CA1201282A - Well completion fluid compositions - Google Patents
Well completion fluid compositionsInfo
- Publication number
- CA1201282A CA1201282A CA000416810A CA416810A CA1201282A CA 1201282 A CA1201282 A CA 1201282A CA 000416810 A CA000416810 A CA 000416810A CA 416810 A CA416810 A CA 416810A CA 1201282 A CA1201282 A CA 1201282A
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- Prior art keywords
- composition
- iodide
- bromide
- alkyl
- chloride
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/22—Synthetic organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
ABSTRACT
A composition and method for well completion and work-over. The composition comprises water, various halogen salts and an acetylenic alcohol. Optionally, other ingredients can be added to the composition. The method is carried out by contacting the well at sufficient hydrostatic pressure to control the well.
A composition and method for well completion and work-over. The composition comprises water, various halogen salts and an acetylenic alcohol. Optionally, other ingredients can be added to the composition. The method is carried out by contacting the well at sufficient hydrostatic pressure to control the well.
Description
.LL COMPLETION FLUID COMPOSITIONS
This invention relates to well completion and -~orkover fluid compositions and more particularly to a high density well completion and workover fluid composition that may be employed in petroleum recovery operations without excessive corrosion to ferrous metal tubing and pipe with which the composition may come into contact.
Current practice when completing wells, such as oil and gas wells, is to have drilling fluid, such as mud, salt water, water, or oil, in the well casing and to perforate the _asing with a bullet shaped charge, or chemical or punch-type perforator. When the pressure of the formation traversed by the well exceeds the hydrostatic pressure of the column of oil or water at the completion depth, it is customary to use a composition with a density great enough to exceed the for-mation pressure in order to control the well while perforat-ing the casing in performing other routine completion and workover operations. These compositions are prepared by dis-solving certain inorganic salts in water.
These compositions, which have been employed during completion and workover operations, have certain undesirable consequences. For example, these compositions are usually somewhat corrosive and, thereore, cause corrosion to the ferrous metal conduits with which the composition comes in contact. This problem is particularly acute in petroleum "
recovery operations which require a high density composition as the increased concentration ofsa~sin the fluid composi-tion result in greater corrosion damage to the ferrous con-duits.
For various reasons, it has become the practice in the petroleum industry to drill deeper and deeper wells and very often also to complete these wells at a plurality of zonesA
This, of course, has presented additional new unique prob-lems in the art of completing and producing wells. Also, the closely related problems of workover on wells has been greatly magnified by the advent of and specifically in mul-tiple completion wells which is at least in part due to prior completion factors. For example, after completing operations on an oil well to place it into production, a campletion fluid again is employed to fill the annular space between the casing and the tubing above packers ard left there throughout the life of the well or until rework ing is required.
The purpose of using such annulus or filled-up fluids to fill the annulus space between tubing and casing above the packer after a well is completed and producing is to maintain a hydrostatic pressure at the top of the packer.
A pressure desired at such poin-ts is one slightly greater than the highest pressure of all the producing formations.
In this way, the hydrocarbons being produced exert only a slightly lesser pressure on the bottom side of the packer than the completion fluid exerts on the top side of the packer.
Thus, by reducing the differential pressure between the top and bottom of the packer, the crude oil or other fluids exit-ing from the formation will not leak or bleed around the packer and/or control of the well will not be lost. The dis-advantages and deleterious consequences of bleeding around packers by such fluids are well known to those skilled in the art. The consequences of losing control of the well are stlll better known. Similarly and especially with regard to multiple completion wells, the consequences of a completion fluid which is corrosive to ferrous metals is well known and appreciated by those skilled in the art.
In drilling deeper and deeper wells in search for petro-leum producing formations, the temperatures encountered have increased to an extent that difficulties nonexistent thereto-fore have been encountered. Temperatures in the order of 200 to 250F or even higher may be encountered in oil and gas wells. At these temperatures, the completion fluids may form corrosive fluids which will damage ferrous metal tubing and pipe with which it may come into contact. It is, therefore, desirable to provide a well completion fluid which will be noncorrosive to ferrous metal conduits wi-th which i-t may come in contact.
Tempera-ture, as a rule, increases literally with depth.
