Viscoelastic surfactant composition having improved rheological properties and method of using for treating subterranean formations

• US 20060025321A1
• Filed: 07/30/2004
• Published: 02/02/2006
• Est. Priority Date: 07/30/2004
• Status: Active Grant

• Current Assignee: Ecolab USA Incorporated (Ecolab, Inc.)
• Original Assignee: Nalco Company (Ecolab, Inc.)
• Inventors: Taylor, Grahame N., Moss, David Kelly, Treybig, Duane S.
• Granted Patent: US 7,244,698 B2
• Time in Patent Office: Days
• US Class Current: 510/382
• CPC Class Codes: C09K 2208/30 Viscoelastic surfactants [VES]
• CPC Class Codes: C09K 8/68 containing organic compounds

Abstract

A viscoelastic surfactant composition having improved rheological performance comprising one or more quaternized amidoamine surfactants, one or more tertiary amine amides, one or more polymeric acids and one or more electrolytes, viscosified aqueous fluids comprising the surfactant composition and methods of making and using the viscosified aqueous fluid for treating subterranean formations.

Claims

1. A surfactant composition comprising

(i) one or more quaternized amidoamine surfactants of formula I-IV, or a combination thereof

wherein R₁ and R₇ are independently selected from the group consisting of C₁₂-C₃₀ alkyl, C₁₂-C₃₀ alkenyl, C₁₂-C₃₀ arylalkyl and C₁₂-C₃₀ cycloalkylalkyl;

R₂ and R₃ are independently selected at each occurrence from hydrogen and C₁-C₄ alkyl;

R₄, R₅, R₆, R₈ and R₉ are independently selected from C₁-C₄ alkyl, C₁-C₄ alkoxyalkyl and C₁-C₄ hydroxyalkyl;

X and Y are independently selected from halide, alkyl sulfate and sulfate;

p is an integer from 1 to about 10;

m and n are independently integers of 1 to about 4;

Z is —

CH₂(CH₂)_qCH₂SO₃⁻

or —

CH₂CH(OH)CH₂SO₃⁻

; and

q is 1 or 2,

(ii) one or more tertiary amine amides of formula V or VI, or a combination thereof

wherein R₁, R₂, R₃, R₄, R₅, R₇, R₈, p, m and n are as defined in step (i); and

(iii) one or more polymeric acids.

2. The surfactant composition of claim 1 wherein the polymeric acids are selected from the group consisting of sulfonated polystyrenes, sulfonated polynaphthalenes, sulfonated styrene-maleic anhydride polymers, polyacrylic acid, polymethacrylic acid and poly acrylic methacrylic acid polymers.

3. The surfactant composition of claim 2 wherein the polymeric acid has a molecular weight of at least about 25,000.

4. The surfactant composition of claim 1 further comprising one or more electrolytes.

5. The surfactant composition of claim 1 wherein the electrolytes are selected from the group consisting of organic and inorganic salts of ammonia and alkali or alkaline-earth metals.

6. The surfactant composition of claim 1 wherein R₁ and R₇ are independently selected from the group consisting of C₁₅-C₃₀ alkyl and C₁₂-C₃₀ alkenyl.

7. The surfactant composition of claim 1 wherein R₁ and R₇ are independently selected from the group consisting of C₁₅-C₃₀ alkenyl.

8. The surfactant composition of claim 1 wherein R₁ and R₇ are independently selected from the group consisting of C₁₈-C₃₀ alkenyl.

9. The surfactant composition of claim 1 wherein R₁ and R₇ are independently selected from the group consisting of C₂₂-C₃₀ alkenyl.

10. The surfactant composition of claim 1 wherein p is an integer of 2 to about 6 and m and n are both 2.

11. The surfactant composition of claim 1 wherein R₁ and R₇ are independently selected from the group consisting of C₁₈-C₃₀ alkenyl;

R₂ and R₃ are hydrogen;

R₄, R₅, R₆, R₈ and R₉ are independently selected from C₁-C₂ alkyl, C₂-C₃ hydroxyalkyl and C₆-C₈ arylalkyl;

p is 2 or 3;

m and n are both 2 and X and Y are independently selected from Cl and CH₃O—

SO₂—

O—

.

