IP Library Granted Patent US 12,305,496
Granted Patent B1
US 12,305,496 · App. 18/644,800 · Granted May 20, 2025

Hydraulic treatment of subterranean formations using oxidant, nanoparticles, and carbon dioxide

Inventors: Murtadha J. AlTammar (Dhahran, SA); Hassan Sakar Alqahtani (Dammam, SA); Khalid Mohammed M. Alruwaili (Dammam, SA); Katherine Leigh Hull (Houston, TX); Younane N. Abousleiman (Norman, OK)
Assignee: Saudi Arabian Oil Company
E21B43/267E21B43/164
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Quick Facts
Patent No.
US 12,305,496
App. No.
18/644,800
Granted
May 20, 2025
Kind
B1
Abstract

A method of treating kerogen is provided. The method includes: generating a fracture network in a subterranean formation including kerogen by injecting a treatment fluid through a wellbore into the subterranean formation, the treatment fluid including water, an oxidant, and nanoparticles, the treatment fluid oxidizing a portion of the kerogen in the subterranean formation while generating the fracture network; and injecting carbon dioxide (CO 2 ) through the wellbore into the subterranean formation, the CO2 penetrating the subterranean formation through the facture network.

Claims (24)

1. A method of treating kerogen, the method comprising:

generating a fracture network in a subterranean formation comprising kerogen by injecting a first treatment fluid through a wellbore into the subterranean formation, the first treatment fluid comprising water, an oxidant, and nanoparticles, the first treatment fluid oxidizing a portion of the kerogen in the subterranean formation while generating the fracture network;

injecting a second treatment fluid comprising carbon dioxide (CO 2 ) through the wellbore into the subterranean formation, the CO 2 penetrating the subterranean formation through the facture network; and

alternately repeating the step of injecting the first treatment fluid and the step of injecting the second treatment fluid, wherein each injection step generates an additional fracture network.

2. The method of claim 1 , further comprising, prior to generating the fracture network, generating an initial fracture network in the subterranean formation, wherein the treatment fluid enters the initial fracture network, and wherein the fracture network generated by injecting the treatment fluid is an extended fracture network of the initial fracture network.

3. The method of claim 2 , wherein generating the initial fracture network comprises injecting the CO 2 into the subterranean formation.

4. The method of claim 3 , wherein the method comprises more than a dozen stages of injections, and at least the last stage of injection is performed using the second treatment fluid.

5. The method of claim 1 , wherein injecting the second treatment fluid comprises generating an additional fracture network in the subterranean formation.

6. The method of claim 1 , further comprising, while injecting the second treatment fluid, injecting the oxidant and the nanoparticles.

7. The method of claim 1 , wherein the injected second treatment fluid is at a supercritical state.

8. The method of claim 1 , wherein the first treatment fluid and the second treatment fluid are injected simultaneously.

9. The method of claim 1 , wherein the oxidant comprises a chlorite or bromate.

10. The method of claim 1 , wherein the oxidant comprises a salt of an alkali metal or alkaline earth metal.

11. The method of claim 1 , wherein the oxidant comprises a persulfate, perborate, percarbonate, peroxide, O 2 , O 3 , N 2 O, NO, or NO 2 .

12. The method of claim 1 , wherein the nanoparticles comprise silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), zinc oxide (ZnO), aluminum oxide (Al 2 O 3 ), cerium oxide (CeO 2 ), iron oxide (Fe 2 O 3 ), silver oxide (AgO), magnesium oxide (MgO), nickel oxide (NiO), zirconium oxide (ZrO), cadmium oxide (CdO).

13. A method of hydraulic fracturing, the method comprising:

generating an initial fracture network in a subterranean formation by injecting a CO 2 through a wellbore into the subterranean formation,

injecting a first fluid through the wellbore into the subterranean formation, the first fluid comprising a solvent, an oxidant and nanoparticles, the injected first fluid oxidizing a portion of the subterranean formation and extending the initial fracture network;

injecting a second fluid through the wellbore into the subterranean formation, the second fluid comprising carbon dioxide (CO 2 ), the CO 2 penetrating the subterranean formation through the extended facture network and dissolving another portion of the subterranean formation; and

alternately repeating the steps of injecting the first fluid and the second fluid, the repeating generating an additional fracture network.

14. The method of claim 13 , further comprising injecting the first fluid, the second fluid, or another fluid between two steps among the steps of injecting while alternately repeating the steps of injecting the first fluid and the second fluid.

15. The method of claim 13 , further comprising, while injecting the second fluid, injecting another fluid comprising the oxidant and the nanoparticles.

16. The method of claim 15 , wherein the solvent comprises a brine solution derived from seawater, wherein the oxidant comprises sodium bromate or sodium chlorite, and wherein the nanoparticles are silica nanoparticles.

17. The method of claim 13 , wherein the concentration of the oxidant in the first fluid is between 1 pounds per thousand gallons (pptg) (0.12 g/L) to 100 pptg (12.0 g/L).

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 13, 2024
From: ARAMCO SERVICES COMPANY
To: SAUDI ARAMCO UPSTREAM TECHNOLOGY COMPANY
Reel/Frame 068269/0178 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 13, 2024
From: SAUDI ARAMCO UPSTREAM TECHNOLOGY COMPANY
To: SAUDI ARABIAN OIL COMPANY
Reel/Frame 068273/0042 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 21, 2024
From: HULL, KATHERINE LEIGH; ABOUSLEIMAN, YOUNANE N.
To: ARAMCO SERVICES COMPANY
Reel/Frame 067483/0601 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 21, 2024
From: ALTAMMAR, MURTADHA J.; ALQAHTANI, HASSAN SAKAR; ALRUWAILI, KHALID MOHAMMED M.
To: SAUDI ARABIAN OIL COMPANY
Reel/Frame 067483/0669 →
References Cited (9)
US 11339321B2 · Hull et al. · 2022 [cited by applicant]
US 20100243248A1 · Golomb et al. · 2010 [cited by applicant]
US 20170066959A1 · Hull et al. · 2017 [cited by applicant]
US 20210113406A1 · Kovacs · 2021 [cited by applicant]
US 20210198558A1 · Hull · 2021 [cited by examiner]
CA 2247483C · 2009 [cited by examiner]
Hull et al., “Chemomechanical effects of oxidizer-CO2 systems upon hydraulically fractured unconventional source rock,” The Canadian Journal of Chemical Engineering, Jul. 2021, 100(6):1417-1426, 26 pages. [cited by applicant]
Hull et al., “Oxidative kerogen degradation: a potential approach to hydraulic fracturing in unconventionals,” Ene1 1rgy & Fuels, May 2010, 33(6):4758-4766, 11 pages. [cited by applicant]
Zheng et al., “A Nanoparticle Assisted CO2 Huff-N-Puff Field Test in the Eagle Ford Shale,” presented at the SPE Improved Oil Recovery Conference, held virtually, Aug. 31, 2020, 17 pages. [cited by applicant]