IP Library › Granted Patent US 11,505,738
Granted Patent B2
US 11,505,738 · App. 16/908,371 · Granted Nov 22, 2022

Methods, treatment fluids and systems for differential acidizing of a siliceous material

Inventors: Aaron M. Beuterbaugh (Spring, TX); Enrique Antonio Reyes (Tomball, TX)
Assignee: Halliburton Energy Services, Inc.
C09K8/72C09K8/528C09K8/70C09K8/76E21B43/26
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Quick Facts
Patent No.
US 11,505,738
App. No.
16/908,371
Granted
Nov 22, 2022
Kind
B2
Abstract

The rapid reaction of hydrofluoric acid with siliceous materials can make it difficult to increase the permeability of subterranean formations containing siliceous minerals. Methods for stimulating a subterranean formation can comprise: providing a latent hydrofluoric acid composition comprising a degradable matrix, and a hydrofluoric acid precursor dispersed in the degradable matrix; introducing a first treatment fluid containing the latent hydrofluoric acid composition in a non-dissolved form into a wellbore penetrating a subterranean formation comprising a siliceous material; differentially depositing the latent hydrofluoric acid composition upon a portion of the siliceous material in one or more locations; degrading at least a portion of the degradable matrix, thereby exposing at least a portion of the hydrofluoric acid precursor; converting the exposed hydrofluoric acid precursor into hydrofluoric acid; and reacting the hydrofluoric acid with the siliceous material where the latent hydrofluoric acid composition was deposited.

Claims (29)

1. A treatment fluid comprising:

an aqueous carrier fluid;

an organic co-solvent in an amount of about 1% to about 50% by volume of the treatment fluid;

a latent hydrofluoric acid composition present in a non-dissolved form in the carrier fluid, the latent hydrofluoric acid composition comprising a degradable matrix and a hydrofluoric acid precursor dispersed in the degradable matrix, wherein the degradable matrix coats the hydrofluoric acid precursor, wherein the hydrofluoric acid precursor comprises at least one acid precursor selected from the group consisting of: fluorosulfuric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, difluorophosphoric acid, hexafluorosilicic acid, potassium hydrogen difluoride, sodium hydrogen difluoride, polyvinylammonium fluoride, polyvinylpyridinium fluoride, pyridinium fluoride, imidazolium fluoride, ammonium fluoride, tetrafluoroborate salts, hexafluoroantimonate salts, hexafluorophosphate salts, bifluoride salts, perfluorinated organic compounds, TiF 4 , TiF S6 2− , cesium fluoride, boron trifluoride, boron trifluoride complexes, or combinations thereof; and

wherein the treatment fluid has a pH value of 3 or lower.

2. The treatment fluid of claim 1 , further comprising a plurality of fluid loss control particulates.

3. The treatment fluid of claim 2 , wherein the fluid loss control particulate has at least one dimension ranging between about 0.1 μm to about 500 μm.

4. The treatment fluid of claim 1 , wherein the degradable matrix comprises at least one degradable polymer selected from the group consisting of polysaccharides, proteins, aliphatic polyesters, poly(hydroxyalkanoates), poly(β-hydroxyalkanoates), poly(ω-hydroxy alkanoates), polylactides, polyglycolides, poly(ϵ-caprolactone)s, poly(hydroxybutyrate)s, poly(alkylene dicarboxylates), polyanhydrides, poly(hydroxy ester ether)s, poly(ether ester)s, poly(ester amide)s, polycarbamates (i.e., polyurethanes), polycarbonates, poly(orthoester)s, poly(amino acid)s, poly(ethylene oxide), polyphosphazenes, polyvinyl alcohol, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, acetyl cellulose, hydroxyethyl cellulose, shellac, dextran, guar, xanthan, starch, a scleroglucan, a diutan, poly(vinyl pyrollidone), polyacrylamide, polyacrylic acid, poly(diallyldimethylammonium chloride), poly(ethylene glycol), polylysine, polymethacrylamide, polymethacrylic acid, poly(vinylamine), any derivative thereof, any copolymer thereof, any salt thereof, and any combination thereof.

5. The treatment fluid of claim 1 , wherein the degradable matrix is acid-degradable.

6. The treatment fluid of claim 1 , wherein the degradable matrix comprises an acid-degradable polymer.

7. The treatment fluid of claim 6 , wherein the acid-degradable polymer comprises polylactic acid, any derivative thereof, or any combination thereof.

8. The treatment fluid of claim 1 , wherein the degradable matrix undergoes degradation to expose at least a portion of the hydrofluoric acid precursor to reactive conditions.

9. The treatment fluid of claim 1 , wherein the hydrofluoric acid precursor comprises a solid material.

10. The treatment fluid of claim 1 , wherein the hydrofluoric acid precursor is loaded in the degradable matrix in an amount of about 1% to about 50% by weight of the latent hydrofluoric acid composition.

11. A treatment fluid comprising:

an aqueous carrier fluid;

an organic co-solvent in an amount of about 1% to about 50% by volume of the treatment fluid;

a latent hydrofluoric acid composition present in a non-dissolved form in the carrier fluid, the latent hydrofluoric acid composition comprising a degradable matrix, a hydrofluoric acid precursor dispersed in the degradable matrix, wherein the degradable matrix coats the hydrofluoric acid precursor, and a plurality of fluid loss control particulates,

wherein the hydrofluoric acid precursor comprises at least one acid precursor selected from the group consisting of: fluorosulfuric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, difluorophosphoric acid, hexafluorosilicic acid, potassium hydrogen difluoride, sodium hydrogen difluoride, polyvinylammonium fluoride, polyvinylpyridinium fluoride, pyridinium fluoride, imidazolium fluoride, ammonium fluoride, tetrafluoroborate salts, hexafluoroantimonate salts, hexafluorophosphate salts, bifluoride salts, perfluorinated organic compounds, TiF 4 , TiF S6 2− , cesium fluoride, boron trifluoride, boron trifluoride complexes, or combinations thereof; and

wherein the treatment fluid has a pH value of 3 or lower.

12. The treatment fluid of claim 11 , wherein the fluid loss control particulate has at least one dimension ranging between about 0.1 μm to about 500 μm.

13. The treatment fluid of claim 11 , wherein the degradable matrix is acid-degradable.

14. The treatment fluid of claim 11 , wherein the degradable matrix comprises an acid-degradable polymer.

15. The treatment fluid of claim 14 , wherein the acid-degradable polymer comprises polylactic acid, any derivative thereof, or any combination thereof.

16. The treatment fluid of claim 11 , wherein the hydrofluoric acid precursor is loaded in the degradable matrix in an amount of about 1% to about 50% by weight of the latent hydrofluoric acid composition.

17. The treatment fluid of claim 1 , wherein the degradable matrix fully or partially coats the hydrofluoric acid precursor.

18. The treatment fluid of claim 11 , wherein the degradable matrix fully or partially coats the hydrofluoric acid precursor.

19. The treatment fluid of claim 1 , wherein the pH value is between about 1 and about 3.

20. The treatment fluid of claim 11 , wherein the pH value is between about 1 and about 3.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 22, 2020
From: BEUTERBAUGH, AARON M.; REYES, ENRIQUE ANTONIO
To: HALLIBURTON ENERGY SERVICES, INC.
Reel/Frame 053005/0162 →
Continuity (2)
Division 15754048
Related Publication 20200317995A1 · Oct 8, 2020
Cited By (1)
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