This invention relates to well completion and -~orkover fluid compositions and more particularly to a high density well completion and workover fluid composition that may be employed in petroleum recovery operations without excessive corrosion to ferrous metal tubing and pipe with which the composition may come into contact.
Current practice when completing wells, such as oil and gas wells, is to have drilling fluid, such as mud, salt water, water, or oil, in the well casing and to perforate the _asing with a bullet shaped charge, or chemical or punch-type perforator. When the pressure of the formation traversed by the well exceeds the hydrostatic pressure of the column of oil or water at the completion depth, it is customary to use a composition with a density great enough to exceed the for-mation pressure in order to control the well while perforat-ing the casing in performing other routine completion and workover operations. These compositions are prepared by dis-solving certain inorganic salts in water.
These compositions, which have been employed during completion and workover operations, have certain undesirable consequences. For example, these compositions are usually somewhat corrosive and, thereore, cause corrosion to the ferrous metal conduits with which the composition comes in contact. This problem is particularly acute in petroleum "
recovery operations which require a high density composition as the increased concentration ofsa~sin the fluid composi-tion result in greater corrosion damage to the ferrous con-duits.
For various reasons, it has become the practice in the petroleum industry to drill deeper and deeper wells and very often also to complete these wells at a plurality of zonesA
This, of course, has presented additional new unique prob-lems in the art of completing and producing wells. Also, the closely related problems of workover on wells has been greatly magnified by the advent of and specifically in mul-tiple completion wells which is at least in part due to prior completion factors. For example, after completing operations on an oil well to place it into production, a campletion fluid again is employed to fill the annular space between the casing and the tubing above packers ard left there throughout the life of the well or until rework ing is required.
The purpose of using such annulus or filled-up fluids to fill the annulus space between tubing and casing above the packer after a well is completed and producing is to maintain a hydrostatic pressure at the top of the packer.
A pressure desired at such poin-ts is one slightly greater than the highest pressure of all the producing formations.
In this way, the hydrocarbons being produced exert only a slightly lesser pressure on the bottom side of the packer than the completion fluid exerts on the top side of the packer.
Thus, by reducing the differential pressure between the top and bottom of the packer, the crude oil or other fluids exit-ing from the formation will not leak or bleed around the packer and/or control of the well will not be lost. The dis-advantages and deleterious consequences of bleeding around packers by such fluids are well known to those skilled in the art. The consequences of losing control of the well are stlll better known. Similarly and especially with regard to multiple completion wells, the consequences of a completion fluid which is corrosive to ferrous metals is well known and appreciated by those skilled in the art.
In drilling deeper and deeper wells in search for petro-leum producing formations, the temperatures encountered have increased to an extent that difficulties nonexistent thereto-fore have been encountered. Temperatures in the order of 200 to 250F or even higher may be encountered in oil and gas wells. At these temperatures, the completion fluids may form corrosive fluids which will damage ferrous metal tubing and pipe with which it may come into contact. It is, therefore, desirable to provide a well completion fluid which will be noncorrosive to ferrous metal conduits wi-th which i-t may come in contact.
Tempera-ture, as a rule, increases literally with depth.
2~
~anv factors affecting temperature may vary in subterranean locations and the subterranean temperatures even in comparably close locations may vary considerably. The occurence of such and the reasons, therefore, are well known in the art. Thus, despite the general rule that temperature increases with depth, comparably high temperatures are sometimes encountered at relatively shallow depths, for example, at 3,000 feet.
At depths beginning at about 15,000 feet, high temperatures are encountered without exception regardless of location.
High tempexa-tures, then, may be encountered at a depth below 3,000 feet. These temperatures, when encountered regardless of depth, extenuate or accelerate the disadvan-tages of prior art completion and packer fluids In an effort to overcome the foregoing problems, high density salt solutions for use as well completion fluid compositions has been proposed. For instance, United States Patent 3,126,950 discloses a completion packer fluid made up of a water solution of calcium chloride and zinc chloride and optionally a corrosion inhibitor. United States Patent 4,292,183 discloses a high density fluid composition consist-ing of zinc bromide and calcium bromide in water having a density in the range of about 14.5 up to 18.0 pounds per gallon and a pH in the range of 3.5 up to 6Ø
These high density fluid compositions have had limited utility. Severe downhole corrosion problems and corrosion l of 1~3 to above ground equipmen-t has been encountered with their use.
