Skip to main content

Chemical Reactions and Related Phase Behavior in Supercritical Co2 and Co2/Ionic Liquid Mixtures

  • Conference paper
Green Chemical Reactions

Part of the book series: NATO Science for Peace and Security Series ((NAPSC))

  • 2551 Accesses

Abstract

Supercritical (SC) CO2 and ionic liquids (ILs) are two types of solvents with special properties, which have been used as reaction media for different chemical reactions. In this chapter, some recent work about the effect of phase behavior on chemical reactions in SC CO2 and SC CO2/IL biphasic systems are discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. (a) M.A. McHugh, and V.J. Krukonis, Supercritical Fluid Extraction, (Butterworth Heinmann, Boston, 1994, 2nd ed.); (b) S. Machmudah, A. Sulaswatty, M. Sasaki, M. Goto, and T. Hirose, Supercritical CO2 extraction of nutmeg oil: Experiments and modeling, J. Supercrit. Fluids 39, 30-39 (2006).

    Google Scholar 

  2. (a) P.G. Jessop, and W. Leitner, Chemical Synthesis using Supercritical Fluids(WileyVCH: Meinheim, 1999); (b) A. Baiker, Supercritical fluids in heterogeneous catalysis, Chem. Rev. 99, 453-473 (1999); (c) E. J. Beckman, Supercritical and near-critical CO2 in green chemical synthesis and processing, J. Supercrit. Fluids 28, 121-191 (2004); (d) P.G. Jessop, T. Ikariya, and R. Noyori, Homogeneous catalysis in supercritical fluids, Chem. Rev. 99, 475-493(1999).

    Google Scholar 

  3. (a) A.I. Cooper, Polymer synthesis and processing using supercritical carbon dioxide, J. Mater. Chem. 10, 207-234(2000); (b) K.P. Johnston, P.S. Shah, Materials scienceMaking nanoscale materials with supercritical fluids, Science 303, 482-483(2004); (c) C. A. Eckert, L. K. Barbara, and P. G., Debenedetti, Supercritical fluids as solvents for chemical and materials processing, Nature, 383, 313-318(1996); (d) T. Sarbu, T. Styranec, and E. J. Beckman, Non-fluorous polymers with very high solubility in supercritical CO2 down to low pressures, Nature, 405, 165-168(2000).

    Google Scholar 

  4. (a) I. Song, M. Spuller, G. Levitin, and D.W. Hess, Photoresist and residue removal using gas-expanded liquids, J. Electrochem. Soc. 153(4), G314-G318 (2006); (b) J.A. Keagy, X.G. Zhang, K.P. Johnston, E. Busch, F. Weber, P.J. Wolf, and T. Rhoad, Cleaning of patterned porous low-k dielectrics with water, carbon dioxide and ambidextrous surfactants, J. Supercrit. Fluids 39(2), 277-285(2006); (c) X.G. Zhang, J.Q. Pham, N. Ryza, P.F. Green, and K.P. Johnston, Chemical-mechanical photoresist drying in supercritical carbon dioxide with hydrocarbon surfactants, J. Vac. Sci. Technol. B 22 (2), 818-825(2004).

    Google Scholar 

  5. (a) J.A. Darr, and M. Poliakoff, New directions in inorganic and metal-organic coordination chemistry in supercritical fluids, Chem. Rev. 99, 495-542(1999); (b) P.E. Savage, Organic chemical reactions in supercritical water, Chem. Rev. 99, 603-622(1999); (c) A.J. Mesiano, E.J. Beckman, and A.J. Russell, Supercritical biocatalysis, Chem. Rev. 99, 623-634(1999).

    Google Scholar 

  6. (a) T. Welton, Room-temperature ionic liquids. Solvents for synthesis and catalysis, Chem. Rev. 99, 2071-2084(1999); (b) P. Wasserscheid, W. Keim, Ionic liquids-New “solutions” for transition metal catalysis, Angew. Chem., Int. Ed. 39, 3773-3789(2000); (c) M.J. Earle, and K.R. Seddon, Ionic liquids. Green solvents for the future, Pure Appl. Chem. 72, 1391-1398(2000); (d) R. Sheldon, Catalytic reactions in ionic liquids, Chem. Commun. 2399-2407(2001).

    Google Scholar 

  7. S.V. Dzyuba, and R.A. Bartsch, Recent advances in applications of room-temperature ionic liquid/supercritical CO2 systems, Angew. Chem., Int. Ed. 42(2), 148-150(2003).

