Method of fracturing with phenothiazine stabilizer
View Patent ↗Compositions and methods of treating high temperature subterranean formations of up to about 500° F. (260° C.) are provided. The compositions and methods utilize a high molecular weight synthetic copolymer and a pH buffer than maintains a pH in a range of about 4.5 to about 5.25 for the compositions. The high molecular weight synthetic copolymer is derived from acrylamide, acrylamidomethylpropanesulfonic acid, and vinyl phosphonate.
1. A method of fracturing a subterranean formation having a temperature of from about 300° F. (149° C.) to about 500° F. (260° C.), the method comprising the step of contacting a high temperature well treatment fluid comprising water; a high molecular weight copolymer derived from acrylamide, acrylamidomethylpropanesulfonic acid, and vinyl phosphonate; a crosslinking agent; a stabilizer comprising phenothiazine or a combination of sodium thiosulfate and phenothiazine, and a pH buffer that maintains a pH of the high temperature well treatment fluid in a range of about 4.5 to about 5.25 with at least a portion of the subterranean formation at pressures sufficient to fracture the subterranean formation.
2. The method of claim 1 , wherein the pH buffer comprises acetic acid, sodium acetate, formic acid, or combinations thereof and is present in a range of about 1 gallon per 1,000 gallons high temperature well treatment fluid to about 3 gallons per 1,000 gallons high temperature well treatment fluid.
3. The method of claim 1 , wherein the high temperature well treatment fluid can be pumped at a temperature of up to about 500° F. (260° C.) for a period of up to about 2 hours.
4. The method of claim 1 , wherein the crosslinking agent is zirconium oxychloride, zirconium acetate, zirconium lactate, zirconium malate, zirconium glycolate, zirconium lactate triethanolamine, zirconium citrate, titanium lactate, titanium malate, titanium citrate, titanium, aluminum, iron, antimony, a zirconate-based compound, zirconium triethanolamine, an organozirconate, or combinations thereof.
5. The method of claim 1 , wherein the high temperature well treatment fluid comprises a breaker that allows the high temperature well treatment fluid to be broken down in a controlled manner, the breaker comprising sodium bromate, ammonium persulfate, sodium persulfate, sodium perborate, sodium percarbonate, calcium peroxide, magnesium peroxide, sodium periodate, an alkaline earth metal percarbonate, an alkaline earth metal perborate, an alkaline earth metal peroxide, an alkaline earth metal perphosphate, a zinc peroxide, a zinc perphosphate, a zinc perborate, a zinc percarbonate, a boron compound, a perborate, a peroxide, a perphosphate, or combinations thereof.
6. A method of fracturing a subterranean formation having a temperature of from about 300° F. (149° C.) to about 500° F. (260° C.), the method comprising: contacting water with a high molecular weight copolymer derived from acrylamide, acrylamidomethylpropanesulfonic acid, and vinyl phosphonate to form a water-soluble polymer, contacting the water-soluble polymer with a crosslinking agent, a stabilizer comprising phenothiazine or a combination of sodium thiosulfate and phenothiazine, and a pH buffer to produce a gelling fluid; and contacting at least a portion of the subterranean formation with the gelling fluid at pressures sufficient to fracture the formation, the pH buffer maintaining a pH of the gelling fluid in a range of about 4.5 to about of about 5.25.
7. The method of claim 6 , wherein the high molecular weight copolymer is present in a range of about 10 gallons per 1,000 gallons gelling fluid to about 25 gallons per 1,000 gallons gelling fluid.
8. The method of claim 6 , further comprising a crosslinking agent selected from the group consisting of zirconium oxychloride, zirconium acetate, zirconium lactate, zirconium malate, zirconium glycolate, zirconium lactate triethanolamine, zirconium citrate, titanium lactate, titanium malate, titanium citrate, titanium, aluminum, iron, antimony, a zirconate-based compound, zirconium triethanolamine, an organozirconate, and combinations thereof.
9. The method of claim 6 , wherein the high gelling fluid comprises a breaker that allows the gelling fluid to be broken down in a controlled manner, the breaker comprising sodium bromate, ammonium persulate, sodium persulfate, sodium perborate, sodium percarbonate, calcium peroxide, magnesium peroxide, sodium periodate, an alkaline earth metal percarbonate, an alkaline earth metal perborate, an alkaline earth metal peroxide, an alkaline earth metal perphosphate, a zinc peroxide, a zinc perphosphate, a zinc perborate, a zinc percarbonate, a boron compound, a perborate, a peroxide, a perphosphate, or combinations thereof and wherein the gelling fluid further comprises a surfactant selected from the group consisting of alkoxypoly(ethyleneoxy)ethanol, an ethoxylated alcohol having from 10 to 18 carbon molecules, and combinations thereof.
10. The method of claim 6 , wherein the gelling fluid can be pumped at a temperature of up to about 500° F. (260° C.) for a period of up to about 2 hours.
11. The method of claim 1 , wherein the high molecular weight copolymer has a K-value of greater than about 375.
12. The method of claim 1 , wherein the high molecular weight copolymer is present in a range of about 10 gallons per 1,000 gallons high temperature well treatment fluid to about 25 gallons per 1,000 gallons high temperature well treatment fluid.
13. The method of claim 1 , wherein the high molecular weight copolymer further comprises a monomer selected from the group consisting of an alkali metal of acrylamidomethylpropanesulfonic acid, an ammonium salt of acrylamidomethylpropanesulfonic acid, styrene sulfonate, vinyl sulfonate, N-vinylpyrolidone, N-vinylformamide, N-vinylacetamide, N,N-diallylacetamide, methacrylamide, acrylamide, N,N-dimethylacrylamide, methacrylamide, a divalent cation from calcium salt, a divalent cation from magnesium salt, and combinations thereof.
14. The method of claim 1 , wherein the high temperature well treatment fluid further comprises a surfactant selected from the group consisting of alkoxypoly(ethyleneoxy)ethanol, an ethoxylated alcohol having from 10 to 18 carbon molecules, and combinations thereof.
15. The method of claim 5 , wherein the breaker is sodium bromate, ammonium persulate, sodium persulfate, sodium perborate, sodium percarbonate, calcium peroxide, magnesium peroxide, sodium periodate, or combinations thereof.
16. The method of claim 6 , wherein the high molecular weight copolymer has a K-value of greater than about 375.
17. The method of claim 6 , wherein the pH buffer comprises acetic acid, sodium acetate, formic acid, or combinations thereof and is present in a range of about 1 gallon per 1,000 gallons gelling fluid to about 3 gallons per 1,000 gallons gelling fluid.
18. The method of claim 6 , wherein the high molecular weight copolymer further comprises a monomer selected from the group consisting of an alkali metal of acrylamidomethylpropanesulfonic acid, an ammonium salt of acrylamidomethylpropanesulfonic acid, styrene sulfonate, vinyl sulfonate, N-vinylpyrolidone, N-vinylformamide, N-vinylacetamide, N,N-diallylacetamide, methacrylamide, acrylamide, N,N-dimethylacrylamide, methacrylamide, a divalent cation from calcium salt, a divalent cation from magnesium salt, and combinations thereof.
19. The method of claim 6 , wherein the gelling fluid further comprises a surfactant selected from the group consisting of alkoxypoly(ethyleneoxy)ethanol, an ethoxylated alcohol having from 10 to 18 carbon molecules, and combinations thereof.
20. The method of claim 9 , wherein the breaker is sodium bromate, ammonium persulate, sodium persulfate, sodium perborate, sodium percarbonate, calcium peroxide, magnesium peroxide, sodium periodate, or combinations thereof.