US4304676A
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Methods and compositions for dissolving silicates in subterranean formations
Assignee: Halliburton Co
•
Filing: 1980-03-11
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Granted: 1981-12-08
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Expires: 2000-03-11
Abstract
Abstract Hydrofluoric acid compositions and methods for dissolving siliceous materials in subterranean formations to stimulate the production of fluids therefrom are provided. The presence of aluminum in the compositions retards the reaction rates thereof to thereby enable deeper penetration of formations by the acid compositions.
Inventors
- 👤 Bobby E. Hall
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 21:15
CPC Classifications
C; C09; C09K; C09K8/00; C09K8/60; C09K8/62; C09K8/72; C09K8/74; Y; Y10; Y10S; Y10S507/00; Y10S507/933
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
127 words
An aqueous acid composition for dissolving siliceous materials said composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound, soluble in said mineral acid, which upon dissolution in said mineral acid produces aluminum III ions, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions of from about 1 to 1 to about 6 to 1.
Claim 2
Dependent Claim
127 words
An aqueous acid composition for dissolving siliceous materials said composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound, soluble in said mineral acid, which upon dissolution in said mineral acid produces aluminum III ions, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions of from about 1 to 1 to about 6 to 1.
Claim 3
Dependent Claim
66 words
The acid composition of claim 1 wherein said aluminum compound is represented by the general formula (Al.sup.+3).sub.n (M.sup.+1).sub.z (X.sup.-a).sub.m the hydrates of such compounds and mixtures thereof wherein: X is selected from the group consisting of anions derived from mineral acids, anions derived from organic acids, an hydroxyl group and mixtures thereof; M is selected from hydrogen and ammonium; z is 0 or 1; and 3n+z=am.
Claim 4
Dependent Claim
26 words
The acid composition of claim 1 wherein X is selected from the group consisting of hydroxyl, sulfate, phosphate, nitrate, chloride, bromide, fluoride, formate, acetate and citrate.
Claim 5
Dependent Claim
144 words
An aqueous acid composition for dissolving siliceous materials said composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound soluble in said mineral acid which produces aluminum III ions upon dissolution in said mineral acid, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration in the range of from about 0.05 to about 6 gram-moles of fluoride ion per liter of solution and said aluminum compound is present in said composition in an amount sufficient to produce an ion concentration molar ratio of said fluoride ions to said aluminum III ions in the range of from about 1 to 1 to about 6 to 1.
Claim 6
Dependent Claim
144 words
An aqueous acid composition for dissolving siliceous materials said composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound soluble in said mineral acid which produces aluminum III ions upon dissolution in said mineral acid, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration in the range of from about 0.05 to about 6 gram-moles of fluoride ion per liter of solution and said aluminum compound is present in said composition in an amount sufficient to produce an ion concentration molar ratio of said fluoride ions to said aluminum III ions in the range of from about 1 to 1 to about 6 to 1.
Claim 7
Dependent Claim
48 words
The acid composition of claim 4 wherein said aluminum compound is selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, and mixtures thereof, the hydrates of such salts and mixtures of such salts and hydrates.
Claim 8
Dependent Claim
35 words
The acid composition of claim 5 wherein said fluoride compound is selected from the group consisting of ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 F·HF), hydrogen fluoride (HF), aluminum fluoride and mixtures thereof.
Claim 9
Dependent Claim
26 words
The acid composition of claim 6 wherein said mineral acid is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and mixtures thereof.
Claim 10
Dependent Claim
49 words
The acid composition of claim 7 wherein said fluoride ion concentration is in the range of from about 0.25 to about 3 gram-moles of fluoride ion per liter and said ion concentration molar ratio is in the range of from about 2 to 1 to about 5 to 1.
Claim 11
Dependent Claim
31 words
The acid composition of claim 8 wherein said mineral acid is present in an amount in the range of from about 0.1 to about 30 percent by weight of said composition.
Claim 12
Dependent Claim
17 words
The acid composition of claim 9 wherein said fluoride compound and said aluminum compound is aluminum fluoride.
