Method of pumping aqueous fluid containing surface modifying treatment agent into a well

• US 9,701,892 B2
• Filed: 03/10/2015
• Issued: 07/11/2017
• Est. Priority Date: 04/17/2014
• Status: Active Grant

• Current Assignee: Baker Hughes Holdings LLC (Baker Hughes Company)
• Original Assignee: Baker Hughes Incorporated (Baker Hughes Company)
• Inventors: Monroe, Terry D., Bhaduri, Sumit, Qu, Qi
• Primary Examiner(s): RUNYAN, SILVANA C
• Application Number:
  US14/643,245
• Publication Number:
  US 20150299561A1
• Time in Patent Office: 854 Days
• Field of Search: 1663051, 166300, 16625001, 166 901
• CPC Class Codes: C09K 2208/28 Friction or drag reducing additives
• CPC Class Codes: C09K 8/584 characterised by the use of specific surfactants
• CPC Class Codes: C09K 8/602 containing surfactants
• CPC Class Codes: C09K 8/68 containing organic compounds
• CPC Class Codes: C09K 8/72 Eroding chemicals, e.g. acids
• CPC Class Codes: C09K 8/74 combined with additives added for specific purposes
• CPC Class Codes: C09K 8/86 containing organic compounds
• CPC Class Codes: E21B 37/06 using chemical means for preventing or limiting , e.g. eliminating, the deposition of paraffins or like substances
• CPC Class Codes: E21B 43/16 Enhanced recovery methods for obtaining hydrocarbons
• CPC Class Codes: E21B 43/20 Displacing by water
• CPC Class Codes: E21B 43/24 using heat, e.g. steam injection
• CPC Class Codes: E21B 43/25 Methods for stimulating production by vibrating earth formations E21B43/003
• CPC Class Codes: E21B 43/27 by use of eroding chemicals, e.g. acids

Abstract

A well treatment fluid contains a surface modifying treatment agent having an anchor and a hydrophobic tail. The surface modifying treatment agent is an organophosphorus acid derivative. After the well treatment fluid is pumped into a well penetrating the subterranean formation, the anchor binds to the surface of the formation. The subterranean formation is a siliceous formation or a metal oxide-containing subterranean formation. The anchor bonds to a Si atom when the formation is a siliceous formation and to the metal of the metal oxide when the formation is a metal oxide-containing formation. After being bound to the surface of the formation, frictional drag within the well is reduced. This allows for faster recovery of formation fluids. The bonding of the surface modifying treatment agent onto the formation may further be enhanced by first pre-treating the formation with an aqueous fluid. By increasing the number of sites for the surface modifying treatment agent to bind onto the surface of the subterranean formation, productivity is improved.

Claims

1. A method of treating a siliceous subterranean formation penetrated by a well comprising:

(a) preparing an aqueous treatment fluid comprising;

(i) a surface modifying treatment agent having an anchor and a hydrophobic tail wherein the hydrophobic tail is attached to the anchor; and

(ii) an aqueous media comprising an organic acid;

(b) pumping the aqueous treatment fluid into a well penetrating the subterranean formation; and

(c) binding the surface modifying treatment agent to a surface of the subterranean formation by attaching the anchor to the formation.

2. The method of claim 1, wherein the organic acid of the aqueous media is selected from the group consisting of acetic acid, formic acid, citric acid, oxalic acid, malonic acid, succinic acid, malic acid, tartaric acid, phthalic acid ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, glycolic acid, N-hydroxyethyl-N, N′

, N′

-ethylenediaminetriacetic acid, hydroxyethyliminodiacetic acid, diethylenetriaminepentaacetic acid, cyclohexylenediaminetetraacetic acid and mixtures thereof.

3. The method of claim 2, wherein the organic acid of the aqueous media is selected from the group consisting of acetic acid, formic acid, citric acid and mixtures thereof.

4. The method of claim 1, wherein the amount of organic acid in the aqueous media is between from about 0.5 to about 25 volume percent.

5. The method of claim 1, wherein the aqueous treatment fluid is prepared on the fly.

6. The method of claim 1, wherein the anchor of the surface modifying treatment agent originates from an organophosphoric acid, organophosphonic acid or an organophosphinic acid.

