Supercritical extraction combined with catalytic oxidation

Abstract

Organometallic chemistry, chemistry of compounds containing metal–carbon bonds or compounds in which an organic molecule (sometimes with a net negative charge) is bonded to a metal atom through an oxygen or nitrogen atom, is one of the most rapidly growing areas of chemical research. Organometallic compounds are being extensively utilized as reagents in preparation and processing of advanced inorganic materials, as catalysts in production of a wide variety of chemicals and as chemotherapy drugs. Supercritical fluid (SCF) science and technology is another rapidly growing field due to the interesting and desirable properties of SCFs as solvents. The combination of organometallic chemistry and SCFs is a relatively new research area with significant potential. Some applications include (1) use of organotransition metal complexes as homogeneous catalysts for reactions in SCFs [D.A. Morgenstern, R.M. LeLacheur, D.K. Morita, S.L. Borkowsky, S. Feng, G.H. Brown, L. Luan, M.F. Gross, M.J. Burk, W. Tumas, Supercritical carbon dioxide as a substitute solvent for chemical synthesis and catalysis, in: P.T. Anastas, T.C. Williamson (Eds.), Green Chemistry: Designing Chemistry for the Environment, American Chemical Society, Washington, DC, 1996, p. 132 and G.P. Jessop, T. Ikariya, R. Noyori, Homogeneous catalysis in supercritical fluids, Science 269 (1995) 1065], (2) impregnation of polymers with various organometallic complexes from SCF solutions for property enhancement or for subsequent in-situ chemical transformations within such matrices [J.J. Watkins, T.J. McCarthy, Polymer/metal nanocomposite synthesis in supercritical CO2, Chem. Mater. 7 (1995) 1991, and A.I. Cooper, S.G. Kazarian, M. Poliakoff, Supercritical fluid impregnation of polyethylene films, a new approach to studying equilibria in matrices; the hydrogen bonding of fluoroalcohols to (η5-C5Me5)Ir(CO) and the effect on CH activation, Chem. Phys. Lett. 206 (1993) 175], (3) decomposition of organometallic complexes in SCFs for formation of inorganic powders with controlled size distribution [M. Barj, J.F. Bocquet, K. Chhor, C. Pommier, Submicronic MgAl2O4 powder synthesis in supercritical ethanol, J. Mater. Sci. 27 (1992) 2187], (4) SCF extraction of heavy metals from various matrices by formation of organometallic complexes [K.E. Laintz, C.M. Wai, C.R. Yonker, R.D. Smith, Extraction of metal ions from liquid and solid materials by supercritical carbon dioxide, Anal. Chem. 64 (1992) 2875]. At the University of Connecticut, our research efforts are concentrated on evaluation of technical and economical feasibility of some of these applications. The three primary research thrusts in our group have been the utilization of supercritical carbon dioxide (scCO2) as a solvent in rhodium catalyzed homogeneous hydroformylation reactions [D.R. Palo, C. Erkey, Homogeneous catalytic hydroformylation of 1-octene in supercritical carbon dioxide using a novel rhodium catalyst with fluorinated aryl phosphine ligands, Ind. Eng. Chem. Res. 37 (1998) 4203], impregnation of polyurethane foams with organometallic oxidants from scCO2 solutions and subsequent vapor phase polymerization in these foams for production of electrically conductive composite foams [Y. Fu, D.R. Palo, C. Erkey, R.A. Weiss, Synthesis of conductive polypyrrole/polyurethane foams via a supercritical fluid process, Macromolecules 30 (1997) 7611], and investigation of extraction of heavy metals from aqueous solutions by compound formation using scCO2 [J. Murphy, C. Erkey, Copper(II) removal from aqueous solutions by chelation in supercritical carbon dioxide using fluorinated β-diketones, Ind. Eng. Chem. Res. 36 (1997) 5371]. Advances in these areas greatly depend on our understanding the interactions of SCFs and organometallic complexes and how these interactions affect a particular application. The subject matter of this review is extraction of heavy metals from aqueous solutions in the presence of SCFs. Since solvent extraction of heavy metals is utilized on a commercial scale, the replacement of organic solvents by SCFs has been the major driving force behind our research efforts. Therefore, this review was prepared to highlight the areas important for commercial scale application of the technology. In Section 1, an introduction to solvent extraction of metals is given. A brief introduction to the possible advantages of using SCFs is also presented in the same section. The fundamentals of extraction with different types of extractants (cation exchangers, solvating extractants and ion-pair extractants) are given in Sections 2, 3 and 4, together with the studies in the literature on metal extraction using SCFs for each type of extractant. Thermodynamics of extraction is particularly emphasized due to its governing role in the economical feasibility of a large scale process. The experimental methods that are utilized in evaluation of thermodynamic behavior of such systems are provided in Section 5. The current methods to recycle the extractants are presented in Section 6. The kinetics of extraction is described in Section 7 where no studies using SCFs have been reported to date and a brief conclusion is provided in Section 8.