Claim 13
Dependent Claim
50 words
The acid composition of claim 9 wherein said fluoride ion concentration is in the range of from about 0.5 to about 1.5 gram-moles of fluoride ion per liter and said mineral acid is present in an amount in the range of from about 5 to about 20 percent by weight.
Claim 14
Dependent Claim
125 words
An acid composition for dissolving siliceous material comprised of water; hydrofluoric acid; a mineral acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and mixtures thereof present in said composition in an amount in the range of from about 0.1 to about 30 percent by weight; an aluminum compound selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, the hydrates thereof and mixtures thereof; wherein the fluoride ion concentration is in the range of from about 0.05 to about 6 gram-moles per liter and the ion concentration molar ratio of said fluoride ion to aluminum ion is in the range of 1 to 1 to 6 to 1.
Claim 15
Dependent Claim
125 words
An acid composition for dissolving siliceous material comprised of water; hydrofluoric acid; a mineral acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and mixtures thereof present in said composition in an amount in the range of from about 0.1 to about 30 percent by weight; an aluminum compound selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, the hydrates thereof and mixtures thereof; wherein the fluoride ion concentration is in the range of from about 0.05 to about 6 gram-moles per liter and the ion concentration molar ratio of said fluoride ion to aluminum ion is in the range of 1 to 1 to 6 to 1.
Claim 16
Dependent Claim
58 words
The acid composition of claim 12 wherein said mineral acid is hydrochloric acid and said aluminum compound is aluminum chloride hydrate and wherein said mineral acid is present in an amount of about 15 percent by weight, said fluoride ion concentration is about 0.75 gram-moles per liter and said ion concentration molar ratio is about 4 to 1.
Claim 17
Independent Claim
127 words
A method of retarding the reaction rate of an aqueous acid composition said composition having a pH value of no more than 2 and containing a mineral acid and hydrofluoric acid with a siliceous material comprising adding to said aqueous acid composition an aluminum compound soluble in said mineral acid to produce aluminum III ions prior to reacting said composition with said siliceous material, wherein said hydrofluoric acid is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions of from about 1 to 1 to about 6 to 1.
Claim 18
Independent Claim
127 words
A method of retarding the reaction rate of an aqueous acid composition said composition having a pH value of no more than 2 and containing a mineral acid and hydrofluoric acid with a siliceous material comprising adding to said aqueous acid composition an aluminum compound soluble in said mineral acid to produce aluminum III ions prior to reacting said composition with said siliceous material, wherein said hydrofluoric acid is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions of from about 1 to 1 to about 6 to 1.
Claim 19
Dependent Claim
47 words
The method of claim 14 wherein said aluminum compound is selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, and mixtures thereof, the hydrates of such salts and mixtures of such salts and hydrates.
Claim 20
Independent Claim
144 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound, soluble in said mineral acid, which upon dissolution in said mineral acid produces aluminum III ions, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions of from about 1 to 1 to about 6 to 1.
Claim 21
Independent Claim
144 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound, soluble in said mineral acid, which upon dissolution in said mineral acid produces aluminum III ions, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions of from about 1 to 1 to about 6 to 1.
Claim 22
Dependent Claim
65 words
The method of claim 16 wherein said aluminum compound is represented by the general formula (Al.sup.+3).sub.n (M.sup.+1).sub.z (X.sup.-a).sub.m the hydrates of such compounds and mixtures thereof wherein: X is selected from the group consisting of anions derived from mineral acids, anions derived from organic acids, an hydroxyl group and mixtures thereof; M is selected from hydrogen and ammonium; z is 0 or 1; and 3n+z=am.
Claim 23
Dependent Claim
25 words
The method of claim 17 wherein X is selected from the group consisting of hydroxyl, sulfate, phosphate, nitrate, chloride, bromide, fluoride, formate, acetate and citrate.
Claim 24
Independent Claim
145 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition comprised of water; hydrofluoric acid; a mineral acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and mixtures thereof present in said composition in an amount in the range of from about 0.1 to about 30 percent by weight; an aluminum compound selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, the hydrates thereof and mixtures thereof; wherein the fluoride ion concentration is in the range of from about 0.05 to about 6 gram-moles per liter and the ion concentration molar ratio of said fluoride ion to aluminum ion is in the range of 1 to 1 to 6 to 1.
