CA2049365A1 - Acid inhibitor composition for use in well acidizing operations - Google Patents
Acid inhibitor composition for use in well acidizing operationsInfo
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- CA2049365A1 CA2049365A1 CA 2049365 CA2049365A CA2049365A1 CA 2049365 A1 CA2049365 A1 CA 2049365A1 CA 2049365 CA2049365 CA 2049365 CA 2049365 A CA2049365 A CA 2049365A CA 2049365 A1 CA2049365 A1 CA 2049365A1
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- acid
- alcohol
- acidizing fluid
- antimony
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Abstract
ABSTRACT OF THE DISCLOSURE
A well acidizing fluid is shown containing an acid solution effective to increase the permeability of a subterranean formation and containing a corrosion inhibiting composition which is a mixture of a complex substituted keto-amine, an acetylenic alcohol, an alkanol, a rosin acid component, a non-ionic surfactant, and an antimony compound.
A well acidizing fluid is shown containing an acid solution effective to increase the permeability of a subterranean formation and containing a corrosion inhibiting composition which is a mixture of a complex substituted keto-amine, an acetylenic alcohol, an alkanol, a rosin acid component, a non-ionic surfactant, and an antimony compound.
Description
BACKGF~OUND OF THE INVENT~ON
3 I. Field ~f the Invention:
The present invention relates to compositions and 6 methods for acidizing subterranean formations in the 7 vicinity of a well bore. More specifically, the 8 invention relates to the acidizing of a subterranean 9 formation using an acidic solution containing a corrosion inhibitor which substantially reduces the 11 corrosive effects of the acidic solution on metals in 12 contact with the acidic solution.
14 2. Description o~ tlle Prior Art:
16 Acidization of oil-bearing strata is a well known 17 method of increasing oil production. The main 18 constituent of the treatment formulation is the acid, 19 usually hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, or mixtures thereof.
22 As the acid is moved from its manufacturing source 23 to the well borehole, and into the geological 24 formation, it comes into contact with metals in various 25 forms. Although commercial hydrochloric acid is 26 available at a concentration of about 30 to 40 percent 27 by weight, concentrated acid is generally diluted with 28 water to about 15 percent for most well acidizing jobs.
29 However, the strength of acid used in well stimulation may range from 1 to 30 weight percent HCl, depending 31 upon various well conditions. To prevent metal ions 32 (the most common being iron) from becoming dissolved in 7 ~
1 the acid, the acid may be stored in non-reactive or 2 lined storage vessels prior to use.
4 Without the presence of an effective corrosion inhihitor, the acidic solution attacks and deteriorates 6 most metals which are contacted. Corrosion by the 7 acidic solution of the tubular goods in the well bore ~ and of the other equipment used to carry out the 9 treatment is o~ major concern to operators. The expense of repairing or replacing corrosion damaged equipment 11 is extremely high. The corrosion problem is also 12 heightened by the elevated temperatures found in deeper 13 geological formations being treated.
It is accordingly an object of the present 16 invention to provide a well acidizing solution which 17 substantially inhibits the deleterious effects of a 18 treatment acid on the equipment used in the acidizing 19 treatment.
21 Another object of the invention is to provide a 22 corrosion inhibitor for a well acidizing solution which 23 is effective to overcome the problems associated with 24 corrosion resulting from contact of the acidic solution with ferrous and other metals at el~vated temperatures 26 in the range from 150F to 400F and even higher.
~ V i' f3 ~ 'J ~i SUMMARY OF THE INVENTION
3 I. Field ~f the Invention:
The present invention relates to compositions and 6 methods for acidizing subterranean formations in the 7 vicinity of a well bore. More specifically, the 8 invention relates to the acidizing of a subterranean 9 formation using an acidic solution containing a corrosion inhibitor which substantially reduces the 11 corrosive effects of the acidic solution on metals in 12 contact with the acidic solution.
14 2. Description o~ tlle Prior Art:
16 Acidization of oil-bearing strata is a well known 17 method of increasing oil production. The main 18 constituent of the treatment formulation is the acid, 19 usually hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, or mixtures thereof.
22 As the acid is moved from its manufacturing source 23 to the well borehole, and into the geological 24 formation, it comes into contact with metals in various 25 forms. Although commercial hydrochloric acid is 26 available at a concentration of about 30 to 40 percent 27 by weight, concentrated acid is generally diluted with 28 water to about 15 percent for most well acidizing jobs.
29 However, the strength of acid used in well stimulation may range from 1 to 30 weight percent HCl, depending 31 upon various well conditions. To prevent metal ions 32 (the most common being iron) from becoming dissolved in 7 ~
1 the acid, the acid may be stored in non-reactive or 2 lined storage vessels prior to use.
4 Without the presence of an effective corrosion inhihitor, the acidic solution attacks and deteriorates 6 most metals which are contacted. Corrosion by the 7 acidic solution of the tubular goods in the well bore ~ and of the other equipment used to carry out the 9 treatment is o~ major concern to operators. The expense of repairing or replacing corrosion damaged equipment 11 is extremely high. The corrosion problem is also 12 heightened by the elevated temperatures found in deeper 13 geological formations being treated.
It is accordingly an object of the present 16 invention to provide a well acidizing solution which 17 substantially inhibits the deleterious effects of a 18 treatment acid on the equipment used in the acidizing 19 treatment.
21 Another object of the invention is to provide a 22 corrosion inhibitor for a well acidizing solution which 23 is effective to overcome the problems associated with 24 corrosion resulting from contact of the acidic solution with ferrous and other metals at el~vated temperatures 26 in the range from 150F to 400F and even higher.
