# US 10,501,687 B2 · Encapsulation and controlled delivery of strong mineral acids

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- Number: US 10,501,687 B2
- Document ID: US10501687B2
- Status: Granted
- Kind: B2
- Application number: 15/456,015
- Filed: 2017-03-10
- Published: 2017-06-29
- Granted: 2019-12-10
- Earliest claimed: 2014-07-17
- Assignees: Aramco Services Company; Rti International
- Applicants: Aramco Services Company; RTI International
- Inventors: Leah M. Johnson; Ghaithan Al-Muntasheri; Ginger Denison Rothrock; Sarah Sheperd
- Web page: https://patentgrep.com/patent/US10501687B2

## CPC

- C09K 8/882: {obtained by reactions only involving carbon-to-carbon unsaturated bonds}
- C09K 8/72: Eroding chemicals, e.g. acids
- C09K 8/725: {Compositions containing polymers}
- C09K 8/82: Oil-based compositions (C09K8/64 takes precedence)
- C09K 8/92: characterised by their form or by the form of their components, e.g. encapsulated material (C09K8/70 takes precedence)
- E21B 43/25: Methods for stimulating production {(by vibrating earth formations E21B43/003)}
- C09K 2208/14: Double emulsions, i.e. oil-in-water-in-oil emulsions or water-in-oil-in-water emulsions
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS

## 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.

## Claims

### Claim 1

A polymer-encapsulated mineral acid solution comprising:
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.

### Claim 2 (depends on 1)

The capsule 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.

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 1)

The capsule 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.