Increasing subterranean mobilization of organic contaminants and petroleum by aqueous thermal oxidation

• US 6,387,278 B1
• Filed: 02/16/2000
• Issued: 05/14/2002
• Est. Priority Date: 02/16/2000
• Status: Expired due to Fees

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America), University The Regents of The California
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Aines, Roger D., Leif, Roald N., Eaker, Craig, Newmark, Robin L., Knauss, Kevin G.
• Primary Examiner(s): Hoey, Betsey Morrison
• Application Number:
  US09/505,289
• Time in Patent Office: 818 Days
• Field of Search: 210/747, 210/758, 210/763, 210/170, 210/908, 405/128.7, 405/128.75
• US Class Current: 210/747.8
• CPC Class Codes: B09C 1/02 Extraction using liquids, e.g. washing, leaching , flotation
• CPC Class Codes: B09C 1/08 chemically
• CPC Class Codes: B09C 2101/00 In situ
• CPC Class Codes: C02F 1/02 by heating methods of steam generation F22B; preheating boiler feed-water or accumulating preheated boiler feed-water F22D
• CPC Class Codes: C02F 1/72 by oxidation C02F1/4672 takes precedence
• CPC Class Codes: C02F 1/722 Oxidation by peroxides
• CPC Class Codes: C02F 1/78 with ozone C02F1/4672 takes precedence
• CPC Class Codes: C02F 2101/30 Organic compounds
• CPC Class Codes: C02F 2101/32 Hydrocarbons, e.g. oil
• CPC Class Codes: C02F 2103/06 Contaminated groundwater or leachate
• CPC Class Codes: C09K 23/00 Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
• CPC Class Codes: C09K 8/52 Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
• CPC Class Codes: E21B 43/16 Enhanced recovery methods for obtaining hydrocarbons
• CPC Class Codes: E21B 43/24 using heat, e.g. steam injection
• CPC Class Codes: E21B 43/243 Combustion in situ
• CPC Class Codes: Y10S 210/908 Organic

Abstract

In situ hydrous pyrolysis/partial oxidation of organics at the site of the organics constrained in an subsurface reservoir produces surfactants that can form an oil/water emulsion that is effectively removed from an underground formation. The removal of the oil/water emulsions is particularly useful in several applications, e.g., soil contaminant remediation and enhanced oil recovery operations. A portion of the constrained organics react in heated reservoir water with injected steam containing dissolved oxygen gas at ambient reservoir conditions to produce such surfactants.

Claims

1. A method for producing surfactants from accumulations of constrained organics at a subsurface site in a subsurface reservoir, said method comprising:

injecting steam and an oxidant into the subsurface site containing constrained organics to form a mixture containing predetermined portions of (a) condensed water from the stream and (b) the oxidant, water from the subsurface site and the constrained organics from the reservoir;

allowing hydrous pyrolysis/partial oxidation of the mixture to produce surfactants that form an oil/water emulsion with a second portion of the constrained organics and condensed water from the steam and/or water occurring naturally in the reservoir; and

removing the oil/water emulsion from the subsurface reservoir.

2. The method of claim 1 wherein the oil/water emulsion comprises a lower surface tension than a removed second portion of the constrained organics containing no surfactants.

3. The method of claim 1 wherein the oxidant is selected from the group consisting of oxygen-containing fluid, oxygen gas, air, peroxide ions, and ozone.

4. The process of claim 1 wherein temperature conditions of the hydrous pyrolysis/partial oxidation of the mixture at the site are lower than that required to essentially degrade a majority of the organics in the reservoir.

5. A method for removing constrained organics from a subsurface reservoir, said method comprising:

elevating the temperature of the subsurface reservoir above the naturally occurring temperature of said reservoir,

introducing steam into said reservoir,

allowing at least a portion of said steam to condense in said reservoir,

introducing an oxidant into said reservoir so as to contact water from condensed steam and/or water occurring naturally in the reservoir,

producing surfactant precursors and/or surfactants at the site of the constrained organics contained in said reservoir,

forming oil/water emulsions stabilized by said surfactant precursors and/or said surfactants, and

removing said oil/water emulsions from said reservoir.

6. The method of claim 5 wherein the oxidant is selected from the group consisting of oxygen-containing fluid, oxygen gas, air, peroxide ions, and ozone.

7. The method of claim 5 wherein the oil/water emulsion comprises a lower surface tension than a removed second portion of the constrained organics containing no surfactants.

8. An enhanced oil recovery method comprising:

injecting steam and an oxidant into a subsurface reservoir containing constrained crude oil and liquid water;

producing surfactants by in situ hydrous pyrolysis/partial oxidation of a first portion of the crude oil;

forming an oil/water emulsion from the produced surfactants, the liquid water and a second portion of the crude oil; and

removing the oil/water emulsion from the subsurface reservoir.

9. The method of claim 8 wherein at least a portion of said steam is allowed to condense in said reservoir prior to or during said producing of said surfactants.

10. The method of claim 8 further comprising steam flooding the underground reservoir prior to injecting steam and the oxidant into the reservoir.

11. The method of claim 8 wherein during said producing of said surfactants said reservoir has an elevated temperature relative to the normal temperature of the reservoir.

12. An environmental restoration method comprising:

injecting oxygen-containing gas and steam into subsurface soil containing constrained organic contaminants and condensate water;

producing surfactants by in situ hydrous pyrolysis/partial oxidation of the organic contaminants;

forming an oil/water emulsion from the produced surfactants, the condensate water and a second portion of the constrained organic contaminants; and

removing the oil/water emulsion from the subsurface soil.

13. The method of claim 12 further comprising inducing underground stripping prior to injecting the oxygen-containing gas and steam.

14. A process for in situ hydrous pyrolysis/partial oxidation of chlorinated or fuel hydrocarbons or other volatile contaminants, comprising:

(a) inducing hydrous pyrolysis/partial oxidation at a site of contamination by introducing steam and oxygen under pressure to a site of contamination;

(b) optionally relieving the build-in pressure;

(c) allowing the hydrous pyrolysis/partial oxidation resulting in partial oxidation of a first portion of the contaminants to produce surfactants; and

(d) removing from the site of contamination a contaminant/surfactant/water emulsion formed from mixing the produced surfactants with a second portion of the contaminants.

15. The process of claim 14 further comprising inducing hydrous pyrolysis/partial oxidation at a temperature between 75°

C. and 200°

C.

16. The process of claim 14 further comprising introducing a catalyst for partial oxidation of organics to the site.

17. The process of claim 16 wherein the catalyst is an oxidant selected from the group consisting of manganese dioxide and ferric oxide.

18. The process of claim 16 wherein the catalyst is present in the soil at the site naturally.

19. The process of claim 14 further comprising heating the ground by a method selected from the group consisting of direct electrical resistance heating, radio frequency, and microwave heating.

20. The process of claim 14 wherein the introduction of steam or oxygen is repeated multiple times.

21. The process of claim 14 wherein the contaminant is selected from the group consisting benzene, toluene, ethylbenzene, m-xylene, o-xylene, p-xylene, methyl tert-butyl ether, pentachlorophenol, phenol, 2-methylphenol, 4-methylphenol, 2,4-dimethylphenol, benzoic acid, napthalene, 2-methylnapthalene, acenaphthene, dibenzofuran, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b and k) fluoranthenes, benzo (a) pyrene, other hydrocarbons or chlorinated hydrocarbons, and mixtures thereof.