~ V i' f3 ~ 'J ~i SUMMARY OF THE INVENTION
3 These and other objects are accomplished through 4 the use of a treatment solution whlch contains a corrosion inhibitor which substantially reduces the 6 corrosive effect of the acid on ferrous and other 7 metals without reducing the eff~ctiveness of the acidic 8 solution in treating the subterranean formation. The 9 acidizing solution is introduced into the subterranean formation through a well bore at a flow rate and 11 pressure sufficient to permit the acid to dissolve 12 formation materials or foreign materials in the 13 vicinity of the well bore. The acidic solution can 14 comprise, for instance, a solution of hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, 16 citric acid and mixtures thereof. The corrosion 17 inhibitor comprises a mixture of:
19 a complex substituted keto-amine:
21 an acetylenic alcohol:
23 an alkanol;
a rosin acid component;
27 a non-ionic surfactant; and 29 an antimony compound.
31 Preferably, the corrosion inhibitor composition is 32 added to the acid solution in an amount effective to 33 reduce the corrosive effect of the acid solution on the 23 1 rJ ~
1 ferrous metal, the corrosion inhibitor composition 2 comprising a mixture o~ the following components by 3 weight percent, based on the total weight of corrosion 4 inhibitor:
6 (a) a complex substituted keto-amine which 7 is a condensation product preparPd by a Mannich 8 reaction of formaldehyde, primary amines and ketones, 9 the complex substituted keto-amine being present in the range from about 30-40 % by weight;
12 (b) an acetylenic alcohol, wherein the 13 acetylenic alcohol has the general formula:
17 Rl- C- C- C--OH
19 ~2 21 wherein Rl, R2 and R3 are selected from the 22 group consisting of hydrogen, alkyl, phenyl, 23 substituted phenyl and hydroxy-alkyl radicals, the 24 acetylenic alcohol being present in the range from about 5-25 % by weight;
27 (c) an alkanol, present in the range from 28 about 10-20 weight percent;
(d) a rosin acid component, present in the 31 range from about 1-10 weight percent; and 2 ~ ~, 3 ~ ^~
1 (e) a non-ionic surfactant, present in the 2 range from about 5-20 weight percent.
4 The corrosion inhibitor also has added thereto an antimony compound present in an amount effective to 6 provide an antimony concentration of from about 0.0007 7 to about 0.04 molar solution to the corrosive acid.
9 Additional objects, features and advantages will be apparent in the written description which follows.
DETAlLEr) DESCRIPTION OF THE INVENTION
3 The acidizing treatment fluids of the invention 4 are solutions containing one or more commonly available acids. The acidizing treatment fluids can be 6 comprised, for example, of hydrochloric acid or 7 mixtures of hydrochloric acid with hydrofluoric acid, 8 acetic acid, formic acid, citric acid and mixtures 9 thereof. The acid concentration may range between about 1~ and about 30%, by weight of the treatment 11 fluid, depending upon the type of acid used and well 12 conditions present.
14 The acidizing fluid of the invention also contains a corrosion inhibitor composition which is a mixture of 16 a complex substituted keto-amine, an acetylenic 17 alcohol, an alkanol, a rosin acid component, a non-18 ionic surfactant, and an antimony compound.
The complex substituted keto-amine is a 21 condensation product prepared by a Mannich reaction of 22 formaldehyde, primary amines and ketones as described 23 in U.S. Patent No. 3,071,590, entitled "Condensation 24 Products of Formaldehyde, Primary Amines and Ketones", issued January 1, 1963, to Gardner, the disclosure of 26 which is incorporated herein by reference. Preferably, 27 the complex substituted keto-amine is of the formulao ~ ,", 31 ~ t~ Cl~C11~n~CIt~t~ ]~
32 h~
2 ~3 L C,~ .~ J . j 3 wherein R' is selected from the group 4 consisting of alkyl and alkenyl of 8 to 22 total carbon atoms, R " is selected from the group consisting of 6 alkyl of from 1 to 19 carbon atoms, phenyl, benzyl, 7 biphenyl and thienyl; X is an acid radical selected 8 from the group consisting of Cl, S04 and Br; n is an 9 integer from 1 to 2 inclusive, and v is an integer inverse to that of n whereby to satisfy the valence of 11 the imidazoline radical.
13 Particularly, preferred complex substituted keto-14 amines are selected form the group consisting of:
16 2-heptadecenyl-1-(N-butanone-3)-aminoethyl 17 imidazoline dihydrochloride;
19 5-methyl-2-hexadecyl-1-(N-alpha-methyl-cyclohexanone)-aminoisopropyl imidazoline sulfate;
22 2-heptadecyl-1-(N-4-methyl, pentanone-3)~
23 aminoethyl imidazoline dihydrochloride;
2-undecyl-1-(N-butanone-3)-aminoethyl 26 imidazonline dihydrochloride;and 28 2~undecyl-1-(N-phenyl-3, propanone-3)-29 aminoethyl imidazoline dihydrochloride.
31 The complex substituted amine component o~ the 32 acidizing fluid is present in the range from about 30 ~ ~'J ''~ J,,J1 1 to 40 weight percent, based on the total weight of the 2 corrosion inhibitor.
4 The acetylenic alcohol component of the corrosion inhibitor includes any of the acetylenic alcohols 6 having the general formula:
17 wherein R1, R2 and R3 are hydrogen, alkyl, 18 phenyl, substituted phenyl or hydroxy-alkyl radicals.
19 Preferably, R1 comprises hydrogen~ Preferably, R2 comprises hydrogen, methyl, ethyl or propyl radicals.
21 Preferably, R3 comprises an alkyl radical having the 22 general formula CnH2n, where n is an integer from l to 23 10.
So~e examples of acetylenic alcohols which can be 26 utilized for the purposes of the present invention 27 include methyl butynol, methyl pentynol, hexynol, ethyl 28 octynol, propargyl alcohol, berlzylbutynol, 29 ethynlcyclohexanol, and the like. The preferred acetylenic alcohol is propargyl alcohol. The acetylenic 31 alcohol component is present in the corrosion inhibitor 32 composition in the range from about 5 to 25 weight %
33 based on the total weight of the corrosion inhibitor.
r~
2 Propargyl alcohol is a commercially available 3 acetylenic primary alcohol. It is a colorless, volatile 4 liquid which is miscible in water and many organic solvents. Propargyl alcohol has a density at 20'C of 6 0.9715, a boiling point of 114C and a viscosity at 7 20C in Cp. of 1.68.