Claim 25
Independent Claim
145 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition comprised of water; hydrofluoric acid; a mineral acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and mixtures thereof present in said composition in an amount in the range of from about 0.1 to about 30 percent by weight; an aluminum compound selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, the hydrates thereof and mixtures thereof; wherein the fluoride ion concentration is in the range of from about 0.05 to about 6 gram-moles per liter and the ion concentration molar ratio of said fluoride ion to aluminum ion is in the range of 1 to 1 to 6 to 1.
Claim 26
Dependent Claim
57 words
The method of claim 19 wherein said mineral acid is hydrochloric acid and said aluminum compound is aluminum chloride hydrate and wherein said mineral acid is present in an amount of about 15 percent by weight, said fluoride ion concentration is about 0.75 gram-moles per liter and said ion concentration molar ratio is about 4 to 1.
Claim 27
Independent Claim
161 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound soluble in said mineral acid which produces aluminum III ions upon dissolution in said mineral acid, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration in the range of from about 0.05 to about 6 gram-moles of fluoride ion per liter of solution and said aluminum compound is present in said composition in an amount sufficient to produce an ion concentration molar ratio of said fluoride ions to said aluminum III ions in the range of from about 1 to 1 to about 6 to 1.
Claim 28
Independent Claim
161 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound soluble in said mineral acid which produces aluminum III ions upon dissolution in said mineral acid, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration in the range of from about 0.05 to about 6 gram-moles of fluoride ion per liter of solution and said aluminum compound is present in said composition in an amount sufficient to produce an ion concentration molar ratio of said fluoride ions to said aluminum III ions in the range of from about 1 to 1 to about 6 to 1.
Claim 29
Dependent Claim
47 words
The method of claim 21 wherein said aluminum compound is selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, and mixtures thereof, the hydrates of such salts and mixtures of such salts and hydrates.
Claim 30
Dependent Claim
34 words
The method of claim 22 wherein said fluoride compound is selected from the group consisting of ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 F.HF), hydrogen fluoride (HF), aluminum fluoride and mixtures thereof.
Claim 31
Dependent Claim
25 words
The method of claim 23 wherein said mineral acid is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and mixtures thereof.
Claim 32
Dependent Claim
48 words
The method of claim 24 wherein said fluoride ion concentration is in the range of from about 0.25 to about 3 gram-moles of fluoride ion per liter and said ion concentration molar ratio is in the range of from about 2 to 1 to about 5 to 1.
Claim 33
Dependent Claim
30 words
The method of claim 25 wherein said mineral acid is present in an amount in the range of from about 0.1 to about 30 percent by weight of said composition.
Claim 34
Dependent Claim
16 words
The method of claim 26 wherein said fluoride compound and said aluminum compound is aluminum fluoride.
Claim 35
Dependent Claim
49 words
The method of claim 26 wherein said fluoride ion concentration is in the range of from about 0.5 to about 1.5 gram-moles of fluoride ion per liter and said mineral acid is present in an amount in the range of from about 5 to about 20 percent by weight.
Claim 36
Independent Claim
173 words
The method of retarding the reaction rate of an aqueous acid composition with a siliceous material said composition having a pH value of no more than 2 and containing a mineral acid and hydrofluoric acid comprising adding to said aqueous acid composition an aluminum compound soluble in said mineral acid to produce aluminum III ions prior to reacting said composition with said siliceous material, wherein said hydrofluoric acid is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions greater than 6 to 1 whereby said fluoride ion concentration is reduced by spending hydrofluoric acid by an amount sufficient to produce a molar ratio of no more than 6 to 1 at which point retardation commences and continues until the molar ratio of said fluoride ions to said aluminum III ions is about 1 to 1.
Claim 37
Independent Claim
173 words
The method of retarding the reaction rate of an aqueous acid composition with a siliceous material said composition having a pH value of no more than 2 and containing a mineral acid and hydrofluoric acid comprising adding to said aqueous acid composition an aluminum compound soluble in said mineral acid to produce aluminum III ions prior to reacting said composition with said siliceous material, wherein said hydrofluoric acid is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said aluminum compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions greater than 6 to 1 whereby said fluoride ion concentration is reduced by spending hydrofluoric acid by an amount sufficient to produce a molar ratio of no more than 6 to 1 at which point retardation commences and continues until the molar ratio of said fluoride ions to said aluminum III ions is about 1 to 1.
