Hostname: page-component-586b7cd67f-t7fkt Total loading time: 0 Render date: 2024-11-25T20:54:30.796Z Has data issue: false hasContentIssue false
  • English
  • Français

Polymer Pendant Crown Thioethers for Removal of Mercury from Acidic Waste Streams-Characterization and Extraction Performance

Published online by Cambridge University Press:  11 February 2011

Theodore F. Baumann ,
Glenn A. Fox ,
Art J. Nelson ,
Joy C. Andrews ,
Darrell B. Bishop  and
John G. Reynolds
Theodore F. Baumann
Affiliation:
University of California, Lawrence Livermore National Laboratory, Livermore, CA 94551 and
Glenn A. Fox
Affiliation:
University of California, Lawrence Livermore National Laboratory, Livermore, CA 94551 and
Art J. Nelson
Affiliation:
University of California, Lawrence Livermore National Laboratory, Livermore, CA 94551 and
Joy C. Andrews
Affiliation:
Department of Chemistry, California State University Hayward, Hayward CA 94542
Darrell B. Bishop
Affiliation:
Department of Chemistry, California State University Hayward, Hayward CA 94542
John G. Reynolds
Affiliation:
University of California, Lawrence Livermore National Laboratory, Livermore, CA 94551 and
Get access

Abstract

The removal and immobilization of mercury(II) ions from industrial waste streams is a difficult and expensive problem requiring a robust extractant that is resistant to corrosive conditions. We have now developed an acid-resistant thiacrown polymer that has potential utility as a selective and cost-effective Hg2+ extractant. A new crown thioether, 2-hydroxymethyl-1,4,8,11,14-pentathiacycloheptadecane ([17] aneS5-OH), was synthesized through reaction of 2,3-dimercapto-1-propanol with 4,7,10-trithiatridecane-1,13-di-p-toluenesulfonate; then treated with thionyl chloride to form 2-chloromethyl-1,4,8,11,14-pentathiacycloheptadecane ([17] aneS5-Cl); followed by conversion to 2-(N-methyl)aminomethyl-1,4,8,11,14-pentathiacycloheptadecane ([17] aneS5-NHMe), through reaction with methylamine. The synthesis of the 4-vinylbenzyl-substituted thiacrown was readily accomplished by treating with 4-vinylbenzyl chloride. Co-polymerization of the 4-vinylbenzyl-substituted thiacrown with DVB (80% divinylbenzene) using AIBN as the radical initiator generated the highly cross-linked crown thioether polymer. The polymer based material was tested for Hg(II) extraction activity from acidic solutions. The material was found to extract 95+% of the Hg in a pH range of around 1.5 to over 6.0, with contact times of less than 30 min and in the presence of high concentration of competing ions such as Pb, Cd, Al, and Fe. The spent polymer could also be stripped of the Hg2+ and reused without sufficient loss of loading capacity. Characterization of the binding sites by XPS and XAS show only some of the S atoms in the thiacrown participate in the binding of Hg. Our results indicate this polymer has the potential to treat highly acidic wastes efficiently. This thiacrown polymer is far more effective in extracting Hg2+ from aqueous solution than previously reported Hg2+ extrac-tants, not only being very fast and efficient and selective, but also independent of pH.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 757: Symposium II – Scientific Basis for Nuclear Waste Management XXVI , 2002 , II11.9
Copyright
Copyright © Materials Research Society 2003

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1. Baumann, T. F., Reynolds, J. G., and Fox, G. A.. Chem. Commun. 1637–1638 (1998).Google Scholar
2. Cooper, S. R.. Acc. Chem. Res. 21, 141 (1988).Google Scholar
3. (a) Sevdi'c, D., and Meider, H.. J. Inorg. Nucl. Chem., 43, 153 (1981).Google Scholar
(b) Sevdi'c, D., Fekete, L., and Meider, H.. J. Inorg. Nucl. Chem. 42, 885 (1980).Google Scholar
(c) Sevdi'c, D., and Meider, H.. J. Inorg. Nucl. Chem. 39, 1409 (1977).Google Scholar
4. Moyer, B. A., Case, G. N., Alexandratos, S. D., Kriger, A. A.. Anal. Chem. 65, 3389 (1993).Google Scholar
5. (a) Yamahita, K., Kurita, K., Ohara, K., Tamura, K., Nango, M., and Tsuda, K.. React. Funct. Polymers 31, 47 (1996).Google Scholar
(b) Tomoi, M., Abe, O., Takasu, N., and Kakiuchi, H.. Makromol. Chem. 184, 2431 (1983).Google Scholar
(c) Oue, M., Kimura, K., and Shono, T.. Analyst 113, 551 (1988).Google Scholar
(d) Troansky, E. I., Pogosyan, M. S., Samoshina, N. M., Nikishin, G. I., Samoshin, V. V., Shpigun, L. K., Kopytova, N. E., and Kamilova, P. M.. Mendeleev Commun. 9 (1996).Google Scholar
6. Baumann, T. F., Reynolds, J. G., and Fox, G. A., Reac. Func. Polym. 44, 111–120 (2000).Google Scholar
7. Nelson, A. J., Reynolds, J. G., Baumann, T. F., and Fox, G. A., Appl. Surf. Sci. 167, 205–215 (2000).Google Scholar
8. Bishop, D. B., McCool, G. D., Nelson, A. J., Reynolds, J. G., Baumann, T. F., Fox, G. A., DeWitt, J. G., Andrews, J. C., Microchemical Journal 71 (2–3), 247–254 (2002).Google Scholar
9. Wolf, R. E. Jr, Hartman, J. R., Foxman, B. M., Cooper, S. R., J. Am. Chem. Soc. 109, 4328 (1987).Google Scholar