9 The alkanol component of the corrosion inhibitor composition can be, for example, methyl, ethyl, propyl, 11 isopropyl, butyl, pentyl, hexyl, heptyl, octyl and 12 other higher liquid members of these aliphatic 13 alcohols. The preferred alkanol component is isopropyl 14 alcohol because of its commercial availability. The alkanol component is preferably present in an amount 16 sufficient to maintain the other components of the 17 corrosion inhibitor in homogeneous admixture.
18 Preferably, the alXanol component is present in the 19 range from about lo to 20 weight %, based on the total weight of corrosion inhibitor composition.
22 The rosin acid component can be, for exa~ple, 23 abietic, sapiatic, or the pimaric type acids derived by 24 distillation of the oleoresin obtained from various species of pine trees. These materials are used 26 extensively in protective coatings, printing ink 27 formulations, and the like. The rosin acid component 28 is preferably present in the range from about 1 to 10 29 weight %, based on the total weight of corrosion inhibitor.
32 The non-ionic surfactant component useful in the 33 corrosion inhibitor compositions of the invention ~ f~ ~? g 1 include ethoxylates of alkyl phenols, primary fatty 2 alco~ols, secondary fatty alcohols, and the like, 3 including alkyl and alkylaryl polyether alcohols such 4 as the reaction product of trimethyl-l-heptanol with seven mols of ethylene oxide, the reaction products of 6 octyl or nonyl phenol with, e.g., from about 8 to 30 7 mols or more of ethylene oxide, 8 polyoxyethylenepolyoxypropylene block copolymers, and g the like. A suitable non-ionic surfactant for purposes of the present invention is commercially available from 11 the ~hom & Haas Company as the Titron N-101 and is an 12 ethoxylated nonyl phenol. The non-ionic surfactant is 13 preferably present in the range from about 5 to 20 14 weight %, based on the total weight of corrosion inhibitor.
17 The antimony component of the corrosion inhibitor 18 of the invention can be any antimony compound capable 19 of reacting with the other components of the corrosion inhibitor to substantially reduce the corrosive effect 21 of the acidic fluid on metals, particularly ferrous 22 metals, in contact with the acidizing fluid.
23 Preferably, the antimony compound is selected from the 24 group consisting of antimony trioxide, antimony pentoxide, antimony trichloride, antimony 26 pentachloride, alkali metal salts of pyroantimonate, 27 antimony adducts of ethylene glycol and solutions 28 containing ethylene glycol, water and the oxidized 29 product of hydrogen peroxide and at least one member selected from the group consisting of trivalent 31 antimony compounds. The most preferred antimony 32 compound is antimony trioxide. Preferably, a suf~icient 33 guantity of the antimony compound is present in the r,~ r-1 acidizing fluid to obtain a solution having a 2 concentration o~ ~rom about 0.007 to abouk 0.04 molar.
3 The antimony component can be admixed with the other 4 component of the corrosion inhibitor composition to form a premixed inhibitor or it may be formulated in 6 situ in an acidic solution by the addition of a 7 sufficient quantity of the antimony compound and a 8 quantity of the other constituents which may be 9 premixed.
11 The method of the invention can be carried out by 12 first admixing an aqueous fluid with the acid to 13 provide an acidic solution of a desired concentration.
14 The corrosion inhibiting composition is then admixed with the solution in an amount sufficient to 16 substantially reduce the corrosion rate of the acid on 17 metals in contact with the acid. When the corrosion 18 inhibiting composition is generated in situ, all of the 19 components except the antimony compound are preferably admixed prior to the addition of the antimony compound.
21 The amount of corrosion inhibitor utilized in the 22 practice of the invention can vary over a substantial 23 range. Preferably, the inhibitor is present in an 24 amount of from about 10 to 30 gallons per 1000 gallons of acidic solution. The concentration of corrosion 26 inhibitor will vary, however, depending upon the 27 concentration of the acid solution and the temperature 28 at which the acidic solution will contact the metal 29 surfaces.
31 The aqueous acidic solution is introduced into the 3~ subterranean formation whereb~ either foreign material 33 in the well bore or in the formation or formation 2 ~3 :~ ~ t'3~
1 materials are dissolved to increase the permeability of 2 the formation. The increased permeabi]ity permits 3 better flow of hydrocarbon fluids through the formation 4 and into its well bore. The pumping rate and pressure utilized will depend upon the characteristics of the 6 formation and whether or not fracturing of the 7 formation is desired. After the aqueous acidic 8 solution has been injected, the well may be shut in for 9 a period of time. The shut in period may depend on various factors such as the type of acid employed, the 11 type of formation, the objective of the treatment, etc.
12 If there is pressure on the well, pressure then can be 13 released and the spent or at least partially spent 14 aqueous acidic solution, containing salks formed by the reaction of the acid, is permitted to flow back into 16 the well bore and is pumped or flowed to the surface 17 for appropriate disposal.
19 The following examples are intended to be illustrative of the invention:
24 To determine the effect of antimony concentration on the inhibitor composition, the following tests were 26 performed: An acidic aqueous solution was prepared hy 27 adding concentrated hydrochloric acid to water to form 28 a 10% HCl solution. ~ corrosion inhibitor composition 29 was prepared as described above by mixing together the complex substituted keto amine, propargyl alcohol, 31 isopropanol, rosin acids and non-ionic surfactant.
32 Then, a quantity of antimony compound as set forth 2 ~J ~
1 below was added to the treating acid and co-mixed with 2 the other constituents of the corrosion inhibitor.
