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253

Fig. 10. Photograph of the separation of the PGM and base metals in a two-phase (mixed mode) P-CAC system

sition after iridium as the last precious metal to leave the annular column, the base metals were stripped of the cation-exchange resin by using a step-eluent (23 mol/l HCl). In this eluent the base metals were not retained by either of the two stationary phases. Therefore a fraction consisting of the sum of the base metals could be collected finally at the end of the annular column (Fig. 10). It has been found from batch experiments that the base metals Fe, Ni and Co are fully adsorbed by the cation-exchange resin when the hydrochloric acid concentration of the eluent does not exceed 0.4 M. If the concentration exceeds 0.4 M the base metals start to break through. The same thing happens when the hyRhodium Palladium

base metals
Platin Iridium IV base metals (Fe, Ni, Co)

elution angle []
Fig. 11. Experimental chromatogram of a separation of a solution containing PGMs and base

metals using a mixed mode P-CAC system1

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J. Wolfgang

drochloric acid concentration of the feed solution exceeded 4 M. The minimum height of the cation-exchange resin in the P-CAC depends on the concentration of the base metals present in the feed solution. The height is directly proportional to the maximum capacity of the resin. The maximum capacity of the resin for the mixture of all three cations was calculated from the adsorption isotherm. The adsorption isotherm represents the equilibrium of a compound between the liquid and the solid phase in chromatography; isotherms can be estimated by batch shaking experiments. It was also shown that the feed inlet band of the PGMs broadens when it passes through the cation-exchange resin layer. This means that the concentration of the platinum group metals in the sample decreases accordingly, which depending on the exact conditions results in dilution factors between 2 and 10. Figure 11 shows the experimental chromatogram of the separation of a mixture used in the studies.

7 Conclusion
Several applications throughout the last two decades have shown that starting from batch chromatography experiments a scale-up to a continuous annular chromatograph is easy and straightforward. It has also been shown that many operating modes, including isocratic, step and displacement elution are possible on a CAC. The apparatus retains its relative mechanical simplicity in comparison with fixed-bed processes. No precise timing of a valve system for the introduction of feed and the product removal are needed. The key advantages of annular chromatography over fixed-bed operations are likely the simplicity of the apparatus, its productivity and resolution improvement, and its truly continuous operational capabilities. A very promising application of the P-CAC technology, which at the time this article was written was undergoing intensive studies, is to couple the continuous chromatograph to a continuous fermenter system. Continuous bioreactors are receiving attention as an efficient method of producing biochemicals. For this application it was necessary to develop a P-CAC unit where the column can be autoclaved by steam. The coupling of a continuous fermentation to a continuous capturing step promises a significant improvement in terms of throughput and product yield. Compared to the SMB system the annular chromatography allows the continuous separation of a multicomponent mixture as it is most often the case in biopharmaceutical separations.

8 References
1. 2. 3. 4. 5. Broughton DB (1961) U.S. Patent 2 985:589 Wolfgang J (1996) PhD Thesis, Technische Universitt Graz Giddings JC (1962) Anal Chem 34 Martin AJP (1949) Discuss Faraday Soc 7:32 Scott CD, Spence RD, Sisson WG (1976) J Chromatogr 126:381

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6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46.

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Received: July 2001