the present invention provides a solution for, or at least mitigates the above described problem. The present invention provides a new well completion composition and a method for use of said composi-tion. Thus, in accordance with the broad aspect of the concept of the invention, there is provided a composition for use as a well completion, pack-ing and perforation medium comprising water; a salt selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, ammonium chloride, ammonium bro-mide, ammonium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potas-sium iodide, calcil~m chloride, calcium bromide, calcium iodide, zinc chloride, zinc bromide and zinc iodide and mix tures thereof; and, a compound selected from the group con-sisting o.f acetylenic alcohols having the general formula:
H - C - C - C - OH
P' wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said composition has a density of about 9.0 pounds to abou-t 21.5 pounds per gallon of composition.
Optionally other ingredien-ts may be added to the above de-scribed compos1tion. For instance, an organic amine selected ~3~2~2 from the group consisting of mono, di and tri-alkyl amines having from about two to about six carbon atoms in each al.~yl moiety, six membered N-heterocyclic amines, quinolines and quaternized derivatives of quinolines, quaternized pyri-dines, alkyl pyridines having from one to five nuclear alkyl substituents per pyridine moiety wherein said alkyl substi-tuents have from one to 12 carbon atoms and mixtures thereof may be added.
When desixed, an acid selected from the group consist-ing of formic acid, acetic acid, proprionic acid, butyric, glycolic acid and mixtures thereof may be added to the above described composition. The method of the invention comprises contacting the well at sufficient hydrostatic pressure with the composi-tion of the invention.
When the above described method of completion of work-over of wells is employed, the composition is relatively non-corrosive to the ferrous metal conduits with which it comes in contact.
The salts, which may be used in the practice of the present invention, function as weighting agents and increase corrosion inhibition. These salts are presented in the follow-ing Table.
TAsLE I
Salts Suitable as Weighting Agents _ tame FormulaSpecific Gravity Aluminum Bromide AlBr3 3.01 Aluminum Chloride AlCl3 2.44 Aluminum Iodide AlI3 3.98 Ammonium Bromide NH4Br 2.33 Ammonium Chloride NH~Cl 1.53 Ammonium Iodide MH4I 2.51 Calcium Bromide 2 Calcium Chloride CaC12 2.15 Calcium Iodide CaI2 3.96 Potassium Bromide KBr 2.75 Potassium Chloride XC1 1.98 Potassium Iodide KI 3.13 Sodium Bromide NaBr 3.20 Sodium Chloride NaC1 2.16 Sodium Iodide NaI 3.67 Zinc Bromide ZnBr2 2.56 Zinc Chloride ZnC12 2.91 Zinc Iodide ZnI2 4.66 The preferred salts and combinations of salts for use in the present invention are sodium chloride, calcium chloride, calcium bromide and the following combinations oE salts:
sodium chloride and calcium chloride, calcium chloride and or tr calcium bromide, calcium chloride and zinc chloride, calcium bromide and zinc bromide, calcium bromide, zinc bromide and zinc chloride, and zinc chloride and zinc bromide.
The most preferred salts and combinations of salts for 5 use in the invention are calcium chloride, calcium chloride and calcium bromide, calcium bromide and zinc chloride, and calcium bromide and zinc bromide.
The amount of these sal-ts used in the composition of the invention will be the amount necessary to achieve a composition having a density of about 9.0 pounds -to abou-t 21.5 pounds per gallon of composition.
The acetylenic alcohols which inhibit corrosion of ferrous metal and which may be employed in accordance with the present invention have the general formula:
R
H - C - C - C - Ox R
wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical. Examples of suitable acetylenic compounds include methylbutynol, ethyloctynol, methylpentynol, 3, 4 di-hydroxy 1-butyne, 1 ethynylcyclohexanol, 3-methyl-1-nonyn-3-ol, 2-methyl-3-butyn-2-ol, also 1-propyn-3-ol, 1-butyn-3-ol, 1-pentyn-3-ol, 1-heptyn-3-ol, 1-octyn-3-ol, 1-nonyl-3-ol, 1-decyn-3-ol, 3-~2, 4, 6-trimethyl-3-cyclohexenyl)-1-propyne-
~anv factors affecting temperature may vary in subterranean locations and the subterranean temperatures even in comparably close locations may vary considerably. The occurence of such and the reasons, therefore, are well known in the art. Thus, despite the general rule that temperature increases with depth, comparably high temperatures are sometimes encountered at relatively shallow depths, for example, at 3,000 feet.
