Corrosion inhibitors and methods of use

• US 6,866,797 B1
• Filed: 08/03/2001
• Issued: 03/15/2005
• Est. Priority Date: 08/03/2000
• Status: Active Grant

• Current Assignee: BJ Services Company
• Original Assignee: BJ Services Company
• Inventors: Dobbs, James B., Brock, Gene F., Martin, Richard L.
• Primary Examiner(s): Tucker, Philip C.
• Application Number:
  US09/922,231
• Time in Patent Office: 1,320 Days
• Field of Search: 252/389.23, 252/389.2, 507/939, 507/238, 507/240, 507/256
• US Class Current: 252/389.23
• CPC Class Codes: C09K 8/54 Compositions for in situ inhibition of corrosion in boreholes or wells
• CPC Class Codes: C23F 11/10 using organic inhibitors
• CPC Class Codes: C23F 11/141 Amines; Quaternary ammonium compounds
• CPC Class Codes: C23F 11/162 Thioaldehydes; Thioketones
• CPC Class Codes: C23F 11/1673 Esters of phosphoric or thiophosphoric acids
• CPC Class Codes: Y10S 507/939 Corrosion inhibitor

Abstract

A class of quaternary ammonium compounds are found to be effective as corrosion inhibitors. These quaternary ammonium compounds may be used alone or in combination with additional components. For example, phosphate esters can be used with the quaternary ammonium compounds. Moreover, thiocarbonyl compounds can also be added to the corrosion inhibitor compositions. These corrosion inhibitors are effective against ferrous metal corrosion, especially under downhole conditions.

Claims

1. A composition, comprising:

a quaternary ammonium compound of formula (I)

and a phosphate ester of formula (II);

wherein R¹, R², R³, R⁴ are independently a hydrocarbyl group;

X⁻

is selected from the group consisting of halide and sulfate; and

R⁵, R⁶, and R⁷ are independently selected from the group consisting of hydrogen, a hydrocarbyl group, and a polyoxyalkylated alcohol; and

further comprising a thiocarbonyl compound of formula (III)

wherein R⁸ is selected from the group consisting of metal ion, ammonium ion, hydrocarbyl, and heterohydrocarbyl;

X and Y are independently selected from the group consisting of oxygen and sulfur such that at least one of X and Y is sulfur;

Z is selected from the group consisting of OR⁹ and NR¹⁰R¹¹; and

R⁹, R¹⁰, and R¹¹ are independently selected from the group consisting of hydrocarbyl and heterohydrocarbyl.

2. The composition of claim 1, wherein R¹ and R² contain from 1 to 6 carbon atoms;

and R³ and R⁴ contain from 7 to 20 carbon atoms.

3. The composition of claim 1, wherein R¹ and R² contain from 1 to 5 carbon atoms;

and R³ and R⁴ contain from 7 to 15 carbon atoms.

4. The composition of claim 1, wherein R¹ and R² contain from 1 to 3 carbon atoms;

and R³ and R⁴ contain from 8 to 12 carbon atoms.

5. The composition of claim 1, wherein R¹ and R² are decyl;

and R³ and R⁴ are methyl.

6. The composition of claim 5, wherein X³¹ is a halide.

7. The composition of claim 5, wherein X³¹ is chloride.

8. The composition of claim 1, wherein R⁵ is a polyoxyalkylated alcohol of from 2 to 500 carbon atoms.

9. The composition of claim 8, wherein the polyoxyalkylated alcohol comprises an alcohol portion of from 1 to 20 carbon atoms.

10. The composition of claim 8, wherein the polyoxyalkylated alcohol comprises an alcohol portion of from 6 to 14 carbon atoms.

11. The composition of claim 8, wherein R⁶ and R⁷ are hydrogen.

12. The composition of claim 1, wherein the phosphate ester is poly(oxy-1,2-ethandiyl) tridecyl hydroxy phosphate.

13. The composition of claim 1, wherein X is sulfur.

14. The composition of claim 13, wherein Z is NR¹⁰R¹¹.

15. The composition of claim 14, wherein R¹⁰ and R¹¹ are independently hydrocarbyl groups of from 1 to 10 carbon atoms.

16. The composition of claim 14, wherein R¹⁰ and R¹¹ are independently hydrocarbyl groups of from 1 to 5 carbon atoms.

17. The composition of claim 15, wherein Y is sulfur.

18. The composition of claim 17, wherein R⁸ is a metal ion.

19. The composition of claim 1, wherein the thiocarbonyl compound is potassium dimethyl dithiocarbamate.

20. The composition of claim 1, further comprising a solvent.

21. The composition of claim 1, further comprising at least one additive selected from the group consisting of a supplemental corrosion inhibitor, a scale inhibitor, a sufactant, a biocide, a foamer, and an oxygen scavenger.

