Catalysis and Ionic Liquids

Jeff Miller (BP Chemicals) Chemical Industry Vision 2020 Technology Partnership Workshop Barriers to Ionic Liquid Commercialization September 11, 2003

Growth in the Interest in ILs for Catalysis

800

Number of Publications

700 600 500 400 300 200 100 0 1993

Journals Patents

1995

1997

1999

2001

2003

Year

Objectives
Provide a context for initial discussions
Briefly review catalysis with Ionic Liquids Give you a personal view of requirements for commercialization

Speculate as to potential opportunities

Known Catalytic Reactions with ILs (Homogeneous Catalysis)

IL solvent (transition metal catalyst) or Lewis acid catalyst (AlCl3)
Hydrogenation Oligomization/polymerization Hydroformylation Acylation Metathesis Many more

Rates and selectivities can be modified by the IL Reaction mechanisms are similar to those in organic solvents

Whats Required for Commercialization of a Catalytic Process?

Activity, selectivity and life Positive economics
Lower capital Lower operating Lower feedstock costs (60+% of product cost)

Low Risk (technical and business) Compelling demand for catalyst/process/product

Attractive project under any business condition

Commercial Implementation
Incremental (catalyst replacement)
Improved yields Minimum capital Low risk Greater acceptability of new technology First application

New process/product
Large capital expenditure High risk High value (shut down economics) Requires demonstration of intermediate scale Large resistance to change

IFPs Dimerization of Butenes

Dimersol: 30 plant world-wide
No solvent (homogeneous phase) Catalyst and solvent loss

Difasol (IL biphasic process)

70-80% conversion (impure butene) 90-95% dimer selectivity (product insoluble in IL) Retrofit Dimersol plant Better use of catalyst (reduced disposal costs)

Properties of ILs
High solubility for many organic and inorganic compounds Tunable solvent properties (solubility, polarity, etc.) Non-coordinating solvent Low vapor pressure (non-flammable) Moderate to high thermal and stability Electrically conducting

New Opportunities
New Catalysts
ILs have high solubility for inorganic and organic compounds

New Products
Tailored solvent solubility for new reactants

Development of Continuous Processes

Tunable solubility to phase separate reactants, catalysts and products (biphasic catalysis)

Electro-catalytic Reactions
ILs are conducting with soluble metal compounds and hydrocarbons

Attractive Projects
Develop improved technology that has large impact on process or product costs
25-50% reduction in capital/energy Low cost feedstocks

Develop new technology that solves governmental mandates (e.g., environmental regulations) or unsolved problems Develop new technology for replacement of inefficient process

Reviews on IL and Catalysis

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. T. Weldon, Chem. Rev., 1999, 99, 2071-2083. H. Olivier-Bourbigou, J. Mol. Catal. A: Chem., 1999, 146, 285-289. P. Wasserscheid and W. Keim, Angew. Chem. Int. Ed., 2000, 39, 3772-3789. R. Sheldon, Chem. Comm., 2001 (23), 2399-2407. A. Ranwell, A. and M. A. Tshamano, ACS Symp. Ser., 818 (Ionic Liquids), 2002, 147-160. P. Wasserscheid, DGMK Tagungsbericht Proc. of the DGMK-Conference: Chances for Innovative Processes at the Interface between Refining and Petrochemistry, 2002, 97-106. J. Dupont, R.F. de Souze and P.A.Z. Suarez, Chem. Rev., 2002 102, 3667-3692. H. Olivier-Bourbigou and L. Magna, J. Mol. Catal. A: Chem., 2002, 182/183, 419-437. D. Zhao, M. Wu, Y. Kou and E. Min, Catal. Today, 2002, 74, 157-189. V.P.W. Boehm, Applied Homogeneous Catalysis with Organometallic Compounds (2nd Edition,) 2002, 2, Wiley-VCH Verlag, 639-645. P. Wasserscheid, Green Industrial Applications of Ionic Liquids, 2003, Kluwer Academic Pub., 29-47. H. Olivier-Bourbigou and F. Huges, Green Industrial Applications of Ionic Liquids, 2003, Kluwer Academic Pub., 67-84. A.J. Carmichael and D.M. Haddleton, Ionic Liquids in Synthesis, 2003, Wiley-VCH Verlag, 319335. H. Olivier-Bourbigou and A. Forestiere, Ionic Liquids in Synthesis, 2003, Wiley-VCH Verlag, 258-280.