    Article  CAS  Google Scholar 

  8. L.A. Blanchard, D. Hancu, E.J. Bechman, and J.F. Brennecke, Green processing using ionic liquids and CO2, Nature 399, 28-29(1999).

    Article  Google Scholar 

  9. L.A. Blanchard, and J.F. Brennecke, Recovery of organic products from ionic liquids using supercritical carbon dioxide, Ind. Eng. Chem. Res. 40, 287-292(2001).

    Article  CAS  Google Scholar 

  10. W.Z. Wu, J.M. Zhang, B.X. Han, J.W. Chen, Z.M. Liu, T. Jiang, J. He, and W.J. Li, Solubility of room-temperature ionic liquid in supercritical CO2 with and without organic compounds, Chem. Commun. 1412-1413(2003).

    Google Scholar 

  11. W.Z. Wu, W.J. Li, B.X. Han, T. Jiang, D. Shen, Z.F. Zhang, D.H. Sun, and B. Wang, Effect of organic cosolvents on the solubility of ionic liquids in supercritical CO2, J. Chem. Eng. Data 49, 1597-1601(2004).

    Article  CAS  Google Scholar 

  12. J.M. Zhang, C.H. Yang, Z.S. Hou, B.X. Han, T. Jiang, X.H. Li, G.Y. Zhao, Y.F. Li, Z.M. Liu, D.B. Zhao and Y. Kou, Effect of dissolved CO2 on the conductivity of the ionic liquid [bmim][PF6], New J. Chem. 27, 333-336(2003).

    CAS  Google Scholar 

  13. Z.M. Liu, W.Z. Wu, B.X. Han, Z.X. Dong, G.Y. Zhao, J.Q. Wang, T. Jiang, and G.Y. Yang, Study on the phase behaviors, viscosities, and thermodynamic properties of CO2/[C(4)mim][PF6]/methanol system at elevated pressures, Chem.-A Eur. J. 9(16), 3897-3903(2003).

    Article  CAS  Google Scholar 

  14. Z.F. Zhang, W.Z. Wu, H.X. Gao, B.X. Han, B. Wang and Y. Huang, Tri-phase behavior of ionic liquid-water-CO2 system at elevated pressures, Phys. Chem. Chem. Phys. 6, 5051-5055(2004).

    Article  CAS  Google Scholar 

  15. Z.F. Zhang, W.Z. Wu, Z.M. Liu, B.X. Han, H.X. Gao, and T. Jiang, A study of triphasic behavior of ionic liquid-methanol-CO2 systems at elevated pressures, Phys. Chem. Chem. Phys. 6(9), 2352-2357(2004).

    Article  CAS  Google Scholar 

  16. (a) W.K. Gray, F.R. Smail, M.G. Hitzler, S.K. Ross, and M. Poliakoff, The continuous acid-catalyzed dehydration of alcohols in supercritical fluids: A new approach to the cleaner synthesis of acetals, ketals, and ethers with high selectivity, J. Am. Chem. Soc. 121, 10711-10718(1999); (b) M.G. Hitzler, F.R. Smail, S.K. Ross, and M. Poliakoff, Friedel-Crafts alkylation in supercritical fluids: continuous, selective and clean, Chem. Commun. 359-360(1998); (c) P. Licence, W. K. Gray, M. Sokolova, and M. Poliakoff, Selective monoprotection of 1,n-terminal diols in supercritical carbon dioxide: A striking example of solvent tunable desymmetrization, J. Am. Chem. Soc. 127, 293-298(2005).

    Google Scholar 

  17. (a) M.F. Sellin, P.B. Webb, and D.J. Cole-Hamilton, Continuous flow homogeneous catalysis: hydroformylation of alkenes in supercritical fluid-ionic liquid biphasic mixtures, Chem. Commun. 781-782(2001); (b) P.B. Webb, M.F. Sellin, T.E. Kunene, S. Williamson, A.M.Z. Slawin, and D.J. Cole-Hamilton, Continuous flow hydroformylation of alkenes in supercritical fluid-ionic liquid biphasic systems, J. Am. Chem. Soc. 125, 15577-15588(2003).

