Soil remediation method and composition

• US 7,976,241 B2
• Filed: 02/08/2008
• Issued: 07/12/2011
• Est. Priority Date: 03/27/2006
• Status: Active Grant

• Current Assignee: Ethical Solutions, LLC
• Original Assignee: VeruTEK Technologies, Inc.
• Inventors: Collins, John, Hoag, George E.
• Primary Examiner(s): Lorengo; Jerry
• Assistant Examiner(s): Smith; Jennifer A
• Application Number:
  US12/068,653
• Publication Number:
  US 20080207981A1
• Time in Patent Office: 1,250 Days
• Field of Search: 4051281-131, 588312-400
• US Class Current: 405/128.15
• CPC Class Codes: B09C 1/08 chemically
• CPC Class Codes: C11D 3/0084 Antioxidants; Free-radical scavengers
• CPC Class Codes: C11D 3/188 Terpenes
• CPC Class Codes: C11D 3/382 Vegetable products, e.g. soya meal, wood flour, sawdust
• CPC Class Codes: C11D 3/39 Organic or inorganic per-compounds

Abstract

A method for in-situ reduction of contaminants in soil.

Claims

1. A method for reducing the concentration of a contaminant in a soil, comprising:

introducing an oxidant and a surfactant into a subsurface containing the soil;

allowing the surfactant to solubilize or desorb the contaminant; and

allowing the oxidant to oxidize the solubilized contaminant in the subsurface, so that the amount of the contaminant in the soil is substantially reduced,

wherein the overall rate of oxidization of the contaminant is controlled to a predetermined value and the overall rate of solubilization of the contaminant is controlled to a predetermined value by selecting the oxidant and surfactant and adjusting the concentrations of the surfactant and oxidant, so that the rate of oxidation of the contaminant is greater than, less than, or equal to the rate of solubilization of the contaminant,

wherein at least 40% of the initial mass of contaminant is destroyed in situ in the subsurface,

wherein the surfactant resists oxidation by the oxidant, and the surfactant increases oxidation of the contaminant, and

wherein the contaminant comprises a nonaqueous phase liquid (NAPL).

2. The method of claim 1, wherein the rate of oxidation of the contaminant is greater than the rate of solubilization of the contaminant.

3. The method of claim 1, wherein the oxidant and surfactant are introduced through pressurized injection.

8. The method of claim 1, wherein the oxidant does not degrade the surfactant prior to a time at which contaminant is solubilized and oxidized.

9. The method of claim 1, wherein the oxidant and surfactant are introduced into the subsurface containing the soil to achieve a concentration of surfactant greater than the critical micelle concentration.

10. The method of claim 9, wherein the oxidant and surfactant are introduced into the subsurface containing the soil to achieve a concentration of surfactant of at least three times the critical micelle concentration.

11. The method of claim 9, wherein the oxidant and surfactant are introduced into the subsurface containing the soil to achieve a concentration of surfactant of at least ten times the critical micelle concentration.

12. The method of claim 1, further comprising optimizing the hydrophile/lipophile (HLB) ratio of a surfactant or HLB ratios of a mixture of surfactants in an injected mixture comprising the surfactant and the oxidant for components of the contaminant in order to maximize the solubility of the contaminant.

13. The method of claim 1, wherein the surfactant and the oxidant are introduced simultaneously.

14. The method of claim 1, wherein the surfactant and the oxidant are introduced sequentially.

15. The method of claim 1, further comprising introducing a solvent into the subsurface.

16. The method of claim 15, wherein the solvent is selected from the group consisting of a biodegradable solvent, a naturally occurring biodegradable solvent, d-limonene, and combinations.

17. The method of claim 1, wherein the surfactant is made from a naturally occurring plant oil.

18. The method of claim 17, wherein the naturally occurring biodegradable plant oil is selected from the group consisting essentially of castor oil, coca oil, coconut oil, soy oil, cotton seed oil, and combinations.

19. The method of claim 1, further comprising introducing an activator into the subsurface.

20. The method of claim 1, wherein the oxidant and surfactant are selected to have a density less that that of water and are introduced above the water table, controlling migration of volatile organic and inorganic contaminants into the unsaturated zone above the water table.

21. The method of claim 1, wherein the oxidant reacts with micellularized contaminant.

22. The method of claim 19, wherein the activator is selected from the group consisting essentially of a metal, ferrous ion, a chelated metal, chelated iron, a transition metal, a complexed metal, a metallorganic complex, Fe(II), Fe(III), Fe(II)-chelate, Fe(II)-EDTA, Fe(III)-EDTA, Fe(II)-citric acid, Fe(III)-citric acid, Fe(II)-NTA, and combinations.