At depths beginning at about 15,000 feet, high temperatures are encountered without exception regardless of location.
High tempexa-tures, then, may be encountered at a depth below 3,000 feet. These temperatures, when encountered regardless of depth, extenuate or accelerate the disadvan-tages of prior art completion and packer fluids In an effort to overcome the foregoing problems, high density salt solutions for use as well completion fluid compositions has been proposed. For instance, United States Patent 3,126,950 discloses a completion packer fluid made up of a water solution of calcium chloride and zinc chloride and optionally a corrosion inhibitor. United States Patent 4,292,183 discloses a high density fluid composition consist-ing of zinc bromide and calcium bromide in water having a density in the range of about 14.5 up to 18.0 pounds per gallon and a pH in the range of 3.5 up to 6Ø
These high density fluid compositions have had limited utility. Severe downhole corrosion problems and corrosion l of 1~3 to above ground equipmen-t has been encountered with their use.
the present invention provides a solution for, or at least mitigates the above described problem. The present invention provides a new well completion composition and a method for use of said composi-tion. Thus, in accordance with the broad aspect of the concept of the invention, there is provided a composition for use as a well completion, pack-ing and perforation medium comprising water; a salt selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, ammonium chloride, ammonium bro-mide, ammonium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potas-sium iodide, calcil~m chloride, calcium bromide, calcium iodide, zinc chloride, zinc bromide and zinc iodide and mix tures thereof; and, a compound selected from the group con-sisting o.f acetylenic alcohols having the general formula:
H - C - C - C - OH
P' wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said composition has a density of about 9.0 pounds to abou-t 21.5 pounds per gallon of composition.
Optionally other ingredien-ts may be added to the above de-scribed compos1tion. For instance, an organic amine selected ~3~2~2 from the group consisting of mono, di and tri-alkyl amines having from about two to about six carbon atoms in each al.~yl moiety, six membered N-heterocyclic amines, quinolines and quaternized derivatives of quinolines, quaternized pyri-dines, alkyl pyridines having from one to five nuclear alkyl substituents per pyridine moiety wherein said alkyl substi-tuents have from one to 12 carbon atoms and mixtures thereof may be added.
When desixed, an acid selected from the group consist-ing of formic acid, acetic acid, proprionic acid, butyric, glycolic acid and mixtures thereof may be added to the above described composition. The method of the invention comprises contacting the well at sufficient hydrostatic pressure with the composi-tion of the invention.
When the above described method of completion of work-over of wells is employed, the composition is relatively non-corrosive to the ferrous metal conduits with which it comes in contact.
The salts, which may be used in the practice of the present invention, function as weighting agents and increase corrosion inhibition. These salts are presented in the follow-ing Table.
TAsLE I
Salts Suitable as Weighting Agents _ tame FormulaSpecific Gravity Aluminum Bromide AlBr3 3.01 Aluminum Chloride AlCl3 2.44 Aluminum Iodide AlI3 3.98 Ammonium Bromide NH4Br 2.33 Ammonium Chloride NH~Cl 1.53 Ammonium Iodide MH4I 2.51 Calcium Bromide 2 Calcium Chloride CaC12 2.15 Calcium Iodide CaI2 3.96 Potassium Bromide KBr 2.75 Potassium Chloride XC1 1.98 Potassium Iodide KI 3.13 Sodium Bromide NaBr 3.20 Sodium Chloride NaC1 2.16 Sodium Iodide NaI 3.67 Zinc Bromide ZnBr2 2.56 Zinc Chloride ZnC12 2.91 Zinc Iodide ZnI2 4.66 The preferred salts and combinations of salts for use in the present invention are sodium chloride, calcium chloride, calcium bromide and the following combinations oE salts:
sodium chloride and calcium chloride, calcium chloride and or tr calcium bromide, calcium chloride and zinc chloride, calcium bromide and zinc bromide, calcium bromide, zinc bromide and zinc chloride, and zinc chloride and zinc bromide.
The most preferred salts and combinations of salts for 5 use in the invention are calcium chloride, calcium chloride and calcium bromide, calcium bromide and zinc chloride, and calcium bromide and zinc bromide.