31. A method of inhibiting corrosion of iron and ferrous base materials, comprising:

contacting a material with the composition of claim 1.

32. A method of inhibiting corrosion of iron and ferrous base materials, comprising:

contacting a material with the composition of claim 31.

22. A composition, comprising:

a quaternary ammonium compound of formula (I)

wherein R¹, R², R³, R⁴ are independently a hydrocarbyl group;

a phosphate ester of formula (II);

wherein X⁻

is selected from the group consisting of halide and sulfate; and

R⁵, R⁶, and R⁷ are independently selected from the group consisting of hydrogen, a hydrocarbyl group, and a polyoxyalkylated alcohol; and

a thiocarbonyl compound of formula (III);

wherein R⁸ is selected from the group consisting of metal ion, ammonium ion, hydrocarbyl, and heterohydrocarbyl;

X and Y are selected from the group consisting of oxygen and sulfur, such that at least one of X and Y is sulfur; and

R¹⁰ and R¹¹ are independently selected from the group consisting of hydrocarbyl and heterohydrocarbyl.

23. The composition of claim 22, wherein

R¹ and R² are independently a hydrocarbyl group of from 1 to 6 carbon atoms;

R³ and R⁴ are independently a hydrocarbyl group of from 7 to 20 carbon atoms;

R⁵ is a polyoxyalkylated alcohol of from 2 to 500 carbon atoms;

R⁶ and R⁷ are independently hydrogen or a hydrocarbyl group of from 1 to 20 carbon atoms;

X is sulfur; and

R¹⁰ and R¹¹ are independently hydrocarbyl groups of from 1 to 10 carbon atoms.

24. The composition of claim 22, wherein the quaternary ammonium compound is didecyl dimethyl ammonium chloride;

the phosphate ester is poly(oxy-1,2-ethandiyl) tridecyl hydroxy phosphate; and

the thiocarbonyl compound is potassium dimethyl dithiocarbamate.

25. The composition of claim 22, further comprising a solvent.

26. The composition of claim 25, further comprising at least one additive selected from the group consisting of a supplemental corrosion inhibitor, a scale inhibitor, a sufactant, a biocide, a foamer, and an oxygen scavenger.

27. The composition of claim 26, wherein

the quaternary ammonium compound is present at 1-92% by weight;

the phosphate ester is present at 1-92% by weight;

the thiocarbonyl compound is present at 1-92% by weight;

the solvent is present at 5-95% by weight; and

the at least one additive is present at 1-92% by weight.

28. The composition of claim 26, wherein

the quaternary ammonium compound is present at 1-50% by weight;

the phosphate ester is present at 1-50% by weight;

the thiocarbonyl compound is present at 1-50% by weight;

the solvent is present at 20-80% by weight; and

the at least one additive is present at 1-50% by weight.

29. The composition of claim 26, wherein

the quaternary ammonium compound is present at 1-20% by weight;

the phosphate ester is present at 1-20% by weight;

the thiocarbonyl compound is present at 1-20% by weight;

the solvent is present at 50-75% by weight; and

the at least one additive is present at 1-20% by weight.

30. The composition of claim 26, wherein the quaternary ammonium compound, the phosphate ester, and the thiocarbonyl compound are present at a 1:

1;

1 ratio by volume.

33. A method of inhibiting corrosion of iron and ferrous base materials, comprising:

contacting a material with the composition of claim 24.

34. A method of making a corrosion inhibitor, comprising:

combining a quaternary ammonium compound of formula (I)

with a phosphate ester of formula (II)

and further with a thiocarbonyl compound of formula (III)

wherein R¹, R², R³, R⁴ are independently a hydrocarbyl group;

X⁻

is selected from the group consisting of halide and sulfate;

R⁵, R⁶, and R⁷ are independently selected from the group consisting of hydrogen, a hydrocarbyl group, and a polyoxyalkylated alcohol;

R⁸ is selected from the group consisting of metal ion, ammonium ion, hydrocarbyl, and heterohydrocarbyl;

X and Y are independently selected from the group consisting of oxygen and sulfur such that at least one of X and Y is sulfur;

Z is selected from the group consisting of OR⁹ and NR¹⁰R¹¹; and

R⁹, R¹⁰, and R¹¹ are independently selected from the group consisting of hydrocarbyl and heterohydrocarbyl.