Traceable metal-organic frameworks for use in subterranean formations

Patent metadata

Field	Value
Publication number	US-10060242-B2
Application number	US-201415523530-A
Country	US
Kind code	B2
Filing date	Dec 5, 2014
Priority date	Dec 5, 2014
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

Systems and methods for the use of traceable metal-organic frameworks in subterranean formations are provided. In one embodiment, the methods comprise: introducing a fluid into a wellbore penetrating at least a portion of a subterranean formation, the fluid comprising a base fluid and a solid particle comprising a metal-organic framework comprising at least one detectable component, wherein the metal-organic framework further comprises at least one metal ion and an organic ligand that is at least bidentate and that is bonded to the metal ion; and detecting one or more signals from the at least one detectable component.

First claim

What is claimed is:

1. A method comprising:
introducing a fluid into a wellbore penetrating at least a portion of a subterranean formation, the fluid comprising a base fluid and a solid particle comprising a metal-organic framework comprising at least one detectable component, wherein the metal-organic framework is not coated or encapsulated and further comprises at least one metal ion and an organic ligand that is at least bidentate and that is bonded to the metal ion; and
detecting one or more signals from the at least one detectable component.

2. The method of claim 1 wherein the at least one detectable component comprises a metal ion selected from the group consisting of Li + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Ti 3+ , Ti 2+ , Zr 4+ , Zr 3+ , Zr 2+ , Hf 4+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh 3+ , Ir 2+ , Ir + , Ni 2+ , Ni + Pd 4+ , Pd 2+ , Pd + , Pt 4+ , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Hg + , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Tl + , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ , Bi + , Gd 3+ , Eu 3+ , Tb 3+ , and any combination thereof.

3. The method of claim 1 wherein the organic ligand comprises the at least one detectable component.

4. The method of claim 1 wherein the at least one detectable component is selected from the group consisting of: a luminescent quantum dot, a perhalogenated compound, a light-absorbing dye, a fluorescent dye, a short-chain aliphatic compound, a chelating agent, a high thermal neutron capture compound, 13 C, 14 C, 1 H, 2 H, 15 N, 31 P, 17 O, 18 O, 19 F, 33 S, 35 Cl, 37 Cl, 79 Br, 81 Br, 127 I, and any combination thereof.

5. The method of claim 1 wherein the at least one detectable component comprises a guest molecule within at least one pore space in the metal-organic framework.

6. The method of claim 5 wherein the guest molecule is selected from the group consisting of: Li + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Ti 3+ , Ti 2+ , Zr 4+ , Zr 3+ , Zr 2+ , Hf 4+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Re 3+ , Re 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh 3+ , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 4+ , Pd 2+ , Pd + , Pt 4+ , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Hg + , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Tl + , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ , Bi + , Eu 3+ , Tb 3+ , and any combination thereof.

7. The method of claim 1 wherein detecting the one or more signals comprises applying a magnetic field to at least the portion of the subterranean formation.

8. The method of claim 1 wherein the at least one detectable component is at least partially radioactive.

9. The method of claim 1 wherein the detecting comprises neutron capture.

10. The method of claim 1 wherein the detecting comprises an x-ray source.

11. The method of claim 1 wherein the detectable component is detected using one or more sensors.

12. The method of claim 1 further comprising generating an image of at least the portion of the subterranean formation using the one or more signals from the at least one detectable component.

13. The method of claim 1 wherein the intensity of the one or more signals depends, at least in part, on at least one condition in at least the portion of the subterranean formation.

14. The method of claim 1 wherein the introducing comprises penetrating the fluid into one or more fractures in at least the portion of the subterranean formation.

15. The method of claim 1 wherein the fluid is introduced into the wellbore using one or more pumps at or above a pressure sufficient to create or enhance one or more fractures in at least the portion of the subterranean formation.

16. The method of claim 1 wherein the metal-organic framework is a proppant particulate.

17. A method comprising:
introducing a fluid into a wellbore penetrating at least a portion of a subterranean formation, the fluid comprising a base fluid and a solid particle comprising a metal-organic framework comprising at least one detectable component, wherein the metal-organic framework is not coated or encapsulated and further comprises at least one metal ion and an organic ligand that is at least bidentate and that is bonded to the metal ion;
depositing the solid particle comprising the metal-organic framework in at least the portion of the subterranean formation; and
detecting one or more signals from the at least one detectable component.

18. The method of claim 17 , wherein at least the portion of the subterranean formation comprises one or more fractures in the subterranean formation.

19. A system comprising:
a metal-organic framework located in a portion of a subterranean formation at the well site comprising at least one detectable component, wherein the metal-organic framework is not coated or encapsulated and comprises at least one metal ion and an organic ligand that is at least bidentate and that is bonded to the metal ion;
one or more sensors detecting one or more signals from the at least one detectable component; and
imaging equipment communicating with the one or more sensors, wherein the one or more sensors are located at a well site.

20. The system of claim 19 wherein the at least one detectable component is selected from the group consisting of: a luminescent quantum dot, a perhalogenated compound, a light-absorbing dye, a fluorescent dye, a short-chain aliphatic compound, a mechanically-interlocked molecular architecture, a chelating agent, a high thermal neutron capture compound, 13 C, 14 C, 1 H, 2 H, 15 N, 31 P, 17 O, 18 O, 19 F, 33 S, 35 Cl, 37 Cl, 79 Br, 81 Br, 127 I, Li + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ti 4+ , Ti 3+ , Ti 2+ , Zr 4+ , Zr 3+ , Zr 2+ , Hf 4+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh 3+ , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 4+ , Pd 2+ , Pd + , Pt 4+ , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Hg + , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Tl + , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ , Bi + , Gd 3+ , Eu 3+ , Tb 3+ , and any combination thereof.

Assignees

• Halliburton Energy Services Inc

Inventors

• Benoit Denise Nicole
• Schultheiss Nathan Carl
• Lu Zheng
• Oliveira Humberto Almeida
• Palla-Venkata Chandra Sekhar

Classifications

• E21B47/092

  by detecting magnetic anomalies · CPC title

• E21B47/111 Primary

  using radioactivity · CPC title

• E21B43/26 Primary

  by forming crevices or fractures · CPC title

• E21B47/0905

  Fixed Constructions · mapped topic