The amount of these sal-ts used in the composition of the invention will be the amount necessary to achieve a composition having a density of about 9.0 pounds -to abou-t 21.5 pounds per gallon of composition.
The acetylenic alcohols which inhibit corrosion of ferrous metal and which may be employed in accordance with the present invention have the general formula:
R
H - C - C - C - Ox R
wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical. Examples of suitable acetylenic compounds include methylbutynol, ethyloctynol, methylpentynol, 3, 4 di-hydroxy 1-butyne, 1 ethynylcyclohexanol, 3-methyl-1-nonyn-3-ol, 2-methyl-3-butyn-2-ol, also 1-propyn-3-ol, 1-butyn-3-ol, 1-pentyn-3-ol, 1-heptyn-3-ol, 1-octyn-3-ol, 1-nonyl-3-ol, 1-decyn-3-ol, 3-~2, 4, 6-trimethyl-3-cyclohexenyl)-1-propyne-
3-ol~
In many instances, the corrcsion protection of the com-position of the invention may be increased by adding an organic amine to the above described acetylenic alcohol.
mines that are suitable for this puxpose include an organic amine selected from the group consisting of mono,di and tri-alkyl amines having from ahout two to abou-t six carbon atoms in each alkyl moiety, six membered N-heterocyclic amines, quinolines and quaternized derivatives of quinolines, alkyl pyridines having from zero to six nuclear alkyl substituents per pyridine moiety wherein said alkyl substituents have from one to 12 carbon atoms and mixtures thereof Examples of these amines include ethylamine, diethylamine, triethyl-amine, propylamine, dipropylamine, tripropylamine, mono, di, tributylamine, mono, di and tripentylamine, mono, di and trihexylamine and isomers of these such as isopropylamine, tertiarybutylamine, aniline, dehydroabiethylamine, pyridine, quaternized derivativesof pyridine, nitro picoline, methyl quinoline alkyl pyridines such as alkyl pyridines having from 1 to 5 nuclear alkyl substituents per pyridine moiety, quinolines, quaternized derivatives of quinolines alkyl quinolines and mixtures.
In some instances, it may be desirable -to include an acid in the composition of the inven-tion. The acid, when present in the composition of the invention will remove acid soluble scales in the well bore or open perforations in the well bore. when an acid is desired, suitable acids which may be employed include formic acid, glycolic acid, acetic acid, proprionic acid, butvric acid and mixtures thereof.
As stated earlier, the acetylenic alcohol maY be used alone with the composition of the invention or an organic amine may be combined with an acetylenic alcohol. The relative proportions of acetylenic alcohol and organic amine may vary over a wide range. Furthermore, it has been found that the concentration of acetylenic alcohol and the concen-tration of the organic amine are not interdependent and thus significant improvement in corrosion protection can be ob-tained by varying the concentration of one of the components without varying that of the other. In general, the acety-lenic alcohol concentration will vary from about 0.2 to about 5.0 percent by volume of the composition. However, lower or higher concentrations will still be effective when an organic amine is added to the composition of the inven-tion. Thus, the amine concentration will vary over a wide range with really no upper or lower limitations. General, the organic amine concentration when desired will vary from about 0.05 to 3.0 volume percent of the composition of the invention.
A particularly affective blend containing an amine and acetylenic alcohol is set forth below.
~'3~
slend I
Chemical: Percent by vol.
Pure propargyl alcohol_ _ _ _ _ _ _ _ _ _ _ _ _ 33.94 Crude propargyl alcohol _ _ _ _ _ _ _ _ _ _ _ 11.31 Ethyl octynol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 16.97 High alkyl pyridines_ _ _ _ _ _ _ _ _ _ _ _ _ _ 3.85 Formladehyde (55%) in methanol_ _ _ _ _ _ _ _ _ 33.94 Another efective composition containing an amine and acetylenic alcohol is yiven below.
Blend II
Chemical: Percent by vol.
