Nanocomposite oil sensors for downhole hydrocarbon detection

• US 9,377,449 B2
• Filed: 03/25/2013
• Issued: 06/28/2016
• Est. Priority Date: 06/15/2009
• Status: Expired due to Fees

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Tour, James M., Hwang, Chih-Chau, Lu, Wei, Ruan, Gedeng, Tomson, Mason B., Kan, Amy, Wang, Lu, Wong, Michael S., Kini, Gautam, Hirasaki, George J., Miller, Clarence
• Primary Examiner(s): Soderquist, Arlen
• Application Number:
  US14/387,291
• Publication Number:
  US 20150050741A1
• Time in Patent Office: 1,191 Days
• Field of Search: 436/25, 436 27- 30, 436/139, 252/408.1
• US Class Current: 1/1
• CPC Class Codes: C09K 2208/10 Nanoparticle-containing well treatment fluids
• CPC Class Codes: C09K 8/03 Specific additives for general use in well-drilling compositions
• CPC Class Codes: E21B 47/11 using tracers; using radioactivity
• CPC Class Codes: G01N 33/241 for hydrocarbon content

Abstract

Various embodiments of the present disclosure pertain to nanocomposites for detecting hydrocarbons in a geological structure. In some embodiments, the nanocomposites include: a core particle; a polymer associated with the core particle; a sulfur-based moiety associated with the polymer; and a releasable probe molecule associated with the core particle, where the releasable probe molecule is releasable from the core particle upon exposure to hydrocarbons. Additional embodiments of the present disclosure pertain to methods of detecting hydrocarbons in a geological structure by utilizing the nanocomposites of the present disclosure.

Claims

1. A nanocomposite suitable for detecting hydrocarbons in a geological structure, wherein the nanocomposite comprises:

a core particle;

a polymer associated with the core particle;

a sulfur-based moiety associated with the polymer; and

a releasable probe molecule associated with the core particle,

wherein the releasable probe molecule is releasable from the core particle upon exposure to hydrocarbons, wherein the releasable probe molecule is triheptylamine (“

THA”

).

2. The nanocomposite of claim 1, wherein the core particle is selected from the group consisting of carbon black, functionalized carbon black, oxidized carbon black, carboxyl functionalized carbon black, carbon nanotubes, functionalized carbon nanotubes, graphenes, graphene oxides, graphene nanoribbons, graphene oxide nanoribbons, metal nanoparticles, silica nanoparticles, silicon nanoparticles, silicon oxide nanoparticles, silicon nanoparticles bearing a surface oxide, and combinations thereof.

3. The nanocomposite of claim 1, wherein the sulfur-based moiety is a sulfate moiety with the following chemical formula:

—

OSO₃R,

wherein R is selected from the group consisting of H, Na, K, Li, NH₄, alkyl groups, aryl groups, phenyl groups, and combinations thereof.

4. The nanocomposite of claim 1, wherein the sulfur-based moiety is a sulfonate moiety with the following chemical formula:

—

SO₃R,

wherein R is selected from the group consisting of H, Na, K, Li, NH₄, alkyl groups, aryl groups, phenyl groups, and combinations thereof.

5. The nanocomposite of claim 1, wherein the nanocomposite has a neutral charge.

6. A method for detecting hydrocarbons in a geological structure, wherein the method comprises:

injecting nanocomposites into the geological structure, wherein the nanocomposites each comprise;

a core particle,

a polymer associated with the core particle,

a sulfur-based moiety associated with the polymer, and

a releasable probe molecule associated with the core particle, wherein the releasable probe molecule releases from the core particle upon exposure to hydrocarbons within the geological structure, wherein the releasable probe molecule comprises triheptylamine (“

THA”

);

collecting a sample of the nanocomposites after flow through the geological structure;

determining an amount of the releasable probe molecules associated with the nanocomposites in the collected sample;

comparing the determined amount with an amount of releasable probe molecules associated with the nanocomposites prior to injection into the geological structure; and

correlating the compared amount to presence of hydrocarbons in the geological structure, wherein a decrease in the amount of releasable probe molecules associated with nanocomposites in the collected sample relative to the amount of the releasable probe molecules associated with the nanocomposites prior to injection into the geological structure is indicative of the presence of hydrocarbons in the geological structure.