4 The acid solution containing corrosion inhibitor and antimony compound at the concentration set forth 6 below, was then heated to a temperature of 350~F under 7 l,OoO psig pressure and a weighted sample of 1020 mild 8 steel was suspended in the solution. The volume ts 9 surface area ratio of the acidic solution to the metal sample is about 25 cc/in2. After six hours, the metal 11 sample was removed from the solution, washed and 12 weighed to determine the corrosion loss (lb/ft2).
14 Test Conditions:
16 Temperature : 350F
17 Steel : 1020 mild steel 18 Acid : 10% HC1 (by weight) 19 Pressure : 1000 psi Duration : 6 hours (at temperature) 22 Results-24 Corrosion Sb2O3 Weight Loss Inhikitor, ~ Conc._~_ppt lb/ft-27 1.0 10 .0011 28 1.0 15 .0008 2Q 1.0 20 .0009 1.5 15 .0017 31 1.5 20 .0027 2 5.J ,'~ r.
1 EX~MPLE II
3 Tests were also performed to test the 4 effectiveness of the corxosion inhibitor of the invention as compared to a prior art formulation 6 containing an acetylenic alcohol, a quaternary ammonium 7 compound, an aromatic hydrocarbon and an antimony 8 compound. These tests were performed by adding the 9 same quantity of inhibitor/antimony compound to 15% HCl acid solutions. The quantity of inhibitor added was 11 1.5% (by volume) and an antimony compound was mixed 12 with the acidic solution in an amount sufficient to 13 provide an antimony concentration of about 0.0197 molar 14 in the acidic aqueous solution. A weighted sample of N-80 grade steel was then suspended in the acid and the 16 solution heated to a temperature of 325F under 1,000 17 psi nitrogen pressure. After 6 hours contact time (at 18 temperature) the metal sample was removed from the acid 19 solution, cleaned and weighed to determine the corrosion weight loss. The effectiveness of each 21 inhibitor composition is illustrated by the following 22 data:
24 RESULTS:
26 Steel Sample Corrosion 27 InhibitorWeight, gm Weight Rate 228 System Initial Final Change, gm lb/ft2 30 Invention 31 Inhibitor/
32 Antimony 40.0388 39.8647 -0.1741 .0125 34 Prior Art 35 Inhibitor/
36 Antimony 42.9500 42.0448 -0.9052 .0652 ~ 3~r-1 The corrosion rate of the present 2 inhibitor/antimony system of 0.0125 lb/ft2 is 3 substantially less than the general oil industry 4 allowable corrosion rate of about 0.05 lb/ft2. In addition to the lower corrosion rate showed hy the 6 present invention s~stem, a difference in the coating-7 film forming protection established on the metal 8 surface by the two inhibitors was also observed. The 9 sample exposed in the inventive syste~ showed a very uniform, fine coating on all metal surfaces, whereas 11 the coating on the comparative sample was irregular, 12 leaving some areas of the metal unprotected. The test 13 results suggest that the components of the inhibitor of 14 the invention react differently with antimony than the prior art components. The resulting synergism has been 16 observed to provide a higher degree of acid corrosion 17 protection.
1~ An invention has been provided with several advantages. The corrosion inhibitor/antimony 21 composition of the invention provides a substantial 22 increase in corrosion protection, at temperatures above 23 300F, over other inhibitor systems tested. Various 24 oil field alloys, such as N-80, mild steel, and 13 Cr stainless steels can be protected with the corrosion 26 inhibitor/antimony system. The composition is 27 compatible with many traditional additives used in 28 acidizing formulations, such as mutual solvents, 29 surfactants, sequestering agents, etc. The inhibitor is stable under all well treatment conditions.
32 While the invention has been shown in only one o~
33 its forms, it is not thus limited but is susceptible to 1 various changes and modifications without departing 2 from the spirit thereof.
:
' -~ 17;-: ;
, : ~
19 a complex substituted keto-amine:
21 an acetylenic alcohol:
23 an alkanol;
a rosin acid component;
27 a non-ionic surfactant; and 29 an antimony compound.
31 Preferably, the corrosion inhibitor composition is 32 added to the acid solution in an amount effective to 33 reduce the corrosive effect of the acid solution on the 23 1 rJ ~
1 ferrous metal, the corrosion inhibitor composition 2 comprising a mixture o~ the following components by 3 weight percent, based on the total weight of corrosion 4 inhibitor:
6 (a) a complex substituted keto-amine which 7 is a condensation product preparPd by a Mannich 8 reaction of formaldehyde, primary amines and ketones, 9 the complex substituted keto-amine being present in the range from about 30-40 % by weight;
12 (b) an acetylenic alcohol, wherein the 13 acetylenic alcohol has the general formula:
17 Rl- C- C- C--OH
19 ~2 21 wherein Rl, R2 and R3 are selected from the 22 group consisting of hydrogen, alkyl, phenyl, 23 substituted phenyl and hydroxy-alkyl radicals, the 24 acetylenic alcohol being present in the range from about 5-25 % by weight;
27 (c) an alkanol, present in the range from 28 about 10-20 weight percent;
(d) a rosin acid component, present in the 31 range from about 1-10 weight percent; and 2 ~ ~, 3 ~ ^~
1 (e) a non-ionic surfactant, present in the 2 range from about 5-20 weight percent.
4 The corrosion inhibitor also has added thereto an antimony compound present in an amount effective to 6 provide an antimony concentration of from about 0.0007 7 to about 0.04 molar solution to the corrosive acid.
9 Additional objects, features and advantages will be apparent in the written description which follows.
DETAlLEr) DESCRIPTION OF THE INVENTION
3 The acidizing treatment fluids of the invention 4 are solutions containing one or more commonly available acids. The acidizing treatment fluids can be 6 comprised, for example, of hydrochloric acid or 7 mixtures of hydrochloric acid with hydrofluoric acid, 8 acetic acid, formic acid, citric acid and mixtures 9 thereof. The acid concentration may range between about 1~ and about 30%, by weight of the treatment 11 fluid, depending upon the type of acid used and well 12 conditions present.
