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

Patent metadata

Field	Value
Publication number	US-9701892-B2
Application number	US-201514643245-A
Country	US
Kind code	B2
Filing date	Mar 10, 2015
Priority date	Apr 17, 2014
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

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.

First claim

What is claimed is:

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:

 and
(c) a derivative of a phosphinic acid of the structure:

wherein:
R and R″ are each independently a radical having a total of 1 to 30 carbon atoms; R′ is H, a metal or a lower alkyl having from 1 to 4 carbon atoms;
x is 1 to 2; y is 1 to 2; x+y=3;
a is 0-1;
b is 1;
c is 1-2;
a+b+c is 3;
d is 0-2;
e is 0-2;
f is 1; and
d+e+f.

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 —(CH 2 ) 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:

wherein R and R″ are a hydrocarbon or substituted hydrocarbon radical having up to 200 carbon atom or a perfluoroalkyl group, and R′ is H, a metal, an amine or an aliphatic or aryl radical aryl.

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:

where A is an oxygen radical or a chemical bond; n is 1 to 20; Y is H, F, C n H 2+1 or C n F 2n+1 ; b is at least 1; m is 0 to 50; p is 1 to 20; and X is H, F or an acid group or an acid derivative.

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

where Y is F or C n F 2n+1 and m is 4 to 20.

14. The method of claim 10 , wherein the surface modifying treatment agent is selected from the group consisting of CF 3 (C n F 2n )CH 2 CH 2 PO 3 H 2 where n is between 3 and 5, and CF 3 (CF 2 ) x O(CF 2 CF 2 ) y —CH 2 CH 2 —PO 3 H 2 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
R 1 4-x SiA x

wherein R 1 is a fluoro-substituted hydrocarbon and A is OR 2 .

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.

21. The method of claim 17 , wherein the hydrophobic organo-silicon material has a formula selected from:
R 1 4-x SiA x and (R 1 3 Si) y B

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

where:
R 1 are identical or different and are a hydrocarbon or substituted hydrocarbon radical containing from 1 to 100 carbon atoms;
A is hydrogen, halogen, OH, OR 2 or

B is NR 3 3-y ;
R 2 is a hydrocarbon or substituted hydrocarbon radical containing from 1 to 12 carbon atoms;
R 3 is hydrogen or R 1 ;
x is 1, 2 or 3; and
y is 1 or 2.

22. The method of claim 21 , wherein R 1 is of the structure:

where Y is F or C n F 2n+1 ; m is 4 to 20 and n is 1 to 6; R 2

Assignees

• Baker Hughes Inc

Inventors

• Monroe Terry D
• Bhaduri Sumit
• Qu Qi

Classifications

• E21B43/26

  by forming crevices or fractures · CPC title

• C09K8/584 Primary

  characterised by the use of specific surfactants · CPC title

• E21B43/16 Primary

  Enhanced recovery methods for obtaining hydrocarbons · CPC title

• C09K8/74

  combined with additives added for specific purposes · CPC title

• C09K2208/28

  Friction or drag reducing additives · CPC title