Hazardous or toxic waste destruction or containment – Containment – Solidification – vitrification – or cementation
Reexamination Certificate
2000-06-19
2002-10-01
Silverman, Stanley S. (Department: 1754)
Hazardous or toxic waste destruction or containment
Containment
Solidification, vitrification, or cementation
C588S253000, C588S253000, C405S128500, C405S128750
Reexamination Certificate
active
06459011
ABSTRACT:
REFERENCE TO A “MICROFICHE APPENDIX”
Not applicable
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to pollution abatement. More particularly, the present invention relates to abatement of organic pollutants.
2. General Background of the Invention
BRIEF DESCRIPTION OF PRESENTLY USED TECHNOLOGY AND ITS DISADVANTAGES.
A wide range of technologies is currently available for degradation of pollutants, including chemical and biological techniques. Many of these methods, however, are limited by the presence of non-pollutant compounds (matrix). The matrix can sequester the pollutant away from biologically or chemically active sites. Furthermore, the matrix can scavenge reactive transients in chemical systems, thereby lowering degradation efficiency. Biological systems are often limited by toxic effects, especially when high pollutant concentrations or mixtures are present.
The use of iron(II) and hydrogen peroxide alone is severely limited by matrix species through: 1) sequestration of pollutants away from the bulk aqueous phase, 2) chelation of iron(II) into sites that are physically separate (on a molecular scale) from the location of pollutants, and 3) scavenging of hydroxyl radical by matrix compounds.
Current methods for soil washing involve the use of surfactants or cyclodextrins. These methods exhibit some success in washing organic pollutants from soils or aqueous solutions, but they do not degrade the pollutant. Additional further treatment of the waste is still necessary after its removal from the contaminated site. The second treatment step adds additional costs, makes these methods more complicated, and limits their applicability to in situ remediation.
The following U.S. Patents are incorporated herein by reference: U.S. Pat. Nos.: 6,046,375; 5,967,230; 5,919,982; 5,755,977; 5,741,427; 5,520,483; 5,716,528; 5,585,515; 5,425,881; and 5,190,663.
U.S. Pat. No. 5,425,881 discloses a method for the extraction of an organic pollutant from contaminated soil without further contaminating the soil with organic solvents comprising the step of mixing aqueous solutions of cyclodextrins, or cyclodextrin derivatives selected from the group consisting of alkyl, hydroxyalkyl and acyl substituted cyclodextrin derivatives or cross-linked cyclodextrin polymers or cross-linked cyclodextrin derivatives selected from the group consisting of alkyl, hydroxyalkyl and acyl substituted cyclodextrin derivatives, with the contaminated soil.
U.S. Pat. No. 5,190,663 discloses a process for removing dissolved polynuclear aromatic hydrocarbons from an aqueous composition which comprises the step of contacting said composition with a water insoluble inclusion agent comprising an anchored cyclodextrin, said cyclodextrin having an inclusion cavity diameter of at least about 10 angstroms, wherein the concentration of dissolved organics in said aqueous composition is no greater than about fifteen percent by weight.
U.S. Pat. No. 5,741,427 describes the use of Fenton's reagent for soil remediation. This patent utilizes iron complexing agents to limit the reactivity of H
2
O
2
with iron to allow more substantial subsurface penetration of the reagents before they are consumed. However, the patent does not utilize simultaneous binding of iron and the pollutant, and it does not indicate the use of cyclodextrins.
Commercial applications of Fenton chemistry to remediation of contaminated soil are currently in use. These methods add both iron and peroxide to the saturated zone, and utilize iron chelators and peroxide stabilizers (Greenberg et al., 1997; Watts and Dilly, 1996). Such applications have been successful in remediating the saturated zone after petroleum leakage from an underground storage tank. However, conditions for such remediation have typically been developed from empirical observations of degradation efficiency rather than from a fundamental understanding of the HO. dynamics. Furthermore, a large excess of peroxide is often used. Indeed, Jerome et al. (1997, 1998) concluded that excess peroxide was one of two top cost items in their remediation process at the Savannah River Site, and they concluded that the proportionate peroxide costs would increase with increasing scale of the problem.
In situ remediation techniques based on the use of Fenton's reaction (EPA, 1996; EPA, 2000; Geo-cleanse, 2000) have been found to be inefficient in many soils owing to the high reactivity of the reagents with soil constituents (Jerome et al., 1997; Li et al., 1998; Wang and Brusseau, 1998; Lindsey and Tarr, 2000).
The following references are incorporated herein by reference:
EPA, National Center for Environmental Research, http://es.epa.gov
cerqa_abstracts/centers/hsrc/detection/det9.html, 1996.