14 The acidizing fluid of the invention also contains a corrosion inhibitor composition which is a mixture of 16 a complex substituted keto-amine, an acetylenic 17 alcohol, an alkanol, a rosin acid component, a non-18 ionic surfactant, and an antimony compound.
The complex substituted keto-amine is a 21 condensation product prepared by a Mannich reaction of 22 formaldehyde, primary amines and ketones as described 23 in U.S. Patent No. 3,071,590, entitled "Condensation 24 Products of Formaldehyde, Primary Amines and Ketones", issued January 1, 1963, to Gardner, the disclosure of 26 which is incorporated herein by reference. Preferably, 27 the complex substituted keto-amine is of the formulao ~ ,", 31 ~ t~ Cl~C11~n~CIt~t~ ]~
32 h~
2 ~3 L C,~ .~ J . j 3 wherein R' is selected from the group 4 consisting of alkyl and alkenyl of 8 to 22 total carbon atoms, R " is selected from the group consisting of 6 alkyl of from 1 to 19 carbon atoms, phenyl, benzyl, 7 biphenyl and thienyl; X is an acid radical selected 8 from the group consisting of Cl, S04 and Br; n is an 9 integer from 1 to 2 inclusive, and v is an integer inverse to that of n whereby to satisfy the valence of 11 the imidazoline radical.
13 Particularly, preferred complex substituted keto-14 amines are selected form the group consisting of:
16 2-heptadecenyl-1-(N-butanone-3)-aminoethyl 17 imidazoline dihydrochloride;
19 5-methyl-2-hexadecyl-1-(N-alpha-methyl-cyclohexanone)-aminoisopropyl imidazoline sulfate;
22 2-heptadecyl-1-(N-4-methyl, pentanone-3)~
23 aminoethyl imidazoline dihydrochloride;
2-undecyl-1-(N-butanone-3)-aminoethyl 26 imidazonline dihydrochloride;and 28 2~undecyl-1-(N-phenyl-3, propanone-3)-29 aminoethyl imidazoline dihydrochloride.
31 The complex substituted amine component o~ the 32 acidizing fluid is present in the range from about 30 ~ ~'J ''~ J,,J1 1 to 40 weight percent, based on the total weight of the 2 corrosion inhibitor.
4 The acetylenic alcohol component of the corrosion inhibitor includes any of the acetylenic alcohols 6 having the general formula:
17 wherein R1, R2 and R3 are hydrogen, alkyl, 18 phenyl, substituted phenyl or hydroxy-alkyl radicals.
19 Preferably, R1 comprises hydrogen~ Preferably, R2 comprises hydrogen, methyl, ethyl or propyl radicals.
21 Preferably, R3 comprises an alkyl radical having the 22 general formula CnH2n, where n is an integer from l to 23 10.
So~e examples of acetylenic alcohols which can be 26 utilized for the purposes of the present invention 27 include methyl butynol, methyl pentynol, hexynol, ethyl 28 octynol, propargyl alcohol, berlzylbutynol, 29 ethynlcyclohexanol, and the like. The preferred acetylenic alcohol is propargyl alcohol. The acetylenic 31 alcohol component is present in the corrosion inhibitor 32 composition in the range from about 5 to 25 weight %
33 based on the total weight of the corrosion inhibitor.
r~
2 Propargyl alcohol is a commercially available 3 acetylenic primary alcohol. It is a colorless, volatile 4 liquid which is miscible in water and many organic solvents. Propargyl alcohol has a density at 20'C of 6 0.9715, a boiling point of 114C and a viscosity at 7 20C in Cp. of 1.68.
9 The alkanol component of the corrosion inhibitor composition can be, for example, methyl, ethyl, propyl, 11 isopropyl, butyl, pentyl, hexyl, heptyl, octyl and 12 other higher liquid members of these aliphatic 13 alcohols. The preferred alkanol component is isopropyl 14 alcohol because of its commercial availability. The alkanol component is preferably present in an amount 16 sufficient to maintain the other components of the 17 corrosion inhibitor in homogeneous admixture.
18 Preferably, the alXanol component is present in the 19 range from about lo to 20 weight %, based on the total weight of corrosion inhibitor composition.
22 The rosin acid component can be, for exa~ple, 23 abietic, sapiatic, or the pimaric type acids derived by 24 distillation of the oleoresin obtained from various species of pine trees. These materials are used 26 extensively in protective coatings, printing ink 27 formulations, and the like. The rosin acid component 28 is preferably present in the range from about 1 to 10 29 weight %, based on the total weight of corrosion inhibitor.
32 The non-ionic surfactant component useful in the 33 corrosion inhibitor compositions of the invention ~ f~ ~? g 1 include ethoxylates of alkyl phenols, primary fatty 2 alco~ols, secondary fatty alcohols, and the like, 3 including alkyl and alkylaryl polyether alcohols such 4 as the reaction product of trimethyl-l-heptanol with seven mols of ethylene oxide, the reaction products of 6 octyl or nonyl phenol with, e.g., from about 8 to 30 7 mols or more of ethylene oxide, 8 polyoxyethylenepolyoxypropylene block copolymers, and g the like. A suitable non-ionic surfactant for purposes of the present invention is commercially available from 11 the ~hom & Haas Company as the Titron N-101 and is an 12 ethoxylated nonyl phenol. The non-ionic surfactant is 13 preferably present in the range from about 5 to 20 14 weight %, based on the total weight of corrosion inhibitor.
17 The antimony component of the corrosion inhibitor 18 of the invention can be any antimony compound capable 19 of reacting with the other components of the corrosion inhibitor to substantially reduce the corrosive effect 21 of the acidic fluid on metals, particularly ferrous 22 metals, in contact with the acidizing fluid.