7. The method of claim 6, wherein the releasable probe molecule is non-covalently associated with the core particle.

8. The method of claim 6, wherein the releasable probe molecule is hydrophobic.

9. The method of claim 6, wherein the releasable probe molecule is non-radioactive.

10. The method of claim 6, wherein the polymer is poly(vinyl alcohol) (PVA).

11. The method of claim 6, wherein the sulfur-based moiety is a sulfate moiety with the following chemical formula:

—

OSO₃R,

wherein R is selected from the group consisting of H, Na, K, Li, NH₄, alkyl groups, aryl groups, phenyl groups, and combinations thereof.

12. The method of claim 6, wherein the sulfur-based moiety is a sulfonate moiety with the following chemical formula:

—

SO₃R,

wherein R is selected from the group consisting of H, Na, K, Li, NH₄, alkyl groups, aryl groups, phenyl groups, and combinations thereof.

13. The method of claim 6, wherein:

the polymer is sulfated or sulfonated polyvinyl alcohol,

the core particle is functionalized carbon black, and

the sulfated or sulfonated polyvinyl alcohol is covalently associated with the functionalized carbon black.

14. The method of claim 6, wherein the determining of the amount of releasable probe molecules associated with nanocomposites in the collected sample is determined by mass spectrometry.

15. The method of claim 6, wherein the nanocomposites have a neutral charge.

16. A system for detecting hydrocarbons in a geological structure, wherein the system comprises:

nanocomposites to be injected into the geological structure in combination with measurement equipment configured to determine an amount of releasable probe molecules associated with the nanocomposites, wherein the nanocomposites each comprise;

a core particle,

a polymer associated with the core particle,

a sulfur-based moiety associated with the polymer, and

a releasable probe molecule associated with the core particle, wherein the releasable probe molecule configured to release from the core particle upon exposure to hydrocarbons within the geological structure, wherein the releasable probe molecule comprises triheptylamine (“

THA”

);

equipment configured to inject the nanocomposites into the geological structure;

equipment configured to recover a sample of the nanocomposites after flow through the geological structure;

measurement equipment configured to determine an amount of the releasable probe molecules associated with the nanocomposites in the collected sample;

comparing the determined amount with an amount of releasable probe molecules associated with the nanocomposites prior to injection into the geological structure; and

equipment configured to correlate the compared amount to presence of hydrocarbons in the geological structure, wherein a decrease in the amount of releasable probe molecules associated with nanocomposites in the collected sample relative to the amount of the releasable probe molecules associated with the nanocomposites prior to injection into the geological structure is indicative of the presence of hydrocarbons in the geological structure.

17. The system of claim 16, wherein the sulfur-based moiety is a sulfate moiety with the following chemical formula:

—

OSO₃R,

wherein R is selected from the group consisting of H, Na, K, Li, NH₄, alkyl groups, aryl groups, phenyl groups, and combinations thereof.

18. The system of claim 16, wherein the sulfur-based moiety is a sulfonate moiety with the following chemical formula:

—

SO₃R,

wherein R is selected from the group consisting of H, Na, K, Li, NH₄, alkyl groups, aryl groups, phenyl groups, and combinations thereof.

19. The system of claim 16, wherein:

the polymer is sulfated or sulfonated polyvinyl alcohol,

the core particle is functionalized carbon black, and

the sulfated or sulfonated polyvinyl alcohol is covalently associated with the functionalized carbon black.

20. The system of claim 16, wherein the measurement equipment configured to determine the amount of releasable probe molecules associated with nanocomposites comprises a mass spectrometer.