounts of a weak organic competitive base • [PR3.NiR]+A- + Al2Cl7- + B[PR3.NiR]+A- + AlCl3.B + AlCl4- Selective propene dimerization in chloroaluminates aromatic hydrocarbon

  28. Continuous flow propene dimerization in chloroaluminates 2,3-DMB-1 selectivity versus time DMB-1 • Ionic liquid : 15 mL • propene : atm P • duration : 60 hours • production : 11 liters of products • C6 selectivity : 80-81%/products • 2,3-DMB-1 selectivity : 70-80%/C6 60 hours

  29. Examples of applications of ionic liquids oligomerization • in • chloroaluminates [RNi]+A- acid catalysis Al2Cl7- H+ IL

  30. Examples of applications of ionic liquids selective hydrogenation oligomerisation • in • chloroaluminates [H2RhL2]+A- [RNi]+A- • in non-chloroaluminates • PF6-, BF4- , CF3SO3-, • (CF3SO2)2 N-... acid catalysis Al2Cl7- H+ IL IL HRh(CO)L3 HCo(CO)3L Ni hydroformylation Ru hydrocyanation metathesis of functional olefins

  31. Ni-catalyzed Butadiene Hydrocyanation

  32. Hydrocyanation of butadiene into adiponitrile Industrial catalyst: homogeneous nickel(0)-phosphite complexes

  33. Hydrocyanation Model Reaction Catalytic system: Ni(cod)2 + PPh3 + substrate + ionic liquid

  34. Hydrocyanation Selection of the ionic liquid Catalytic system: Ni(cod)2 + PPh3 + substrate + ionic liquid C. Vallée et al. / Journal of Molecular Catalysis A: Chemical 214 (2004) 71–81

  35. Hydrocyanation charge free active species need to design special ligands to anchor the catalyst in the ionic phase

  36. Hydrocyanation A wide range of ionic phosphorus ligands Advanced Synthesis and Catalysis (2005) accepted

  37. Hydrocyanation + Ni(cod)2 + substrate + [BMMIM][NTf2] No trace of nickel or phosphorus (detection limit = 5 ppm)

  38. Co-catalyzed Olefin Hydroformylation

  39. st 1 GENERATION Co H (CO) 4 200 -300 bar 150 - 180 ° C Homogeneous catalysis Basic or acidic extraction of Co BASF, EXXON. Olefins  C4 Propene SHELL (PBu3). Olefin hydroformylation: industrial processes Biphasic catalysis

  40. Olefin hydroformylation the challenge : to develop an efficient process to hydroformylate higher (internal) olefins with an efficient and simple catalyst recovery

  41. tuneable solubility of olefins in IL • better solubility of olefins in IL than in water Olefin hydroformylation : why ionic liquids ? F. Favre, H. Olivier-Bourbigou, D. Commereuc, L. Saussine, Chem. Commun. 1360, (2001) • partial co-miscibility of ionic liquids and reaction products • loss of ionic liquid (and catalyst) in the products

  42. Olefin Hydroformylation : cobalt catalyst - Nature of the active species : H2/CO 2HCo(CO)4 active cobalt catalyst : neutral Co2(CO)8 - In presence of an organic base, formation of ionic species 3 Co2(CO)8 + 12 bases 2 ([Co(base)6]2+[Co(CO)4]-2) + 8 CO H2/CO H2/CO 6 ([baseH]+[Co(CO)4]-) 6 HCo(CO)4 2 ([Co(base)6]2+[Co(CO)4]-2) - base - base these ionic species have a good affinity for ionic liquids

  43. T and P(CO/H2) Cobalt Recovery CO/H2 olefins possible addition of Co2(CO)8 + base Reaction Separation CO/H CO/H CO/H 2 2 2 [baseH]+[Co(CO)4]- Produits [Co(base)6]+[Co(CO)4]2- 2+ [ Co(base) ] 2[ Co(CO) x 4 HCo(CO)4 Ionic Liquid + base + cobalt ionic liquid recycle Cobalt catalyzed Hydroformylation of olefins CO/H2 • the base may help in the generation of the active Co catalyst • simple cobalt recovery • no by-product generation

  44. Cobalt catalyzed 1-hexene hydroformylation : results - ligand : L/Co=2 - ionic liquid : 6 mL - substrate : hexene-1 : 15 mL - (co-solvent) heptane : 30 mL T = 130°C, P = 100bars Conversion mol H1= / mol Co / h Selectivity - conversion : > 98% - aldehyde selectivity : 75-82 % - recycling of Co « relatively simple » - no need of specially design ligand

  45. Ionic Liquids in Catalysis • Industrial applications: • Some processes using IL have already been industrialized • Ionic liquids are now commercialised and available on ton scale • Better knowledge of their physico-chemical properties • A lot of references : more than 20 chemical reactions have been investigated using ionic liquids ... • Reviews/books : • Multiphasic Homogeneous Catalysis, Wiley-VCH, Weinheim, 2005 • T. Welton, Coord. Chem. Rev. 2004, 248, 2459. • P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, Wiley-VCH, Weinheim 2003. • H. Olivier-Bourbigou, L. Magna, J Mol. Catal. A: Chemical, 2002, 182-183, 419. • A. H. Azizov, Process of Petrochemistry and oil refining, 2002, 8, 1. • J. Dupont, R. F. de Souza, P. A. Z. Suarez, Chem. Rev., 2002, 102, 3667. • C. M. Gordon, Appl. Catal. A: General, 2001, 222, 1-2,101. • R. Sheldon, Chem. Commun., 2001, 23,2399.

  46. Concluding remarks • Ionic liquids probably cannot be used with benefits in all catalytic processes • For some specific reactions, they present significant advantages • they can contribute in improving reaction yield and selectivity • they can stabilize the catalyst • the separation of the catalyst (and the solvent) and their recycling can be simplified • the reactor volume can be lowered

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