23 Preferably, the antimony compound is selected from the 24 group consisting of antimony trioxide, antimony pentoxide, antimony trichloride, antimony 26 pentachloride, alkali metal salts of pyroantimonate, 27 antimony adducts of ethylene glycol and solutions 28 containing ethylene glycol, water and the oxidized 29 product of hydrogen peroxide and at least one member selected from the group consisting of trivalent 31 antimony compounds. The most preferred antimony 32 compound is antimony trioxide. Preferably, a suf~icient 33 guantity of the antimony compound is present in the r,~ r-1 acidizing fluid to obtain a solution having a 2 concentration o~ ~rom about 0.007 to abouk 0.04 molar.
3 The antimony component can be admixed with the other 4 component of the corrosion inhibitor composition to form a premixed inhibitor or it may be formulated in 6 situ in an acidic solution by the addition of a 7 sufficient quantity of the antimony compound and a 8 quantity of the other constituents which may be 9 premixed.
11 The method of the invention can be carried out by 12 first admixing an aqueous fluid with the acid to 13 provide an acidic solution of a desired concentration.
14 The corrosion inhibiting composition is then admixed with the solution in an amount sufficient to 16 substantially reduce the corrosion rate of the acid on 17 metals in contact with the acid. When the corrosion 18 inhibiting composition is generated in situ, all of the 19 components except the antimony compound are preferably admixed prior to the addition of the antimony compound.
21 The amount of corrosion inhibitor utilized in the 22 practice of the invention can vary over a substantial 23 range. Preferably, the inhibitor is present in an 24 amount of from about 10 to 30 gallons per 1000 gallons of acidic solution. The concentration of corrosion 26 inhibitor will vary, however, depending upon the 27 concentration of the acid solution and the temperature 28 at which the acidic solution will contact the metal 29 surfaces.
31 The aqueous acidic solution is introduced into the 3~ subterranean formation whereb~ either foreign material 33 in the well bore or in the formation or formation 2 ~3 :~ ~ t'3~
1 materials are dissolved to increase the permeability of 2 the formation. The increased permeabi]ity permits 3 better flow of hydrocarbon fluids through the formation 4 and into its well bore. The pumping rate and pressure utilized will depend upon the characteristics of the 6 formation and whether or not fracturing of the 7 formation is desired. After the aqueous acidic 8 solution has been injected, the well may be shut in for 9 a period of time. The shut in period may depend on various factors such as the type of acid employed, the 11 type of formation, the objective of the treatment, etc.
12 If there is pressure on the well, pressure then can be 13 released and the spent or at least partially spent 14 aqueous acidic solution, containing salks formed by the reaction of the acid, is permitted to flow back into 16 the well bore and is pumped or flowed to the surface 17 for appropriate disposal.
19 The following examples are intended to be illustrative of the invention:
24 To determine the effect of antimony concentration on the inhibitor composition, the following tests were 26 performed: An acidic aqueous solution was prepared hy 27 adding concentrated hydrochloric acid to water to form 28 a 10% HCl solution. ~ corrosion inhibitor composition 29 was prepared as described above by mixing together the complex substituted keto amine, propargyl alcohol, 31 isopropanol, rosin acids and non-ionic surfactant.
32 Then, a quantity of antimony compound as set forth 2 ~J ~
1 below was added to the treating acid and co-mixed with 2 the other constituents of the corrosion inhibitor.
4 The acid solution containing corrosion inhibitor and antimony compound at the concentration set forth 6 below, was then heated to a temperature of 350~F under 7 l,OoO psig pressure and a weighted sample of 1020 mild 8 steel was suspended in the solution. The volume ts 9 surface area ratio of the acidic solution to the metal sample is about 25 cc/in2. After six hours, the metal 11 sample was removed from the solution, washed and 12 weighed to determine the corrosion loss (lb/ft2).
14 Test Conditions:
16 Temperature : 350F
17 Steel : 1020 mild steel 18 Acid : 10% HC1 (by weight) 19 Pressure : 1000 psi Duration : 6 hours (at temperature) 22 Results-24 Corrosion Sb2O3 Weight Loss Inhikitor, ~ Conc._~_ppt lb/ft-27 1.0 10 .0011 28 1.0 15 .0008 2Q 1.0 20 .0009 1.5 15 .0017 31 1.5 20 .0027 2 5.J ,'~ r.
1 EX~MPLE II
3 Tests were also performed to test the 4 effectiveness of the corxosion inhibitor of the invention as compared to a prior art formulation 6 containing an acetylenic alcohol, a quaternary ammonium 7 compound, an aromatic hydrocarbon and an antimony 8 compound. These tests were performed by adding the 9 same quantity of inhibitor/antimony compound to 15% HCl acid solutions. The quantity of inhibitor added was 11 1.5% (by volume) and an antimony compound was mixed 12 with the acidic solution in an amount sufficient to 13 provide an antimony concentration of about 0.0197 molar 14 in the acidic aqueous solution. A weighted sample of N-80 grade steel was then suspended in the acid and the 16 solution heated to a temperature of 325F under 1,000 17 psi nitrogen pressure. After 6 hours contact time (at 18 temperature) the metal sample was removed from the acid 19 solution, cleaned and weighed to determine the corrosion weight loss. The effectiveness of each 21 inhibitor composition is illustrated by the following 22 data:
24 RESULTS:
26 Steel Sample Corrosion 27 InhibitorWeight, gm Weight Rate 228 System Initial Final Change, gm lb/ft2 30 Invention 31 Inhibitor/
32 Antimony 40.0388 39.8647 -0.1741 .0125 34 Prior Art 35 Inhibitor/
36 Antimony 42.9500 42.0448 -0.9052 .0652 ~ 3~r-1 The corrosion rate of the present 2 inhibitor/antimony system of 0.0125 lb/ft2 is 3 substantially less than the general oil industry 4 allowable corrosion rate of about 0.05 lb/ft2. In addition to the lower corrosion rate showed hy the 6 present invention s~stem, a difference in the coating-7 film forming protection established on the metal 8 surface by the two inhibitors was also observed. The 9 sample exposed in the inventive syste~ showed a very uniform, fine coating on all metal surfaces, whereas 11 the coating on the comparative sample was irregular, 12 leaving some areas of the metal unprotected. The test 13 results suggest that the components of the inhibitor of 14 the invention react differently with antimony than the prior art components. The resulting synergism has been 16 observed to provide a higher degree of acid corrosion 17 protection.
