US4479543A
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US
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Method for deeper penetrating acidizing of siliceous formations
Assignee: Union Oil Company of California
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Filing: 1983-07-28
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Granted: 1984-10-30
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Expires: 2003-07-28
Abstract
Abstract A method for acidizing siliceous subterranean formations wherein the acidizing composition penetrates the formation to a greater extent before spending comprising injecting into the formation first an organosilane or an ester of an organosilane, preferably in a hydrocarbon carrier liquid, and thereafter an aqueous acidizing composition containing (1) a non-oxidizing mineral acid, acid precursor, low molecular weight organic acid or halogenated derivative thereof, and (2) a fluorine-containing acid or salt.
Inventors
- 👤 Leonard J. Kalfayan
- 👤 David R. Watkins
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 11:30
CPC Classifications
C; C09; C09K; C09K8/00; C09K8/60; C09K8/62; C09K8/72
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
95 words
A method for acidizing siliceous materials contained in a subterranean formation penetrated by a well comprising injecting into the said formation: (a) first a slug of an organosilane or an ester of an organosilane, and (b) next a slug of an aqueous acidizing composition comprising a mixture of (1) a first acidizing component selected from the group consisting of non-oxidizing mineral acids, acid precursors, low molecular weight organic acids, and halogenated derivatives of low molecular weight organic acids, and (2) a second acidizing component selected from the group consisting of fluorine-containing acids and fluorine-containing salts.
Claim 2
Independent Claim
95 words
A method for acidizing siliceous materials contained in a subterranean formation penetrated by a well comprising injecting into the said formation: (a) first a slug of an organosilane or an ester of an organosilane, and (b) next a slug of an aqueous acidizing composition comprising a mixture of (1) a first acidizing component selected from the group consisting of non-oxidizing mineral acids, acid precursors, low molecular weight organic acids, and halogenated derivatives of low molecular weight organic acids, and (2) a second acidizing component selected from the group consisting of fluorine-containing acids and fluorine-containing salts.
Claim 3
Dependent Claim
31 words
The method defined in claim 1 wherein the amount of organosilane or ester of an organosilane employed is about 0.5 to 100 gallons per vertical foot of formation to be treated.
Claim 4
Dependent Claim
28 words
The method defined in claim 1 wherein the amount of aqueous acidizing composition employed is about 0.5 to 20 barrels per vertical foot of formation to be treated.
Claim 5
Dependent Claim
41 words
The method defined in claim 1 wherein there is injected into the formation before the organosilane or ester of an organosilane about 0.5 to 100 gallons per vertical foot of formation to be treated of a preflush of a hydrocarbon liquid.
Claim 6
Dependent Claim
28 words
The method defined in claim 4 wherein there is included in the preflush of a hydrocarbon liquid up to about 50 percent by volume of a polymerization catalyst.
Claim 7
Dependent Claim
41 words
The method defined in claim 1 wherein there is injected into the formation following the organosilane or ester of an organosilane about 0.5 to 100 gallons per vertical foot of formation to be treated of a spacer of a hydrocarbon liquid.
Claim 8
Dependent Claim
51 words
The method defined in claim 1 wherein there is injected into the formation following the aqueous acidizing composition about 0.5 to 100 gallons per vertical foot of formation to be treated of an afterflush comprising an aqueous salt solution or a liquid which is substantially immiscible with the aqueous acidizing composition.
Claim 9
Dependent Claim
13 words
The method defined in claim 7 wherein the afterflush is a hydrocarbon liquid.
Claim 10
Dependent Claim
101 words
The method defined in claim 1 wherein the organosilane has the formula: ##STR6## wherein X is a halogen, R 1 is an organic radical having from 1 to 50 carbon atoms, and R 2 and R 3 are the same or different halogens or organic radicals having from 1 to 50 carbon atoms; and the ester of an organosilane has the formula: ##STR7## wherein R 4 , R 5 and R 6 are independently selected from hydrogen and organic radicals having from 1 to 50 carbon atoms and R 7 is an organic radical having from 1 to 50 carbon atoms.
Claim 11
Dependent Claim
143 words
The method defined in claim 1 wherein the organosilane has the formula: ##STR8## wherein X is a halogen selected from the group consisting of chlorine, bromine and iodine, R 1 is an alkyl, alkenyl or aryl group having from 1 to 18 carbon atoms and R 2 and R 3 are the same or different halogens, or alkyl, alkenyl or aryl group having from 1 to 18 carbon atoms; and the ester of an organosilane has the formula: ##STR9## wherein R 4 , R 5 and R 6 are independently selected from hydrogen, amine, alkyl, alkenyl, aryl and carbhydroloxy groups having from 1 to 18 carbon atoms, with at least one R 4 , R 5 and R 6 groups not being hydrogen, and R 7 is selected from an amine, alkyl, alkenyl and aryl group having from 1 to 18 carbon atoms.
Claim 12
Dependent Claim
32 words
The method defined in claim 1 wherein the organosilane or ester of an organosilane is injected as a solution in up to about 50 percent by volume of a hydrocarbon carrier liquid.
Claim 13
Dependent Claim
30 words
The method defined in claim 11 wherein the hydrocarbon carrier is selected from the group consisting of crude oil, an aliphatic hydrocarbon, an aromatic hydrocarbon and a petroleum distillation product.
Claim 14
Dependent Claim
30 words
The method defined in claim 1 wherein there is included in the organosilane or ester of an organosilane injected up to about 50 percent by volume of a polymerization catalyst.
Claim 15
Dependent Claim
21 words
The method defined in claim 1 wherein the ester of an organosilane is an alkylated amine substituted ester of an organosilane.