23. The method of claim 19, wherein the activator is heat.

24. The method of claim 19, wherein the activator is a base or caustic chemical and wherein a region of the subsoil in which the contaminant is present has a pH greater than 10.5.

25. The method of claim 1, wherein the oxidant is selected from the group consisting essentially of a persulfate, sodium persulfate, ozone, hydrogen peroxide, a percarbonate compound, a peroxide, a peroxide containing compound, and combinations.

26. The method of claim 1,

further comprising dissolving a salt in the water to increase the density of the introduced composition.

27. The method of claim 1, wherein the oxidant is introduced in an aqueous solution.

28. The method of claim 27, wherein the aqueous solution has a density approximately equal to water.

29. The method of claim 27, wherein the density of the aqueous solution is in the range of from about 1.0 gram/cm³ to about 1.5 gram/cm³.

30. The method of claim 1, wherein the contaminant and the surfactant form a Winsor Type I system or a submicellar surfactant solution in contact with the contaminant or a microemulsion in the subsurface.

31. The method of claim 1, wherein a mixture in the subsurface comprising the contaminant and the surfactant has an interfacial tension of at least the interfacial tension associated with the critical micelle concentration of the surfactant.

32. The method of claim 1, wherein the contaminant and the surfactant do not form a Winsor Type II system or a reversed-micelle system in the subsurface.

33. The method of claim 1, wherein the mobilization of the contaminant during solubilization and oxidation is minimal.

34. The method of claim 1,

wherein the surfactant is in a quantity sufficient to solubilize the nonaqueous phase liquid contaminant, and

wherein the surfactant forms a Winsor I solution or microemulsion.

35. The method of claim 34, wherein the mass ratio of surfactant to oxidant in the subsurface is in the range of from about 0.005 to 1 to about 0.20 to 1.

36. The method of claim 34, wherein the subsurface comprises an oxidized contaminant and an oxidant residue.

37. The method of claim 1, comprising locally mobilizing the contaminant and oxidizing the contaminant.

38. The method of claim 37, comprising forming a Winsor Type II or III solution or microemulsion to mobilize the contaminant.

39. The method of claim 38, wherein the Winsor Type II or III solution or microemulsion is broken or oxidized to destroy the contaminant.

40. The method of claim 1, further comprising:

collecting a soil sample from the subsurface;

identifying the contaminant as a target for concentration reduction;

choosing the surfactant and optionally choosing a solvent or cosolvent for injection into the subsurface to solubilize the contaminant;

choosing the oxidant and optionally choosing an activator for the oxidant for injection into the subsurface to oxidize the contaminant; and

choosing a quantity of the surfactant for injection into the subsurface to form a Winsor I system or a submicellar surfactant solution or a microemulsion.

41. The method of claim 40, further comprising

determining the type and quantity of surfactant and optionally of cosolvent required to solubilize or desorb the contaminant in a batch experiment.

42. The method of claim 40, further comprising determining the spatial concentration distribution of the contaminant in the subsurface.

43. The method of claim 42, further comprising determining a hydrogeological property of the subsurface,

wherein the hydrogeological property is selected from the group consisting of water saturated zones, water unsaturated zones, hydraulic gradient, saturated thickness, soil composition, hydraulic conductivity, porosity, density, and variation of any of these with time or space.

44. The method of claim 43, further comprising using the determined spatial concentration distribution of the contaminant and the hydrogeological property to determine an optimal location of an injection site for introducing the surfactant and oxidant and optionally the solvent and optionally the activator and an optimal amount of surfactant and oxidant and optionally the solvent and optionally the activator to introduce at each injection site,

wherein determining the optimal location of an injection site comprises modeling the flow of surfactant and oxidant and optionally the solvent and optionally the activator in the subsurface and selecting an injection site from which the surfactant and oxidant and optionally the solvent and optionally the activator will flow to the contaminant, and

wherein determining the optimal amount of surfactant and oxidant and optionally the solvent and optionally the activator comprises determining the amount of surfactant and oxidant and optionally the amount of solvent and optionally the amount of activator to oxidize at least 90% of the contaminant.