1~ An invention has been provided with several advantages. The corrosion inhibitor/antimony 21 composition of the invention provides a substantial 22 increase in corrosion protection, at temperatures above 23 300F, over other inhibitor systems tested. Various 24 oil field alloys, such as N-80, mild steel, and 13 Cr stainless steels can be protected with the corrosion 26 inhibitor/antimony system. The composition is 27 compatible with many traditional additives used in 28 acidizing formulations, such as mutual solvents, 29 surfactants, sequestering agents, etc. The inhibitor is stable under all well treatment conditions.
32 While the invention has been shown in only one o~
33 its forms, it is not thus limited but is susceptible to 1 various changes and modifications without departing 2 from the spirit thereof.
:
' -~ 17;-: ;
, : ~
Claims (17)
1. A well acidizing fluid of the type used in treating subterranean formations in the vicinity of a metal lined borehole penetrating the formation, the acidizing fluid comprising:
an aqueous solution of an acid present in an amount effective to increase the permeability of the formation being treated;
a corrosion inhibitor composition added to the acid solution in an amount effective to reduce the corrosive effect of the acid solution on the metal in contact with the fluid, the corrosion inhibitor composition comprising a mixture of:
a complex substituted keto-amine;
an acetylenic alcohol;
an alkanol;
a rosin acid component:
a non-ionic surfactant; and an antimony compound.
an aqueous solution of an acid present in an amount effective to increase the permeability of the formation being treated;
a corrosion inhibitor composition added to the acid solution in an amount effective to reduce the corrosive effect of the acid solution on the metal in contact with the fluid, the corrosion inhibitor composition comprising a mixture of:
a complex substituted keto-amine;
an acetylenic alcohol;
an alkanol;
a rosin acid component:
a non-ionic surfactant; and an antimony compound.
2. The well acidizing fluid of claim 1, wherein the complex substituted keto-amine is a condensation product prepared by a Mannich reaction of formaldehyde, primary amines and ketones.
3. The well acidizing fluid of claim 2, wherein the complex substituted keto-amine is selected from the group consisting of:
2-heptadecenyl-1-(N-butanone-3)-aminoethyl imidazoline dihydrochloride;
5-methyl-2-hexadecyl-1-(N-alpha-methyl-cyclohexanone)-aminoisopropyl imidazoline sulfate;
2-heptadecyl-1-(N-4-methyl, pentanone-3)-aminoethyl imidazoline dihydrochloride;
2-undecyl-1-(N-butanone-3)-aminoethyl imidazonline dihydrochloride;and 2-undecyl-1-(N-phenyl-3, propanone-3)-aminoethyl imidazoline dihydrochloride.
2-heptadecenyl-1-(N-butanone-3)-aminoethyl imidazoline dihydrochloride;
5-methyl-2-hexadecyl-1-(N-alpha-methyl-cyclohexanone)-aminoisopropyl imidazoline sulfate;
2-heptadecyl-1-(N-4-methyl, pentanone-3)-aminoethyl imidazoline dihydrochloride;
2-undecyl-1-(N-butanone-3)-aminoethyl imidazonline dihydrochloride;and 2-undecyl-1-(N-phenyl-3, propanone-3)-aminoethyl imidazoline dihydrochloride.
4. The well acidizing fluid of claim 3, wherein the antimony compound is selected from the group consisting of antimony trioxide, antimony pentoxide, antimony trichloride, antimony pentachloride, alkali metal salts of pyroantimonate, antimony adducts of ethylene glycol and solutions containing ethylene glycol, water and the oxidized product of hydrogen peroxide and at least one member selected from the group consisting of trivalent antimony compounds.
5. The well acidizing fluid of claim 4, wherein the acetylenic alcohol has the general formula:
wherein R1, R2 and R3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals.
wherein R1, R2 and R3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals.
6. The well acidizing fluid of claim 5, wherein the alkanol is selected from the group consisting of:
methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol and mixtures thereof.
methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol and mixtures thereof.
7. The well acidizing fluid of claim 6, wherein the non-ionic surfactant is an ethoxylated alkyl phenol.
8. The well acidizing fluid of claim 7, wherein the non-ionic surfactant is selected from the group consisting of the ethylene oxide adduct of octyl phenol, nonyl phenol and tridecyl phenol.
9. The well acidizing fluid of claim 8, wherein the acid used to form the acidic solution is selected from the group consisting of:
hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, citric acid and mixtures thereof.
hydrochloric acid, hydrofluoric acid, formic acid, acetic acid, citric acid and mixtures thereof.
10. The well acidizing fluid of claim 9, wherein the rosin acid is selected from the group consisting of abietic, sapietic, pimaric acids, and mixtures thereof.