Claim 16
Dependent Claim
14 words
The method defined in claim 1 wherein the ester of an organosilane is y-aminopropyltriethoxysilane.
Claim 17
Dependent Claim
38 words
The method defined in claim 1 wherein the said first acidizing component is a non-oxidizing mineral acid selected from the group consisting of hydrochloric acid, nitric acid, hydroiodic acid, hydrobromic acid, sulfuric acid, sulfamic acid and phosphoric acid.
Claim 18
Dependent Claim
14 words
The method defined in claim 16 wherein the first acidizing component is hydrochloric acid.
Claim 19
Dependent Claim
44 words
The method defined in claim 1 wherein the said first acidizing component is an acid precursor having the generalized formula: C.sub.x H.sub.y X.sub.z wherein x=1 or 2; y=0, 1 or 2, but y≦x; and z=2x-y+2; and X is selected from chlorine, bromine and/or iodine.
Claim 20
Dependent Claim
29 words
The method defined in claim 18 wherein the acid precursor is selected from the group consisting of tetrachloromethane, trichloromethane, pentachloroethane, tetrachloroethane, bromotrichloromethane, chlorodibromomethane, bromodichloromethane, trichlorodibromomethane, dichlorodibromoethane and mixtures thereof.
Claim 21
Dependent Claim
12 words
The method defined in claim 18 wherein the acid precursor is tetrachloromethane.
Claim 22
Dependent Claim
34 words
The method defined in claim 1 wherein the first acidizing component is a low molecular weight organic acid selected from the group consisting of formic, acetic, citric, propionic and tartaric acids and mixtures thereof.
Claim 23
Dependent Claim
30 words
The method defined in claim 1 wherein the first acidizing component is a low molecular weight halogenated organic acid selected from the group consisting of mono-, di- and trichloroacetic acids.
Claim 24
Dependent Claim
28 words
The method defined in claim 1 wherein the second acidizing component is a fluorine-containing acid selected from the group consisting of hydrofluoric, fluoroboric, hexafluorophosphoric, difluorophosphoric and/or fluorosulfonic acids.
Claim 25
Dependent Claim
44 words
The method defined in claim 1 wherein the second acidizing component is a fluorine-containing salt selected from the group consisting of ammonium fluoride, ammonium bifluoride, ammonium fluoroborate, ammonium hexafluorophosphate, ammonium difluorophosphate, ammonium fluorosulfonate, cesium fluoride, cesium bifluoride, cesium hexafluorophosphate, cesium difluorophosphate and/or cesium fluorosulfonate.
Claim 26
Dependent Claim
14 words
The method defined in claim 1 wherein the second acidizing component is ammonium bifluoride.
Claim 27
Independent Claim
181 words
A method for acidizing siliceous materials contained in a subterranean formation penetrated by a well comprising injecting into the said formation: (a) first a slug of about 0.5 to 100 gallons per vertical foot of formation to be treated of an ester of an organosilane having the formula: ##STR10## wherein R 4 , R 5 and R 6 are independently selected from hydrogen, amine, alkyl, alkenyl, aryl and carbohydroxyl groups having from 1 to 18 carbon atoms, with at least one of the R 4 , R 5 and R 6 groups not being hydrogen, and R 7 is selected from an amine, alkyl, alkenyl and aryl group having from 1 to 18 carbon atoms, and (b) next a slug of about 0.5 to 20 barrels per vertical foot of formation to be treated of an aqueous acidizing composition comprising a mixture containing: [] 5to 12 percent by weight of hydrochloric acid, [2] 1 to 10 percent by weight of fluoride ion added as a second acidizing component selected from the group consisting of hydroflouric acid, ammonium fluoride and ammonium bifluoride.
Claim 28
Independent Claim
181 words
A method for acidizing siliceous materials contained in a subterranean formation penetrated by a well comprising injecting into the said formation: (a) first a slug of about 0.5 to 100 gallons per vertical foot of formation to be treated of an ester of an organosilane having the formula: ##STR10## wherein R 4 , R 5 and R 6 are independently selected from hydrogen, amine, alkyl, alkenyl, aryl and carbohydroxyl groups having from 1 to 18 carbon atoms, with at least one of the R 4 , R 5 and R 6 groups not being hydrogen, and R 7 is selected from an amine, alkyl, alkenyl and aryl group having from 1 to 18 carbon atoms, and (b) next a slug of about 0.5 to 20 barrels per vertical foot of formation to be treated of an aqueous acidizing composition comprising a mixture containing: [] 5to 12 percent by weight of hydrochloric acid, [2] 1 to 10 percent by weight of fluoride ion added as a second acidizing component selected from the group consisting of hydroflouric acid, ammonium fluoride and ammonium bifluoride.
Claim 29
Dependent Claim
21 words
The method defined in claim 26 wherein the ester of an organosilane is an alkylated amine substituted ester of an organosilane.
Claim 30
Dependent Claim
14 words
The method defined in claim 26 wherein the ester of an organosilane is γ-aminopropyltriethoxysilane.
Claim 31
Dependent Claim
48 words
The method defined in claim 26 wherein the ester of an organosilane is injected as a solution up to about 50 percent by volume of a hydrocarbon carrier liquid selected from the group consisting of crude oil, an aliphatic hydrocarbon, an aromatic hydrocarbon and a petroleum distillation product.
Claim 32
Dependent Claim
28 words
The method defined in claim 26 wherein there is included in the ester of an organosilane injected up to about 50 percent by volume of a polymerization catalyst.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-10-30 | 1988-04-30 | 1988-10-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-10-30 | 1992-04-30 | 1992-10-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-10-30 | 1996-04-30 | 1996-10-30 | $7700.00 | Window Closed / Lapsed |