EPA, Urban Watershed Management Branch, http://www.epa.gov/ednnrmrl/projects/urban/fenton.htm Geo-Cleanse, Inc., www.geocleanse.com, 2000.
Jerome, K. M., B. Riha, and B. B. Looney, “Final Report for Demonstration of In Situ Oxidation of DNAPL Using the Geo-Cleanse Technology,” WSRC-TR-97-00283, Westinghouse Savannah River Company, 1997.
Li, Z. M., P. J. Shea, and S. D. Comfort, “Nitrotoluene destruction by UV-catalyzed Fenton oxidation,” Chemosphere 36 (8) 1849-1865, 1998.
Wang, X. and M. L. Brusseau, “Effect of pyrophosphate on the dechlorination of tetrachloroethene by the Fenton reaction,” Env. Toxicol. Chem. 17 1689-1694, 1998.
Lindsey, M. E. and M. A. Tarr, “Inhibition of Hydroxyl Radical Reaction with Aromatics by Dissolved Organic Matter,” Environ. Sci. Technol. 34, 444-449, 2000.
Greenberg, R. S., T. Andrews, P. K. C. Karala, and R. J. Watts, “In-Situ Fenton-Like Oxidation of Volatile Organics: Laboratory, Pilot and Full-Scale Demonstrations.” Presented at
Emerging Technologies in Hazardous Waste Management IX.
Pittsburgh, Pa., 1997.
Watts, R. J., and S. E. Dilly, “Evaluation of iron catalysts for the Fenton-like remediation of diesel-contaminated soils,” J. Haz. Mat. 51, 209-224, 1996.
Jerome, K. M., B. B. Looney, and B. Riha, “Field Demonstration in Situ Fenton's Destruction of DNAPLs,” WSRC-RP-98-0001 1, Westinghouse Savannah River Company, 1998.
Watts, R. J., M. D Udell, P. A. Rauch, S. W. Leung, “Treatment of Pentachlorophenol-Contaminated Soils Using Fenton's Reagent,” Haz. Waste Haz. Mat. 7(4), 335-345, 1990.
Watts, R. J., S. Kong, M. Dippre, W. T. Barnes, “Oxidation of Sorbed Hexachlorobenzene in Soils Using Catalyzed Hydrogen Peroxide,” J. Haz. Mat. 39 33-47, 1994.
Lipczynska-Kochany, E., G. Sprah, S. Harms, “Influence of Some Groundwater and Surface Waters Constituents on the Degradation of 4-chlorophenol by the Fenton Reaction,” Chemosphere 30, 9-20, 1995.
Gau, S. H., F. S. Chang, “Improved Fenton Method to Remove Recalcitrant Organics in Landfill Leachate,” Water Sci. Tech., 34, 455-462, 1996.
Kim, Y. K., I. R. Huh, “Enhancing Biological Treatability of Landfill Leachate by Chemical Oxidation,” Environ. Eng. Sci. 14(1), 73-79, 1997.
Walling, C. “Fenton's Reagent Revisited,” Acc. Chem. Res. 8, 125-131, 1975.
Haber, F., J. Weiss, “The Catalytic Decomposition of Hydrogen Peroxide by Iron Salts,” Proc. Roy. Soc. A 147, 334-351, 1934.
Halliwell, B., J. M. C. Gutteridge, “Formation of Thiobarbituric-acid-reactive Substance from Deoxyribose in the Presence of Iron Salts: The Role of Superoxide and Hydroxyl Radicals,” FEBS Letters, 128, 347-352, 1981.
Sutton, H. C., C. C. Winterboum, “Chelated Iron-catalyzed OH Formation from Paraquat Radicals and H
2
O
2
: Mechanism of Formate Oxidation,” Arch. Biochem. Biophys. 235,106-115, 1984.
Graf, E., J. R. Mahoney, R. G. Bryant, J. W. Eaton, “Iron-catalyzed Hydroxyl Radical Formation.
Stringent Requirement for Free Iron Coordination Site,” J. Biol. Chem. 259(6),3620-3624,1984.
Lindsey, M. E. and M. A. Tarr, “Inhibited Hydroxyl Radical Degradation of Aromatic Hydrocarbons in the Presence of Dissolved Fulvic Acid,” Wat. Res. 34, 2385-2389, 2000.
Lindsey, M. E. and M. A. Tarr, Quantitation of Hydroxyl Radical During Fenton Oxidation Following a Single Addition of Iron And Peroxide,” Chemosphere 41, 409-417, 2
Lindsey Michele E.
Tarr Matthew A.
Garvey, Smith, Nehrbass & Doody, L.L.C.
Nave Eileen E.
Nehrbass Seth M.
Silverman Stanley S.
University of New Orleans Research and Technology Foundation, In
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