Pure pro~argyl alcohol_ _ _ _ _ _ _ _ _ _ _ _ _ 33.94 Crude propargyl alcohol _ _ _ _ _ _ _ _ _ _ _ 11.31 Ethyl octynol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 16.97 ~l~yl pyridines _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 3.85 Diacetone alcohol 33.94 .. _ _ _ Another effective blend containing an amine and acety-lenic alcohol is given below. This blend is very effective when the denslty of the composition of the invention is 20 from about 15.0 pounds per gallon to about 16.5 pounds per gallon and the salts utilized are calcium bromide and zinc chloride and when the density is from about 16.5 pounds per gallon to about 19.2 pounds per gallon and the salts uti.lized are calcium bromide and zinc bromide.
Blend III
Chemical: Percent by vol.
Cnlde quaternized quinoline _ _ _ _ _ _ _ _ _ _ 56.G0 Propargyl alcohol _ 21.00_ _ _ _ _ _ _ _ _ _ _ _ _ Ethyl Octynol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 13.00 15 moles of ethylene oxide adduct of nonyl phenol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 10.00 Cu2I2 _ _ _ _ 0.024 grams per milliter of composition The preferred density of the composition of the inven-tion is from about 16.5 to about 21.5 pounds per gallon of composition.
The concentration of the acid, when employed in the composition of the invention will vary over a great range.
Generally the range of acid is from .2 percent to about 40 volume percent of the composition. The most preferred acid concentration is from abou-t 3 to about 17 volume percent of the composition.
The following examples will serve to more comprehensively illustrate the principles of the invention but in being directed to certain specific compounds in process steps and conditions are not intended to limit the bounds of the invention.
EXAMPLE I
In order to compare -the corrosion inhibiting ability of the composition of -the invention, various samples containing 10 percent by volume of formic acid or acetic acid were pre-~30~
pared with various amounts of calcium chloride. Tests 1 through 5 contained slend I as an inhibitor. slend I, as disclosed earlier, contains the rollowing inyredients: pure propargyl alcohol, crude propargyl alcohol, ethyl octynol, high alXyl pyridines and formaldehyde (55%~ in methanol.
Tests 6 through 10 contained, as an inhibitor, Blend III. Blend III was made up of crude quaternized quinoline, propargyl alcohol, ethyl octynol, and 15 moles of ethylene oxide adduct of nonyl phenol and Cu2I2.
A coupon of A~I Type N-80 steel was placed in the acid composition for a period of eight hours at 200Fo All tests were carried out under atmospheric conditions.
The loss of weight in pounds per square foot was cal-culated as follows:
Corrosion Loss lbs/ft _ _ 455 lg X Surface Area of Coupon in Results of these tests are shown in Table II.
TABLE II
Volume - Surfaco Area Ratio - 25 cc./in.
Corrosion Loss lbs/ft Test InhibitorCaCl~Formic A id Acetlc Acid 1 Blend I - 0.287 0.296 2 Blend I9.5 lhs/gal 0.052 0.029 3 Blend I10.0 lbs/gal 0.023 0.025
In many instances, the corrcsion protection of the com-position of the invention may be increased by adding an organic amine to the above described acetylenic alcohol.
mines that are suitable for this puxpose include an organic amine selected from the group consisting of mono,di and tri-alkyl amines having from ahout two to abou-t six carbon atoms in each alkyl moiety, six membered N-heterocyclic amines, quinolines and quaternized derivatives of quinolines, alkyl pyridines having from zero to six nuclear alkyl substituents per pyridine moiety wherein said alkyl substituents have from one to 12 carbon atoms and mixtures thereof Examples of these amines include ethylamine, diethylamine, triethyl-amine, propylamine, dipropylamine, tripropylamine, mono, di, tributylamine, mono, di and tripentylamine, mono, di and trihexylamine and isomers of these such as isopropylamine, tertiarybutylamine, aniline, dehydroabiethylamine, pyridine, quaternized derivativesof pyridine, nitro picoline, methyl quinoline alkyl pyridines such as alkyl pyridines having from 1 to 5 nuclear alkyl substituents per pyridine moiety, quinolines, quaternized derivatives of quinolines alkyl quinolines and mixtures.
In some instances, it may be desirable -to include an acid in the composition of the inven-tion. The acid, when present in the composition of the invention will remove acid soluble scales in the well bore or open perforations in the well bore. when an acid is desired, suitable acids which may be employed include formic acid, glycolic acid, acetic acid, proprionic acid, butvric acid and mixtures thereof.