45. The method of claim 40, further comprising

determining the spatial concentration distribution of the contaminant;

determining a hydrogeological property of the subsurface; and

using the determined spatial concentration distribution of the contaminant and the hydrogeological property to determine the target depth for the surfactant and oxidant and optionally for the cosolvent and activator.

46. The method of claim 45, further comprising selecting the ratio of the mass of surfactant and oxidant and optionally of cosolvent and activator to the mass of an introduced substance to maximize the fraction of surfactant and oxidant and optionally of solvent and activator that remains at the target depth.

47. The method of claim 17, wherein the surfactant comprises at least one citrus terpene, at least one nonionic surfactant selected from the group consisting of ethoxylated soybean oil, ethoxylated castor oil, ethoxylated coconut fatty acid, and amidified, ethoxylated coconut fatty acid, and water.

48. The method of claim 47, wherein the surfactant comprises from about 10 wt % to about 40 wt % of the at least one citrus terpene and from about 10 wt % to about 40 wt % of the at least one nonionic surfactant.

49. The method of claim 47, wherein the surfactant comprises from about 10 wt % to about 40 wt % of the at least one citrus terpene and from about 10 wt % to about 90 wt % of the at least one nonionic surfactant.

50. The method of claim 1,

wherein the oxidant is introduced with a volume of a solution and wherein the surfactant is introduced with a volume of a solution and

wherein no more than 5% of the combined volume of the solution comprising the oxidant and the volume of the solution comprising the surfactant is extracted from the soil.

51. The method of claim 50, wherein a solution introduced into a substrate containing the soil comprises the oxidant and the surfactant.

53. The method of claim 19, wherein the activator is selected from the group consisting essentially of a peroxide, calcium peroxide, and hydrogen peroxide.

54. The method of claim 1, wherein none of the introduced surfactant is extracted from the soil.

55. The method of claim 1, wherein the oxidant is selected from the group consisting essentially of a persulfate and sodium persulfate.

56. The method of claim 1, wherein the surfactant forms micelles in the subsurface.

57. The method of claim 1, wherein the oxidant comprises hydrogen peroxide, a peroxide, and/or a peroxide containing compound.

4. A method for reducing the concentration of a contaminant in a soil, comprising:

introducing an oxidant and a surfactant into a subsurface containing the soil;

introducing an antioxidant into the subsurface containing the soil;

allowing the surfactant to solubilize or desorb the contaminant; and

allowing the oxidant to oxidize the solubilized contaminant in the subsurface, so that the amount of the contaminant in the soil is substantially reduced,

wherein the overall rate of oxidization of the contaminant is controlled to a predetermined value and the overall rate of solubilization of the contaminant is controlled to a predetermined value by selecting the surfactant, oxidant, and antioxidant and adjusting the concentrations of the surfactant, oxidant, and antioxidant, so that the rate of oxidation of the contaminant is greater than, less than, or equal to the rate of solubilization of the contaminant and

wherein the surfactant resists oxidation by the oxidant.

5. The method of claim 4, wherein the antioxidant is a biodegradable antioxidant.

6. The method of claim 4, wherein the antioxidant is a natural constituent of a plant oil.

7. The method of claim 4, wherein the antioxidant is selected from the group consisting of synthetic organic antioxidants such as beta hydroxy toluene and beta hydroxy anisole.

58. The method of claim 4, wherein the oxidant comprises hydrogen peroxide, a peroxide, and/or a peroxide containing compound.

52. A method for reducing the concentration of a contaminant in a soil, comprising:

introducing an oxidant and a surfactant into a ground surface or above-ground formation, structure, or container containing the soil;

allowing the surfactant to solubilize or desorb the contaminant; and

allowing the oxidant to oxidize the solubilized contaminant, so that the amount of the contaminant in the soil is substantially reduced,

wherein the overall rate of oxidization of the contaminant is controlled to a predetermined value and the overall rate of solubilization of the contaminant is controlled to a predetermined value by selecting the oxidant and surfactant and adjusting the concentrations of the oxidant and surfactant, so that the rate of oxidation of the contaminant is greater than, less than, or equal to the rate of solubilization of the contaminant,

wherein at least 40% of the initial mass of contaminant is destroyed in situ in the ground surface or above-ground formation, structure, or container,

wherein the surfactant resists oxidation by the oxidant, and the surfactant increases oxidation of the contaminant, and

wherein the contaminant comprises a nonaqueous phase liquid (NAPL).

59. The method of claim 52, wherein the oxidant comprises hydrogen peroxide, a peroxide, and/or a peroxide containing compound.