Claim 38
Dependent Claim
47 words
The method of claim 29 wherein said aluminum compound is selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, and mixtures thereof, the hydrates of such salts and mixtures of such salts and hydrates.
Claim 39
Dependent Claim
34 words
The method of claim 29 wherein said fluoride compound is selected from the group consisting of ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 F.HF), hydrogen fluoride (HF), aluminum fluoride and mixtures thereof.
Claim 40
Dependent Claim
25 words
The method of claim 29 wherein said mineral acid is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and mixtures thereof.
Claim 41
Dependent Claim
30 words
The method of claim 32 wherein said mineral acid is present in an amount in the range of from about 0.1 to about 30 percent by weight of said composition.
Claim 42
Dependent Claim
65 words
The method of claim 29 wherein said aluminum compound is represented by the general formula (Al.sup.+3).sub.n (M.sup.+1).sub.z (X.sup.-a).sub.m the hydrates of such compounds and mixtures thereof wherein: X is selected from the group consisting of anions derived from mineral acids, anions derived from organic acids, an hydroxyl group and mixtures thereof; M is selected from hydrogen and ammonium; Z is 0 or 1; and 3n+z=am.
Claim 43
Independent Claim
189 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound, soluble in said mineral acid, which upon dissolution in said mineral acid produces aluminum III ions, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions greater than 6 to 1 whereby said fluoride ion concentration is reduced by spending hydrofluoric acid by an amount sufficient to produce a molar ratio of no more than 6 to 1 at which point retardation commences and continues until the molar ratio of said fluoride ions to said aluminum III ions is about 1 to 1.
Claim 44
Independent Claim
189 words
A method of acidizing a subterranean formation containing siliceous materials to stimulate the production of desired fluids therefrom comprising contacting said formation with an aqueous acid composition having a pH value of no more than 2 and being comprised of at least one mineral acid, at least one fluoride compound which is a source of hydrofluoric acid in said mineral acid, and an aluminum compound, soluble in said mineral acid, which upon dissolution in said mineral acid produces aluminum III ions, wherein said fluoride compound is present in said composition in an amount sufficient to produce a fluoride ion concentration of at least 0.05 gram-moles of fluoride per liter of solution and said compound is present in said composition to produce a molar ratio of fluoride ions to said aluminum III ions greater than 6 to 1 whereby said fluoride ion concentration is reduced by spending hydrofluoric acid by an amount sufficient to produce a molar ratio of no more than 6 to 1 at which point retardation commences and continues until the molar ratio of said fluoride ions to said aluminum III ions is about 1 to 1.
Claim 45
Dependent Claim
47 words
The method of claim 35 wherein said aluminum compound is selected from the group consisting of aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum hydroxide, aluminum ammonium sulfate, aluminum ammonium chloride, aluminum fluoride, and mixtures thereof, the hydrates of such salts and mixtures of such salts and hydrates.
Claim 46
Dependent Claim
34 words
The method of claim 35 wherein said fluoride compound is selected from the group consisting of ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 F.HF), hydrogen fluoride (HF), aluminum fluoride and mixtures thereof.
Claim 47
Dependent Claim
25 words
The method of claim 35 wherein said mineral acid is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and mixtures thereof.
Claim 48
Dependent Claim
30 words
The method of claim 38 wherein said mineral acid is present in an amount in the range of from about 0.1 to about 30 percent by weight of said composition.
Claim 49
Dependent Claim
65 words
The method of claim 35 wherein said aluminum compound is represented by the general formula (Al.sup.+3).sub.n (M.sup.+1).sub.z (X.sup.-a).sub.m the hydrates of such compounds and mixtures thereof wherein: X is selected from the group consisting of anions derived from mineral acids, anions derived from organic acids, an hydroxyl group and mixtures thereof; M is selected from hydrogen and ammonium; z is 0 or 1; and 3n+z=am.
References Cited (Backward Citations)
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