12. The surfactant composition of claim 11 herein R₆ and R₈ are methyl and R₄, R₅ and R₉ are independently selected from the group consisting of methyl, ethyl and hydroxyethyl.

13. The surfactant composition of claim 12 wherein and R₄, R₅ and R₉ are methyl.

14. The surfactant composition of claim 13 wherein p is 2.

15. The surfactant composition of claim 14 wherein the polymeric acid is selected from the group consisting of sulfonated polystyrene and salts thereof and polyacrylic acid and salts thereof.

16. The surfactant composition of claim 15 wherein the sulfonated polystyrene and its salts have a molecular weight of at least about 75,000.

17. The surfactant composition of claim 1 comprising

(a) about 25 to about 80 weight percent of a surfactant mixture comprising

(a1) about 65 to about 99.4 weight percent of the quaternized amidoamine surfactants of formula I-IV, or a combination thereof,

(a2) about 0.5 to about 20 weight percent of the tertiary amine amides of formula V or VI, or a combination thereof and

(a3) about 0.1 to about 15 weight percent of the polymeric acid;

and

(b) about 20 to about 75 weight percent of a solvent system comprising

(b1) about 0 to about 10 weight percent water,

(b2) about 0 to about 45 weight percent of one or more alcohols and

(b3) about 0 to about 45 weight percent of one or more glycols.

18. The surfactant composition of claim 17 wherein the alcohol is isopropanol and the glycol is 1,3-propane diol.

19. The surfactant composition of claim 18 comprising

(a) about 55 to about 65 weight percent of a surfactant mixture comprising

(a1) about 65 to about 99.4 weight percent of the quaternized amidoamine surfactants of formula I-IV, or a combination thereof,

(a2) about 0.5 to about 20 weight percent of the tertiary amine amides of formula V or VI, or a combination thereof and

(a3) about 0.1 to about 15 weight percent of the polymeric acid;

and

(b) about 35 to about 45 weight percent of a solvent system comprising

(b1) about 0 to about 10 weight percent water,

(b2) about 0 to about 45 weight percent isopropanol and

(b3) about 0 to about 45 weight percent glycol.

20. The surfactant composition of claim 19 wherein the solvent system comprises about 0 to about 5 weight percent water, about 20 to about 35 weight percent isopropanol and about 0 to about 35 weight percent 1,3-propane diol.

21. The surfactant composition of claim 19 wherein the solvent system comprises about 3 to about 5 weight percent water, about 20 to about 22 weight percent isopropanol and about 8 to about 12 weight percent 1,3-propane diol.

44. A method of preparing a viscosified surfactant composition comprising adding one or more electrolytes to the surfactant composition of claim 1.

45. A viscosified surfactant composition prepared according to the method of claim 44.

22. A viscosified aqueous surfactant composition comprising

(I) about 1 to about 10 weight percent of a surfactant composition comprising

(a) about 20 to about 75 weight percent of a surfactant mixture comprising

(a1) about 65 to about 99.4 weight percent of the quaternized amidoamine surfactants of formula I-IV, or a combination thereof,

(a2) about 0.5 to about 20 weight percent of the tertiary amine amides of formula V or VI, or a combination thereof and

(a3) about 0.1 to about 15 weight percent of the polymeric acid;

and

(b) about 20 to about 75 weight percent of a solvent system comprising

(b1) about 0 to about 10 weight percent water,

(b2) about 0 to about 45 weight percent of one or more alcohols and

(b3) about 0 to about 45 weight percent of one or more glycols and

(II) about 0.4 to about 20 weight percent of one or more electrolytes; and

(III) about 80 to about 98.5 weight percent water.

23. The viscosified aqueous surfactant composition of claim 22 wherein the alcohol is isopropanol and the glycol is 1,3-propane diol.

24. The viscosified aqueous surfactant composition of claim 22 comprising about 0.4 to about 5 weight percent of one or more electrolytes.

