Encapsulation and controlled delivery of strong mineral acids

Patent metadata

Field	Value
Publication number	US-11041117-B2
Application number	US-201916675024-A
Country	US
Kind code	B2
Filing date	Nov 5, 2019
Priority date	Jul 17, 2014
Publication date	Jun 22, 2021
Grant date	Jun 22, 2021

Abstract

A polymer-encapsulated mineral acid solution and a method for forming the polymer-encapsulated mineral acid solution. Introducing a strong mineral acid solution to a monomer solution occurs such that a primary emulsion that is a water-in-oil type emulsion forms. Introducing the primary emulsion to a second aqueous solution forms a secondary emulsion that is a water-in-oil-in-water type double emulsion. The monomer in the secondary emulsion is cured such a polymerized shell forms that encapsulates the strong mineral acid solution and forms the capsule. The strong mineral acid solution has up to 30 wt. % strong mineral acid. A method of stimulating a hydrocarbon-bearing formation using the polymer-encapsulated mineral acid solution includes introducing a capsule suspension into a fissure in the hydrocarbon-bearing formation to be stimulated through a face in a well bore. The capsule is maintained within the fissure until the polymer shell degrades.

First claim

What is claimed is:

1. A method of stimulating a hydrocarbon-bearing formation using a polymer-encapsulated mineral acid solution, the method comprising:
introducing a polymer-encapsulated mineral acid solution suspension into a fissure traversing the hydrocarbon-bearing formation to be stimulated,
where the polymer-encapsulated mineral acid solution suspension comprises a suspension fluid and the polymer-encapsulated mineral acid solution,
where the polymer-encapsulated mineral acid solution comprises:
a strong mineral acid solution where a strong mineral acid is in a range of from greater than 0 wt. % to about 30 wt. % of the strong mineral acid solution, and
a polymerized shell that encapsulates the strong mineral acid solution such that the polymerized shell encapsulates and prevents interaction with the strong mineral acid solution until the polymerized shell degrades, where the strong mineral acid solution does not degrade the polymerized shell, wherein the polymerized shell comprises a homopolymer, wherein the homopolymer comprises a polymerized monomer having acrylate end group functionality, the polymerized monomer having acrylate end group functionality selected from the group consisting of 1,6-hexanediol diacrylate, 1,1,1-trimethylolpropane triacrylate, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, dipentaerythritol pentaacryalate, and a urethane-acrylate oligomer; and

maintaining the polymer-encapsulated mineral acid solution suspension within the fissure such that the polymerized shell degrades within the fissure, such that the strong mineral acid solution is released into the fissure of the hydrocarbon-bearing formation, and the hydrocarbon-bearing formation is stimulated,
where a well bore is defined by a well bore wall and traverses the hydrocarbon-bearing formation,
where a face is a portion of the well bore wall associated with and operable to provide fluid communication between the hydrocarbon-bearing formation and the well bore, and
where the fissure in the hydrocarbon-bearing formation is accessible through the face.

2. The method of claim 1 where the strong mineral acid is selected from the group consisting of hydrochloric acid (HCl), hydrofluoric acid (HF), sulfuric acid (H2SO4), nitric acid (HNO3) and combinations thereof.

3. The method of claim 1 where the suspension fluid is a brine.

4. The method of claim 1 where the polymerized shell is the resultant of a free-radical chain polymerization reaction.

5. The method of claim 1 where the polymerized shell has a glass transition temperature (Tg) and the Tg is in a range of from 43° C. to 151° C.

6. The method of claim 1 where the polymerized shell does not have a glass transition temperature (Tg).

7. A method of stimulating a hydrocarbon-bearing formation using a polymer-encapsulated mineral acid solution, the method comprising:
introducing a polymer-encapsulated mineral acid solution suspension into a fissure traversing the hydrocarbon-bearing formation to be stimulated,
where the polymer-encapsulated mineral acid solution suspension comprises a suspension fluid and the polymer-encapsulated mineral acid solution,
where the polymer-encapsulated mineral acid solution comprises:
a strong mineral acid solution where a strong mineral acid is in a range of from greater than 0 wt. % to about 30 wt. % of the strong mineral acid solution, and
a polymerized shell that encapsulates the strong mineral acid solution such that the polymerized shell encapsulates and prevents interaction with the strong mineral acid solution until the polymerized shell degrades, where the strong mineral acid solution does not degrade the polymerized shell, wherein the polymerized shell comprises a homopolymer, wherein the homopolymer comprises a polymerized monomer having methacrylate end group functionality, the polymerized monomer having methacrylate end group functionality selected from the group consisting of diurethane dimethacrylate, Bisphenol-A glycerolate dimethacrylate, poly(ethylene glycol) dimethacrylate (having an average poly(ethylene glycol) (PEG) M n of about 600), and 1,6-hexanediol dimethacrylate; and

maintaining the polymer-encapsulated mineral acid solution suspension within the fissure such that the polymerized shell degrades within the fissure, such that the strong mineral acid solution is released into the fissure of the hydrocarbon-bearing formation, and the hydrocarbon-bearing formation is stimulated,
where a well bore is defined by a well bore wall and traverses the hydrocarbon-bearing formation,
where a face is a portion of the well bore wall associated with and operable to provide fluid communication between the hydrocarbon-bearing formation and the well bore, and
where the fissure in the hydrocarbon-bearing formation is accessible through the face.

8. The method of claim 7 where the strong mineral acid is selected from the group consisting of hydrochloric acid (HCl), hydrofluoric acid (HF), sulfuric acid (H2SO4), nitric acid (HNO3) and combinations thereof.

9. The method of claim 7 where the suspension fluid is a brine.

10. The method of claim 7 where the polymerized shell is the resultant of a free-radical chain polymerization reaction.

11. The method of claim 7 where the polymerized shell has a glass transition temperature (Tg) and the Tg is in a range of from 43° C. to 151° C.

12. The method of claim 7 where the polymerized shell does not have a glass transition temperature (Tg).

Assignees

• Aramco Services Co
• Rti Int

Inventors

• Johnson Leah M
• Al-Muntasheri Ghaithan
• Rothrock Ginger Denison
• Shepherd Sarah

Classifications

• C09K8/72 Primary

  Eroding chemicals, e.g. acids · CPC title

• C09K2208/14

  Double emulsions, i.e. oil-in-water-in-oil emulsions or water-in-oil-in-water emulsions · CPC title

• C09K8/92

  characterised by their form or by the form of their components, e.g. encapsulated material (C09K8/70 takes precedence) · CPC title

• C09K8/725

  Compositions containing polymers · CPC title

• C09K8/882 Primary

  obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title