7. The method of claim 6, wherein the organophosphorus acid derivative is at least one member selected from the group consisting of:

(a) a derivative of a phosphoric acid having the structure (RO)_x—

P(O)—

(OR′

)_y;

(b) a derivative of a phosphonic acid of the structure;

8. The method of claim 6, wherein the organophosphoric acid, organophosphonic acid or organophosphinic acid is selected from the group consisting of amino trismethylene phosphonic acid, aminobenzylphosphonic acid, 3-amino propyl phosphonic acid, O-aminophenyl phosphonic acid, 4-methoxyphenyl phosphonic acid, aminophenylphosphonic acid, aminophosphonobutyric acid, aminopropylphosphonic acid, benzhydrylphosphonic acid, benzylphosphonic acid, butylphosphonic acid, carboxyethylphosphonic acid, diphenylphosphinic acid, dodecylphosphonic acid, ethylidenediphosphonic acid, heptadecylphosphonic acid, methylbenzylphosphonic acid, naphthylmethylphosphonic acid, octadecylphosphonic acid, octylphosphonic acid, pentylphosphonic acid, phenylphosphinic acid, phenylphosphonic acid, bis-(perfluoroheptyl) phosphinic acid, perfluorohexyl phosphonic acid, styrene phosphonic acid, and dodecyl bis-1,12-phosphonic acid.

9. The method of claim 1, wherein either (a) the anchor is a metal and the hydrophobic tail is an organo-silicon material, a fluorinated hydrocarbon or both an organo-silicon material and a fluorinated hydrocarbon;

or (b) the anchor is an organophosphorus acid derivative and the hydrophobic group is attached thereto.

10. The method of claim 9, wherein the surface modifying treatment agent is of the formula:

R_f—

(CH₂)_p—

Z

wherein;

R_f is a perfluorinated alkyl group or a perfluorinated alkylene ether group;

p is 2 to 4; and

Z is selected from the group consisting of;

11. The method of claim 10, wherein R″

is aliphatic or aromatic substituent substituted with a perfluorinated alkyl group or a perfluorinated alkylene ether group.

12. The method of claim 11, wherein the perfluoroalkylene ether group of R_f is of the structure:

13. The method of claim 10, wherein the perfluorinated alkyl group is of the structure:

14. The method of claim 10, wherein the surface modifying treatment agent is selected from the group consisting of CF₃(C_nF_2n)CH₂CH₂PO₃H₂ where n is between 3 and 5, and CF₃(CF₂)_xO(CF₂CF₂)_y—

CH₂CH₂—

PO₃H₂ where x is from 0 to 7, y is from 1 to 20 and x+y is less than or equal to 27.

15. The method of claim 10, wherein R or R′

contains a terminal or omega functional groups.

16. The method of claim 15, wherein the terminal or omega functional group is selected from the group consisting of carboxyl, hydroxyl, amino, imino, amido, thio, cyano, sulfonate, carbonate, phosphonic acid or a mixture thereof.

17. The method of claim 9, wherein the anchor is a metal and the hydrophobic tail is an organo-silicon material, a fluorinated hydrocarbon or both an organo-silicon material and a fluorinated hydrocarbon.

18. The method of claim 17, wherein the hydrophobic organo-silicon material is of the formula

R¹_4-xSiA_x

wherein R¹ is a fluoro-substituted hydrocarbon and A is OR².

21. The method of claim 17, wherein the hydrophobic organo-silicon material has a formula selected from:

R¹_4-xSiA_x and (R¹₃Si)_yB

or an organo(poly)siloxane or organo(poly)silazane of the formula;

22. The method of claim 21, wherein R¹ is of the structure:

23. The method of claim 17, wherein the fluorinated hydrocarbon is of the structure:

24. The method of claim 17, wherein the fluorinated hydrocarbon is of the structure:

25. The method of claim 17, wherein the hydrophobic organo-silicon material is an organo(poly)siloxane or an organo(poly)silazane.

26. The method of claim 25, wherein the organo(poly)siloxane or an organo(poly)silazane have units of the formula:

27. The method of claim 17, wherein the hydrophobic organo-silicon material contains additional units of the formula:

R⁵₂SiO₂ where R⁵ is halogen.

19. The method of 17, wherein the metal of the anchor is a Group 3, 4, 5, or 6 metal.

20. The method of claim 19, wherein the metal of the surface modifying treatment agent is selected from the group consisting of Ti, Zr, La, Hf, Ta, W and Nb.