Fracturing method using polyboronic compound

Patent metadata

Field	Value
Publication number	US-9534167-B2
Application number	US-201313736799-A
Country	US
Kind code	B2
Filing date	Jan 8, 2013
Priority date	Oct 21, 2008
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

Polyboronic compounds useful as delayed crosslinking agents may be produced by using a polyamine as base scaffold and incorporating boron via reaction with intermediate borates which may be formed in the condensation reaction between boric acid and a diol. A di-aldehyde, such as glyoxal, may be introduced following caustic treatment of the reaction mixture of polyaminoboronate to form the polyboronic compound.

First claim

What is claimed is:

1. A method of fracturing a subterranean formation comprising the steps of:
a. blending together water and a hydratable polymer capable of gelling in the presence of a crosslinking agent;
b. allowing the hydratable polymer to hydrate to form a hydrated polymer solution; and
c. adding a crosslinking agent comprising a polyboronic compound to the hydrated polymer solution to produce a crosslinked fracturing fluid,
wherein the polyboronic compound is of the formula:
W—NH—(CH 2 ) r -[N(R 9 )—(CH 2 ) r ] s —NH—W  (I)

wherein:
s is 1 to 6;
each R 9 is independently selected from the group consisting of —W or —(CH 2 ) r —NH—W;
each r is independently selected from 2 to 6;
W is a substituent of the formula:

v is either 2 or 3, provided v cannot be both 2 and 3 in the same compound;
each R 10 is independently selected from either —H or R 12 and each R 11 is independently selected from either —H or —OH, provided that R 10 and R 11 in at least one W substituent group is R 12 and —OH, respectively;
each R 12 is independently selected from the group consisting of a linear or branched C 1 -C 6 alkyl or alkenyl group, optionally substituted with —X or —OR 13 ;
X is —Cl or —Br; and
R 13 is a C 1 -C 6 alkyl group; and
d. pumping the fluid into the subterranean formation to fracture the formation.

2. The method of claim 1 , wherein at least two of the W substituent groups of the polyboronic compound are of the formula (II).

3. The method of claim 1 , wherein s is 2 or more.

4. The method of claim 3 , wherein the number of W substituent groups being of formula (II) is from 1 to 4.

5. The method of claim 1 , wherein R 9 is —(CH 2 ) r —NH—W, each r is 2, s is and v is 2.

6. The method of claim 1 , wherein the polyboronic compound is of the formula:

7. The method of claim 1 , wherein the polyboronic compound is prepared by:
(i) forming a polyaminoboronate by contacting a cyclic borate ester with a polymeric amine of the formula H 2 N—(CH 2 ) r -[NH—(CH 2 ) r ] s —NH, wherein r is 2 to 6 and s is 1 to 6 and further wherein the cyclic borate ester is of the formula:

wherein R 14 is the alkyl chain of a alcohol having a boiling point greater than water residue; and
(ii) reacting the polyaminoboronate with a di-aldehyde or di-ketone in caustic to produce the polyboronic compound.

8. The method of claim 7 , wherein the polymeric amine comprises ethylenediamine, diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), 1,2-, 1,3-propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, ethylene propylene triamine, ethylene dipropylene tetramine, diethylene propylene tetramine, ethylene tripropylene pentamine, diethylene dipropylene pentamine, triethylene propylene pentamine, or combinations thereof.

9. The method of claim 1 , wherein the polyboronic compound is prepared by:
(a) contacting a polymeric amine with a cyclic borate ester to form a polyaminoboronate, wherein the cyclic borate ester is of the formula:

wherein R 14 is the alkyl chain of an alcohol having a boiling point greater than water residue; and wherein the polymeric amine comprises ethylenediamine, diethylene triamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), 1,2-, 1,3-propylenediamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, ethylene propylene triamine, ethylene dipropylene tetramine, diethylene propylene tetramine, ethylene tripropylene pentamine, diethylene dipropylene pentamine, triethylene propylene pentamine, or combinations thereof, and
(b) reacting the polyaminoboronate with a di-aldehyde or diketone in the presence of caustic to render the polyboronic compound of formula (I).

10. The method of claim 9 , wherein the cyclic borate ester is prepared by reacting boric acid and a diol in the presence of an alcohol, ROH, having a boiling point higher than the boiling point of water.

11. A method of fracturing a subterranean formation comprising the steps of:
a. crosslinking a fracturing fluid comprising a hydratable polymer by contacting the fracturing fluid with a polyboronic compound to produce a crosslinked fracturing fluid, wherein the polyboronic compound is of the formula:
W—NH—(CH 2 ) r -[N(R 9 )—(CH 2 ) r ] s —NH—W  (I)

wherein:
s is 1 to 6;
each R 9 is independently selected from the group consisting of —W or —(CH 2 ) r —NH—W;
each r is independently selected from 2 to 6;
W is a substituent of the formula:

v is either 2 or 3, provided v cannot be both 2 and 3 in the same compound;

each R 10 is independently selected from either —H or R 12 and each R 11 is independently selected from either —H or —OH, provided that R 10 and R 11 in at least one W substituent group is R 12 and —OH, respectively;
each R 12 is independently selected from the group consisting of a linear or branched C 1 -C 6 alkyl or alkenyl group, optionally substituted with —X or —OR 13 ;
X is —Cl or —Br; and
R 13 is a C 1 -C 6 alkyl group; and
b. injecting the crosslinked fracturing fluid into the subterranean formation to fracture the formation.

12. The method of claim 11 , wherein at least two of the W substituent groups are of the formula (II).

13. The method of claim 11 , wherein s is 2 or more.

14. The method of claim 13 , wherein the number of W substituent groups being of formula (II) is from 1 to 4.

15. The method of claim 11 , wherein R 9 is —(CH 2 ) r —NH—W, each r is 2, s is and v is 2.

16. The method of claim 15 , wherein the polyboronic compound is of the formula:

17. The method of claim 1 , wherein the hydratable polymer is selected from the group consisting of guar gum, a guar gum derivative, locust bean gum, karaya gum, a cellulosic derivative or a mixture.

18. The method of claim 17 , wherein the hydratable polymer is guar gum or a guar gum derivative or a mixture thereof.

19. The method of claim 11 , wherein the hydratable polymer is guar gum, carboxymethyl guar, hydroxypropyl guar, carboxymethyl hydroxypropyl guar or a mixture thereof.

20. A method of fracturing a subterranean formation comprising pumping into the formation at a pressure sufficient to fracture the formation a fracturing fluid having a critical crosslinking concentration, C cc , less than about 15.5 ppt and prepared from:
(i) a hydratable polymer selected from guar gum, derivatized guar or a mixture thereof; and
(ii) a polyboronic compound of the formula:
W—NH—(CH 2 ) r -[N(R 9 )—(CH 2 ) r ] s —NH—W  (I)

wherein:
s is 1 to 6;
ach R 9 is independently selected from the group consisting of —W or —(CH 2 ) r —NH—W;
each r is independently selected from 2 to 6;
W is a substituent of the formula:

Assignees

• Baker Hughes Inc

Inventors

• Legemah Magnus
• Sun Hong
• Guerin Michael

Classifications

• E21B43/26

  by forming crevices or fractures · CPC title

• C09K8/685 Primary

  containing cross-linking agents · CPC title

• C07F5/02

  Boron compounds · CPC title

• C07F5/025 Primary

  Boronic and borinic acid compounds · CPC title