Ex-situ Reductive Dechlorination of Carbon Tetrachloride by Iron Sulfide in Batch Reactor

Choi, Kyung-Hoon;Lee, Woo-Jin

  • Published : 2008.12.28


Ex-situ reductive dechlorination of carbon tetrachloride (CT) by iron sulfide in a batch reactor was characterized in this study. Reactor scaled-up by 3.5 L was used to investigate the effect of reductant concentration on removal efficiency and process optimization for ex-situ degradation. The experiment was conducted by using both liquid-phase and gas-phase volume at pH 8.5 in anaerobic condition. For 1 mM of initial CT concentration, the removal of the target compound was 98.9% at 6.0 g/L iron sulfide. Process optimization for ex-situ treatment was performed by checking the effect of transition metal and mixing time on synthesizing iron sulfide solution, and by determining of the regeneration time. The effect of Co(II) as transition metal was shown that the reaction rate was slightly improved but the improvement was not that outstanding. The result of determination on the regeneration time indicated that regenerating reductant capacity after $1^{st}$ treatment of target compound was needed. Due to the high removal rates of CT, ex-situ reductive dechlorination in batch reactor can be used for basic treatment for the chlorinated compounds.


Iron sulfide;Transition metal;Mixing time;Reductive dechlorination;Regeneration


  1. U.S. Environmental Protection Agency, "National Primary Drinking Water Regulations: Contaminant Specific Fact Sheets, Volatile Organic Chemicals, Technical Version, Office of Water, U.S. Environmental Protection Agency, Washington, D.C. EPA 811-F-95-004-T (1995)
  2. Butler, E. C. and Hayes, K. F., "Factors Influencing Rates and Products in the Transformation of Trichloroethylene by Iron Sulfide and Iron Metal," Environ. Sci. Technol., 35(19), 3884-3891 (2001)
  3. Butler, E. C. and Hayes, K. F., "Effects of Solution Composition and pH on the Reductive Dechlorination of Hexachloroethane by Iron Sulfide," Environ. Sci. Technol., 32(9), 1276-1284 (1998)
  4. Kriegman-King, M. R. and Reinhard, M., "Transformation of Carbon Tetrachloride by Pyrite in Aqueous Solution," Environ. Sci. Technol., 28(4), 692-700 (1994)
  5. Lee, W. and Batchelor, B., "Reductive capacity of natural reductants," Environ. Sci. Technol., 37(3), 535-541 (2003)
  6. Kriegman-King, M. R. and Reinhard, M., "Transformation of Carbon Tetrachloride in the Presence of Sulfide, Biotite, and Vermiculite," Environ. Sci. Technol., 26(11), 2198-2206 (1992)
  7. Hanoch, R. J., Shao, H., and Butler, E. C., "Transformation of carbon tetrachloride by bisulfide treated goethite, hematite, magnetite, and kaolinite," Chemosphere, 63(2), 323-334 (2006)
  8. Hassan, S. M., "Reduction of halogenated hydrocarbons in aqueous media: I. Involvement of sulfur in iron catalysis," Chemosphere, 40(12), 1357-1363 (2000)
  9. U.S. Environmental Protection Agency, In Situ Thermal Treatment of Chlorinated Solvents: Fundamentals and Field Applications, Office of Solid Waste and Emergency Response, U.S. Environmental Protection Agency, Washington, D.C. EPA 542-R-04-010 (2004)
  10. U.S. Environmental Protection Agency, Treatment of volatile organic compounds in drinking water, Drinking Water Research Division, U.S. Environmental Protection Agency, Cincinnati, OH EPA-600/8-83-019 (1983)
  11. U.S. Environmental Protection Agency, Engineered Approaches to In Situ Bioremediation of Chlorinated Solvents: Fundamentals and Field Applications, Solid Waste and Emergency Response, U.S. Environmental Protection Agency, Cincinnati, OH EPA 542-F-00-014 (2000)
  12. Long, J. L., Stensel, H. D., Ferguson, J. F., Strand, S. E., and Ongerth, J. E., "Anaerobic and aerobic treatment of chlorinated aliphatic compounds," J. Environ. Eng., 119(2), 300-320 (1993)
  13. Ohandja, D. G. and Stuckey, C. S., "Biodegradation of PCE in a Hybrid Membrane Aerated Biofilm Reactor," J. Environ. Eng., 133(1), 20-27 (2007)
  14. Gupta, S. K. and Mali, S. C., "Reductive dechlorination of 1,2-dichloroethane using anaerobic sequencing batch reactor (ASBR)," Wat. Sci. Technol., 57(2), 225-229 (2008)
  15. Lide, D. R. (Ed.), CRC handbook of chemistry and physics, 86th, CRC press, Boca Raton, FL (2005)
  16. Kim, Y. -H. and Carraway, E. R., "Dechlorination of Pentachlorophenol by Zero Valent Iron and Modified Zero Valent Irons," Environ. Sci. Technol., 34(10), 2014-2017 (2000)
  17. Contamination episode of carbon tetrachloride (Water quality standard for human health), Water Quality Korea National Water Environmental Information System, http://
  18. Tsai, T. T., Kao, C. M., Yeh, T. Y., and Lee, M. S., "Chemical Oxidation of Chlorinated Solvents in Contaminated Solvents in Contaminated Groundwater: Review," Pract. Periodical of Haz., Toxic, and Radioactive Waste Mgmt., 12(2), 116-126 (2008)
  19. Doherty, R. E., "A History of the Production and Use of Carbon Tetrachloride, Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1-Historical Background; Carbon Tetrachloride and Tetrachloroethylene," Environ. Forensics, 1(2), 69-81 (2000)
  20. Kim, Y. H., Ko, S. O., and Yoo, H. C., "Simultaneous Removal of Tetrachlorocarbon and Chromium (VI) using Zero Valent Iron," J. of KSEE, 24(11), 1949-1956 (2002)
  21. Lee, W. and Batchelor, B., "Reductive dechlorination of chlorinated ethylenes by iron-bearing soil minerals. 1. Pyrite and magnetite," Environ. Sci. Technol., 36(23), 5147-5154 (2002)
  22. Vanstone, N., Elsner, M., Lacrampe-Couloume, G., Mabury, S., and Lollar, B. S., "Potential for Identifying Abiotic Chloroalkane Degradation Mechanisms using Carbon Isotopic Fractionation," Environ. Sci. Technol., 42(1), 126-132 (2008)
  23. Shao, H. and Butler, E. C., "The influence of iron and sulfur mineral fractions on carbon tetrachloride transformation in model anaerobic soils and sediments," Chemosphere, 68(10), 1807-1813 (2007)
  24. Jeong, H. Y. and Hayes, K. F., "Impact of Transition Metals on Reductive Dechlorination Rate of Hexachloroethane by Mackinawite," Environ. Sci. Technol., 37(20), 4650-4655 (2003)
  25. Sakai, S. I., Hayakawa, K., Takatsuki, H., and Kawakami, I., "Dioxin-like PCBs Released from Waste Incineration and Their Deposition Flux," Environ. Sci. Technol., 35(18), 3601-3607 (2000)
  26. Williams, A. G. B. and Scherer, M. M., "Spectroscopic Evidence for Fe(II)-Fe(III) Electron Transfer at the Iron Oxide-Water Interface," Environ. Sci. Technol., 38(18), 4782-4790 (2004)
  27. Fennelly, J. P. and Roberts, A. L., "Reaction of 1,1,1-Trichloroethane with Zero-Valent Methals and Bimetallic Reductants," Environ. Sci. Technol., 32(13), 1980-1988 (1998)