11. A well acidizing fluid of the type used in treating subterranean formations in the vicinity of a ferrous metal lined borehole penetrating the formation, the acidizing fluid comprising:
an aqueous solution of an acid present in an amount effective to increase the permeability of the formation being treated;
a corrosion inhibitor composition added to the acid solution in an amount effective to reduce the corrosive effect of the acid solution on the ferrous metal, the corrosion inhibitor composition comprising a mixture of the following components by weight percent, based on the total weight of corrosion inhibitor:
a complex substituted keto-amine which is a condensation product prepared by a Mannich reaction of formaldehyde, primary amines and ketones, the complex substituted Keto-amine being present in the range from about 30-40 % by weight;
an acetylenic alcohol, wherein the acetylenic alcohol has the general formula:
wherein R1, R2 and R3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals, the acetylenic alcohol being present in the range from about 5-25 % by weight;
an alkanol, present in the range from about 10-20 weight percent;
a rosin acid component, present in the range from about 1-10 weight percent; and a non-ionic surfactant, present in the range from about 5-20 weight percent;
the well acidizing fluid also having added thereto an antimony compound present in an amount effective to provide an antimony concentration of from about 0.0007 to about 0.04 molar solution to the corrosive acid.
an aqueous solution of an acid present in an amount effective to increase the permeability of the formation being treated;
a corrosion inhibitor composition added to the acid solution in an amount effective to reduce the corrosive effect of the acid solution on the ferrous metal, the corrosion inhibitor composition comprising a mixture of the following components by weight percent, based on the total weight of corrosion inhibitor:
a complex substituted keto-amine which is a condensation product prepared by a Mannich reaction of formaldehyde, primary amines and ketones, the complex substituted Keto-amine being present in the range from about 30-40 % by weight;
an acetylenic alcohol, wherein the acetylenic alcohol has the general formula:
wherein R1, R2 and R3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals, the acetylenic alcohol being present in the range from about 5-25 % by weight;
an alkanol, present in the range from about 10-20 weight percent;
a rosin acid component, present in the range from about 1-10 weight percent; and a non-ionic surfactant, present in the range from about 5-20 weight percent;
the well acidizing fluid also having added thereto an antimony compound present in an amount effective to provide an antimony concentration of from about 0.0007 to about 0.04 molar solution to the corrosive acid.
12. The well acidizing fluid of claim 11, wherein the acetylenic alcohol is propargyl alcohol.
13. The well acidizing fluid of claim 12, wherein the alkanol is isopropyl alcohol.
14. The well acidizing fluid of claim 13, wherein the non-ionic surfactant is an ethoxylated alkyl phenol.
15. The well acidizing fluid of claim 14, wherein the antimony compound is antimony trioxide.
16. A method of inhibiting the corrosivity of an acidic solution used in treating subterranean formations at elevated temperatures in the vicinity of a ferrous metal lined borehole penetrating the formation, which method comprises adding to the corrosive acidic solution an inhibiting effective amount of a corrosion inhibitor composition comprising a mixture of the following components by weight percent, based on the total weight of corrosion inhibitor:
a complex substituted keto-amine which is a condensation product prepared by a Mannich reaction of formaldehyde, primary amines and ketones, the complex substituted keto-amine being present in the range from about 30-40 % by weight;
an acetylenic alcohol, wherein the acetylenic alcohol has the general formula:
wherein R1, R2 and R3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals, the acetylenic alcohol being present in the range from about 5-25% by weight;
an alkanol, present in the range from about 10-20% by weight;
a rosin acid component, present in the range from about 1-10% by weight; and a non-ionic surfactant, present in the range from about 5-20% by weight;
the well acidizing fluid also having added thereto an antimony compound present in an amount effective to provide an antimony concentration of from about 0.0007 to about 0.04 molar solution to the corrosive acid.
a complex substituted keto-amine which is a condensation product prepared by a Mannich reaction of formaldehyde, primary amines and ketones, the complex substituted keto-amine being present in the range from about 30-40 % by weight;
an acetylenic alcohol, wherein the acetylenic alcohol has the general formula:
wherein R1, R2 and R3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals, the acetylenic alcohol being present in the range from about 5-25% by weight;
an alkanol, present in the range from about 10-20% by weight;
a rosin acid component, present in the range from about 1-10% by weight; and a non-ionic surfactant, present in the range from about 5-20% by weight;
the well acidizing fluid also having added thereto an antimony compound present in an amount effective to provide an antimony concentration of from about 0.0007 to about 0.04 molar solution to the corrosive acid.
17. The method of claim 16, wherein the complex substituted keto-amine is selected from the group consisting of:
2-heptadecenyl-1-(N-butanone-3)-aminoethyl imidazoline dihydrochloride;
5-methyl-2-hexadecyl-1-(N-alpha-methyl-cyclohexanone)-aminoisopropyl imidazoline sulfate;
2-heptadecyl-1-(N-4-methyl, pentanone-3)-aminoethyl imidazoline dihydrochloride;
2-undecyl-1-(N-butanone-3)-aminoethyl imidazonline dihydrochloride;and 2-undecyl-1-(N-phenyl-3, propanone-3)-aminoethyl imidazoline dihydrochloride.
2-heptadecenyl-1-(N-butanone-3)-aminoethyl imidazoline dihydrochloride;
5-methyl-2-hexadecyl-1-(N-alpha-methyl-cyclohexanone)-aminoisopropyl imidazoline sulfate;
2-heptadecyl-1-(N-4-methyl, pentanone-3)-aminoethyl imidazoline dihydrochloride;
2-undecyl-1-(N-butanone-3)-aminoethyl imidazonline dihydrochloride;and 2-undecyl-1-(N-phenyl-3, propanone-3)-aminoethyl imidazoline dihydrochloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56896490A | 1990-08-17 | 1990-08-17 | |
| US568,964 | 1995-12-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2049365A1 true CA2049365A1 (en) | 1992-02-18 |
Family
ID=24273504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2049365 Abandoned CA2049365A1 (en) | 1990-08-17 | 1991-08-16 | Acid inhibitor composition for use in well acidizing operations |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2049365A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571452A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气集团公司 | Acidizing corrosion inhibitor applicable to high temperature of 140 to 160 DEG C, and preparation and application thereof |
-
1991
- 1991-08-16 CA CA 2049365 patent/CA2049365A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571452A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气集团公司 | Acidizing corrosion inhibitor applicable to high temperature of 140 to 160 DEG C, and preparation and application thereof |
| CN103571452B (en) * | 2012-07-26 | 2016-02-10 | 中国石油天然气集团公司 | One is applicable to 140 DEG C ~ 160 DEG C high-temperature acidification corrosion inhibitors and Synthesis and applications thereof |
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