IP Library Granted Patent US 11,781,057
Granted Patent B2
US 11,781,057 · App. 17/452,913 · Granted Oct 10, 2023

Amphiphilic block copolymer surfactant for attenuating acid reactivity during acid stimulation of carbonate rich reservoirs

Inventors: Sivaprakash Shanmugam (Houston, TX); Amy J. Cairns (Houston, TX); Mohammed Sayed (Katy, TX)
Assignee: SAUDI ARABIAN OIL COMPANY
C09K8/54C08F293/005C09K8/604C09K8/74E21B43/27C08F2438/03C09K2208/32
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Quick Facts
Patent No.
US 11,781,057
App. No.
17/452,913
Granted
Oct 10, 2023
Kind
B2
Abstract

A composition for treating a formation includes a surfactant including an amphiphilic block copolymer having a first block and a second block and an acid. The amphiphilic block copolymer is a reaction product of a first monomer and a second monomer via a reversible addition-fragmentation chain transfer polymerization (RAFT) in a two-step reaction using a chain transfer agent (CTA) and a radical initiator. The surfactant favors adsorption onto a surface of the formation such that a temporary barrier is formed, thereby attenuating a reaction rate between the acid and the formation.

Claims (20)

1. A composition for treating a formation, comprising:

a surfactant including an amphiphilic block copolymer having a first block and a second block; and

an acid,

wherein the amphiphilic block copolymer is a reaction product of a first monomer and a second monomer via a reversible addition-fragmentation chain transfer polymerization (RAFT) in a two-step reaction,

wherein the two-step reaction includes a first step synthesized using the first monomer, a chain transfer agent, and a first radical initiator, and a second step synthesized through chain extension of the first block using the second monomer and a second radical initiator,

wherein the first radical initiator is different from the second radical initiator, and

wherein the surfactant favors adsorption onto a surface of the formation such that a temporary barrier is formed, thereby attenuating a reaction rate between the acid and the formation.

2. The composition of claim 1 , wherein each of the first monomer and the second monomer comprises one or more compounds of formula:

wherein

R 1 and R 2 are independently selected from the group consisting of halogen, H, CN, CF 3 , straight or branched alkyl of C 1 -C 20 , α,β-unsaturated straight or branched alkenyl or alkynyl of C 2 -C 10 , α,β-unsaturated straight or branched alkenyl of C 2 -C 6 substituted with a halogen, C 3 -C 8 cycloalkyl, heterocyclyl C(═Y)R 5 (Y is NR 8 or O, R 5 is C 1 -C 20 alkyl), C(═Y)NR 6 R 7 (R 6 and R 7 are H or C 1 -C 20 alkyl, or R 6 and R 7 together form a 3- to 6-membered ring), and YC(═Y)R 8 (R 8 is H, or straight or branched C 1 -C 20 alkyl or aryl);

R 3 and R 4 are independently selected from the group consisting of halogen, H, C 1 -C 6 alkyl, and COOR 9 , where R 9 is an alkali metal, H, or a C 1 -C 6 alkyl group;

or R 1 and R 3 together form a (CH 2 ) n , or (CH 2 ) n substituted with from 1 to 2n halogen atoms or C 1 -C 4 alkyl; and

at least two of R 1 , R 2 , R 3 , and R 4 are a halogen or H.

3. The composition of claim 1 , wherein the first block comprises one or more of acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl acrylate, acrylamide, N,N′-dimethylacrylamide, or 2-(dimethylamino)ethyl methacrylate.

4. The composition of claim 1 , wherein the second block comprises one or more of methyl acrylate, tert-butyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, stearyl acrylate, or styrene.

5. The composition of claim 1 , wherein the amphiphilic block copolymer has a molecular weight between 1,000 and 10,000 g/mol.

6. The composition of claim 1 , wherein the first block has from 5 to 150 repeating units and the second block has from 5 to 150 repeating units.

7. The composition of claim 1 , wherein the acid comprises one or more of an organic acid or an inorganic acid.

8. The composition of claim 1 , wherein the acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, fluoroboric acid, formic acid, acetic acid, citric acid, lactic acid, sulfamic acid, or chloroacetic acid.

9. The composition of claim 1 , wherein a concentration of the amphiphilic block copolymer is in a range of up to 70 gpt.

Assignments (5)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 18, 2023
From: SAUDI ARAMCO UPSTREAM TECHNOLOGIES COMPANY
To: SAUDI ARABIAN OIL COMPANY
Reel/Frame 065268/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 17, 2023
From: ARAMCO SERVICES COMPANY
To: SAUDI ARAMCO UPSTREAM TECHNOLOGIES COMPANY
Reel/Frame 065255/0318 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 22, 2023
From: ARAMCO SERVICES COMPANY
To: SAUDI ARAMCO UPSTREAM TECHNOLOGIES COMPANY
Reel/Frame 065001/0199 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 22, 2023
From: SAUDI ARAMCO UPSTREAM TECHNOLOGIES COMPANY
To: SAUDI ARABIAN OIL COMPANY
Reel/Frame 065021/0299 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 1, 2021
From: SHANMUGAM, SIVAPRAKASH; CAIRNS, AMY J.; SAYED, MOHAMMED
To: ARAMCO SERVICES COMPANY
Reel/Frame 057980/0363 →
Continuity (1)
Related Publication 20230137416A1 · May 4, 2023