    Google Scholar 

  18. (a) R.A. Brown, P. Pollet, E. McKoon, C.A. Eckert, C.L. Liotta, and P.G. Jessop, Asymmetric hydrogenation and catalyst recycling using ionic liquid and supercritical carbon dioxide, J. Am. Chem. Soc. 123, 1254-1255(2001); (b) P.G. Jessop, R.R. Stanley, R.A. Brown, C.A. Eckert, C.L. Liotta, T.T. Ngo and P. Pollet, Neoteric solvents for asymmetric hydrogenation: supercritical fluids, ionic liquids, and expanded ionic liquids, Green Chem. 5, 123-128(2003).

    Google Scholar 

  19. L. Gao, W.Z. Wu, Z.S. Hou, T. Jiang, B.X. Han, J. Liu, and Z.M. Liu, Transesterification between ethyl acetate and n-butanol in compressed CO2 in the critical region of the reaction system, J. Phys. Chem. B 107, 13093-13099(2003).

    Article  CAS  Google Scholar 

  20. (a) A. Kordikowski, D.G. Robertson, A.I. Aguiar-Ricardo, V.K. Popov, S.M. Howdle, and M. Poliakoff, Probing vapor/liquid equilibria of near-critical binary gas mixtures by acoustic measurements, J. Phys. Chem. 100, 9522-9526(1996); (b) T. Jiang, Z.S. Hou, B.X. Han, L. Gao, Z.M. Liu, J. He, and G.Y. Yang, A study on the phase behavior of the system CO2+CO+H2+1-hexene plus heptanal, Fluid Phase Equilibr. 215 (1), 85-89(2004); (c) H.F. Zhang, Z.M. Liu, and B.X. Han, Critical points and phase behavior of toluene-CO2 and toluene-H2-CO2 mixture in CO2-rich region, J. Supercrit. Fluids 18(3), 185-192(2000); (d) L. Gao, Z.S. Hou, H.F. Zhang, J. He, Z.M. Liu, X.G. Zhang, and B.X. Han, Critical parameters of hexane plus carbon monoxide plus hydrogen and hexane plus methanol plus carbon monoxide plus hydrogen mixtures in the hexane-rich region, J. Chem. Eng. Data 46, 1635-1637(2001).

    Google Scholar 

  21. (a) J. Ke, M.W. George, M. Poliakoff, B.X. Han, and H.K. Yan, How does the critical point change during the hydrogenation of propene in supercritical carbon dioxide? J. Phys. Chem. B 106, 4496-4502(2002); (b) J. Ke, B.X. Han, M.W. George, H.K. Yan, and M. Poliakoff, How does the critical point change during a chemical reaction in supercritical fluids? A study of the hydroformylation of propene in supercritical CO2, J. Am. Chem. Soc. 123, 3661-3670(2001); (c) B.A. Stradi, M.A. Stadtherr, and J.F. Brennecke, Multicomponent phase equilibrium measurements and modeling for the allylic epoxidation of trans-2-hexen-1-ol to (2R, 3R)-(+)-3-propyloxiranemethanol in high-pressure carbon dioxide, J. Supercrit. Fluids 20, 1-13(2001).

    Google Scholar 

  22. (a) H.P. Li, J. Liu, X.G. Zhang, B.X. Han, Z.M. Liu, J. He, L. Gao, Tautomeric reaction equilibrium of ethyl acetoacetate in CO2-n-pentane and CO2-ethanol mixed solvents in the critical region, Fluid Phase Equilibr. 200, 111-119(2002); (b) Z.S. Hou, B.X. Han, X.G. Zhang, H.F. Zhang, and Z.M. Liu, Pressure tuning of reaction equilibrium of esterification of acetic acid with ethanol in compressed CO2, J. Phys. Chem. B 105, 4510-4513(2001); (c) Z.S. Hou, B.X. Han, J.M. Zhang, Z.M. Liu, J. He, X.G. Zhang, G.Y. Yang, n-Pentane isomerization in different phase regions near the critical temperature, J. Supercrit. Fluids 25, 81-90(2003); (d) Y.H. Chang, T. Jiang, B.X. Han, L. Gao, R. Zhang, Z.M. Liu, and W.Z. Wu, Aerobic oxidation of cyclohexanol to cyclohexanone in compressed CO2 and liquid solvents, Ind. Eng. Chem. Res. 42, 6384-6388 (2003).

    Google Scholar 

  23. Z.S. Hou, B.X. Han, L. Gao, Z.M. Liu, and G.Y. Yang, Selective oxidation of cyclohexane in compressed CO2 and in liquid solvents over MnAPO-5 molecular sieve, Green. Chem. 4(5), 426-430(2002).