25. The viscosified aqueous surfactant composition of claim 23 comprising

(I) about 1 to about 10 weight percent of a surfactant composition comprising

(a) about 55 to about 65 weight percent of a surfactant mixture comprising

(a1) about 65 to about 99.4 weight percent of the quaternized amidoamine surfactants of formula I-IV, or a combination thereof,

(a2) about 0.5 to about 20 weight percent of the tertiary amine amides of formula V or VI, or a combination thereof and

(a3) about 0.1 to about 15 weight percent of the polymeric acid;

and

(b) about 35 to about 45 weight percent of a solvent system comprising

(b1) about 0 to about 10 weight percent water,

(b2) about 0 to about 45 weight percent of isopropanol and

(b3) about 0 to about 45 weight percent of one or more 1,3-propane diol and

(II) about 0.4 to about 5 weight percent of one or more electrolytes; and

(III) about 80 to about 98.5 weight percent water.

26. The viscosified aqueous surfactant composition of claim 25 comprising

(I) about 1 to about 10 weight percent of a surfactant composition comprising

(a) about 55 to about 65 weight percent of a surfactant mixture comprising

(a1) about 84 to about 96.6 weight percent of the quaternized amidoamine surfactants of formula I-IV, or a combination thereof,

(a2) about 3 to about 11 weight percent of the tertiary amine amides of formula V or VI, or a combination thereof and

(a3) about 0.4 to about 5 weight percent of the polymeric acid;

and

(b) about 35 to about 45 weight percent of a solvent system comprising

(b1) about 0 to about 10 weight percent water,

(b2) about 0 to about 45 weight percent of isopropanol and

(b3) about 0 to about 45 weight percent of one or more 1,3-propane diol and

(II) about 1 to about 5 weight percent of one or more electrolytes; and

(III) about 80 to about 98.5 weight percent water.

27. The viscosified aqueous surfactant composition of claim 26 comprising

(I) about 1 to about 10 weight percent of a surfactant composition comprising

(a) about 55 to about 65 weight percent of a surfactant mixture comprising

(a1) about 88 to about 92.6 weight percent of the quaternized amidoamine surfactants of formula I-IV, or a combination thereof,

(a2) about 7 to about 11 weight percent of the tertiary amine amides of formula V or VI, or a combination thereof and

(a3) about 0.4 to about 2 weight percent of the polymeric acid;

and

(b) about 35 to about 45 weight percent of a solvent system comprising

(b1) about 0 to about 10 weight percent water,

(b2) about 0 to about 45 weight percent of isopropanol and

(b3) about 0 to about 45 weight percent of one or more 1,3-propane diol and

(II) about 1 to about 5 weight percent of one or more electrolytes; and

(III) about 80 to about 98.5 weight percent water.

28. The viscosified aqueous surfactant composition of claim 22 further comprising one or more particulate proppants suspended therein.

29. The viscosified aqueous surfactant composition of claim 22 further comprising one or more breakers.

30. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is a blend of polypropylene glycol, oleic acid and potassium oleate.

31. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is polypropylene glycol.

32. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is a blend of oxone.

33. The viscosified aqueous surfactant composition of claims 29 wherein the breaker is an oxidizer.

34. The viscosified aqueous surfactant composition of claim 33 where the oxidizer is sodium persulfate, sodium perchlorate, ammonium persulfate, potassium perchlorate, sodium permanganate monohydrate or ammonium perchlorate.

35. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is a poly(acrylic acid-2-acrylamido-2-methylpropanesulfonic acid).

36. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is oleic acid.

37. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is selected from sulfonated polystyrene, sulfonated polynapthalene, and sulfonated styrene-maleic anhydride polymers.

38. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is selected from polyacrylic acid, polymethacrylic acid and acrylic acid-methacrylic acid copolymer.

39. The viscosified aqueous surfactant composition of claim 29 wherein the breaker is selected from ethoxylated nonylphenol formaldehyde resins and ethoxylated nonyl and di-nonyl phenol formaldehyde resins.

40. A method of treating a well in a subterranean formation comprising pumping into the well the viscosified aqueous surfactant composition of claim 22.

41. The method of claim 40 wherein the treating is selected from drilling, hydraulic fracturing, gravel placement, scale removing and mud cake removing operations.

42. A method of fracturing a subterranean formation comprising pumping into the formation at a pressure sufficient to fracture the formation the surfactant composition of claim 24.

43. A method of fracturing a subterranean formation comprising pumping into the formation at a pressure sufficient to fracture the formation the viscosified aqueous surfactant composition of claim 22.