    CAS  Google Scholar 

  24. D. Y. Peng and D. B. Robinson, A new two-constant equation of state, Ind. Eng. Chem. Fundam. 1976, 15, 59-64(1976).

    Article  CAS  Google Scholar 

  25. B. Wang, B.X. Han, T. Jiang, Z.F. Zhang, Y. Xie, W.J. Li, and W.Z. Wu, Enhancing the rate of the Diels-Alder reaction using CO2 + ethanol and CO2 +n-hexane mixed solvents of different phase regions, J. Phys. Chem. B 109, 24203-24210(2005).

    Article  CAS  Google Scholar 

  26. S. Fukuzawa, K. Metoki, S. Esumi, Asymmetric Diels-Alder reactions in supercritical carbon dioxide catalyzed by rare earth complexes, Tetrahedron 59, 10445-10452(2003).

    Article  CAS  Google Scholar 

  27. J. Qian, M.T. Timko, A.J. Allen, C.J. Russell, B. Winnik, B. Buckley, J.I. Steinfeld, and J. W. Tester, Solvophobic acceleration of Diels-Alder reactions in supercritical carbon dioxide, J. Am. Chem. Soc. 126, 5465-5474(2004).

    Article  CAS  Google Scholar 

  28. H.P. Li, B.X. Han, J. Liu, L. Gao, Z.H. Hou, T. Jiang, Z.M. Liu, X.G. Zhang, and J. He, Chemical reaction in binary mixtures near the critical region: Thermal decomposition of 2, 2’-azobis(isobutyronitrile) in CO2/ethanol, Chem.-A Eur. J. 8(24), 5593-5600(2002).

    Article  CAS  Google Scholar 

  29. (a) H.P. Li, J. Liu, H.F. Zhang, S.G. Wang, B.X. Han, F.F. Liu, Co-solvent and pressure effect on the thermal decomposition of 2, 2’-azobis(isobutyronitrile) in supercritical CO2 using UV-Vis spectroscopy, J. Supercrit. Fluids 21, 227-232(2001); (b) Z. Guan, J.R. Combes, Y.Z. Menceloglu, J.M. DeSimone, Homogeneous free radical polymerizations in supercritical carbon dioxide: 2. Thermal decomposition of 2,2’-azobis(isobutyronitrile), Macromolecules 26, 2663-2669(1993).

    Google Scholar 

  30. Z.S. Hou, B.X. Han, Z.M. Liu, T. Jiang and G.Y. Yang, Synthesis of dimethyl carbonate using CO2 and methanol: enhancing the conversion by controlling the phase behavior, Green Chem. 4, 467-471(2002).

    Article  CAS  Google Scholar 

  31. L. Gao, T. Jiang, G.Y. Zhao, T.C. Mu, W.Z. Wu, Z.S. Hou, and B.X. Han, Transesterification between isoamyl acetate and ethanol in supercritical CO2, ionic liquid, and their mixture, J. Supercrit. Fluids 29, 107-111(2004).

    Article  CAS  Google Scholar 

  32. G.Y. Zhao, T. Jiang, W.Z. Wu, B.X. Han, Z.M. Liu, and H.X. Gao, Electro-oxidation of benzyl alcohol in a biphasic system consisting of supercritical CO2 and ionic liquids, J. Phys. Chem. B 108, 13052-13057(2004).

    Article  CAS  Google Scholar 

  33. Z.F. Zhang, W.Z. Wu, B.X. Han, T. Jiang, B. Wang, and Z.M. Liu, Phase separation of the reaction system induced by CO2 and conversion enhancement for the esterification of acetic acid with ethanol in ionic liquid, J. Phys. Chem. B 109, 16176-16179(2005).

    Article  CAS  Google Scholar 

  34. Z.S. Hou, B.X. Han, L. Gao, T. Jiang, Z.M. Liu, Y.H. Chang, X.G. Zhang and J. He, Wacker oxidation of 1-hexene in 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), supercritical (SC) CO2, and SC CO2/[bmim][PF6] mixed solvent, New J. Chem. 26, 1246-1248(2002).

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2008 Springer Science + Business Media B.V

About this paper

Cite this paper

Jiang, T., Han, B. (2008). Chemical Reactions and Related Phase Behavior in Supercritical Co2 and Co2/Ionic Liquid Mixtures. In: Tundo, P., Esposito, V. (eds) Green Chemical Reactions. NATO Science for Peace and Security Series. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8457-7_5

Download citation

Publish with us

Policies and ethics