As stated earlier, the acetylenic alcohol maY be used alone with the composition of the invention or an organic amine may be combined with an acetylenic alcohol. The relative proportions of acetylenic alcohol and organic amine may vary over a wide range. Furthermore, it has been found that the concentration of acetylenic alcohol and the concen-tration of the organic amine are not interdependent and thus significant improvement in corrosion protection can be ob-tained by varying the concentration of one of the components without varying that of the other. In general, the acety-lenic alcohol concentration will vary from about 0.2 to about 5.0 percent by volume of the composition. However, lower or higher concentrations will still be effective when an organic amine is added to the composition of the inven-tion. Thus, the amine concentration will vary over a wide range with really no upper or lower limitations. General, the organic amine concentration when desired will vary from about 0.05 to 3.0 volume percent of the composition of the invention.
A particularly affective blend containing an amine and acetylenic alcohol is set forth below.
~'3~
slend I
Chemical: Percent by vol.
Pure propargyl alcohol_ _ _ _ _ _ _ _ _ _ _ _ _ 33.94 Crude propargyl alcohol _ _ _ _ _ _ _ _ _ _ _ 11.31 Ethyl octynol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 16.97 High alkyl pyridines_ _ _ _ _ _ _ _ _ _ _ _ _ _ 3.85 Formladehyde (55%) in methanol_ _ _ _ _ _ _ _ _ 33.94 Another efective composition containing an amine and acetylenic alcohol is yiven below.
Blend II
Chemical: Percent by vol.
Pure pro~argyl alcohol_ _ _ _ _ _ _ _ _ _ _ _ _ 33.94 Crude propargyl alcohol _ _ _ _ _ _ _ _ _ _ _ 11.31 Ethyl octynol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 16.97 ~l~yl pyridines _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 3.85 Diacetone alcohol 33.94 .. _ _ _ Another effective blend containing an amine and acety-lenic alcohol is given below. This blend is very effective when the denslty of the composition of the invention is 20 from about 15.0 pounds per gallon to about 16.5 pounds per gallon and the salts utilized are calcium bromide and zinc chloride and when the density is from about 16.5 pounds per gallon to about 19.2 pounds per gallon and the salts uti.lized are calcium bromide and zinc bromide.
Blend III
Chemical: Percent by vol.
Cnlde quaternized quinoline _ _ _ _ _ _ _ _ _ _ 56.G0 Propargyl alcohol _ 21.00_ _ _ _ _ _ _ _ _ _ _ _ _ Ethyl Octynol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 13.00 15 moles of ethylene oxide adduct of nonyl phenol _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 10.00 Cu2I2 _ _ _ _ 0.024 grams per milliter of composition The preferred density of the composition of the inven-tion is from about 16.5 to about 21.5 pounds per gallon of composition.
The concentration of the acid, when employed in the composition of the invention will vary over a great range.
Generally the range of acid is from .2 percent to about 40 volume percent of the composition. The most preferred acid concentration is from abou-t 3 to about 17 volume percent of the composition.
The following examples will serve to more comprehensively illustrate the principles of the invention but in being directed to certain specific compounds in process steps and conditions are not intended to limit the bounds of the invention.
EXAMPLE I
In order to compare -the corrosion inhibiting ability of the composition of -the invention, various samples containing 10 percent by volume of formic acid or acetic acid were pre-~30~
pared with various amounts of calcium chloride. Tests 1 through 5 contained slend I as an inhibitor. slend I, as disclosed earlier, contains the rollowing inyredients: pure propargyl alcohol, crude propargyl alcohol, ethyl octynol, high alXyl pyridines and formaldehyde (55%~ in methanol.
Tests 6 through 10 contained, as an inhibitor, Blend III. Blend III was made up of crude quaternized quinoline, propargyl alcohol, ethyl octynol, and 15 moles of ethylene oxide adduct of nonyl phenol and Cu2I2.
A coupon of A~I Type N-80 steel was placed in the acid composition for a period of eight hours at 200Fo All tests were carried out under atmospheric conditions.
The loss of weight in pounds per square foot was cal-culated as follows:
Corrosion Loss lbs/ft _ _ 455 lg X Surface Area of Coupon in Results of these tests are shown in Table II.
TABLE II
Volume - Surfaco Area Ratio - 25 cc./in.
Corrosion Loss lbs/ft Test InhibitorCaCl~Formic A id Acetlc Acid 1 Blend I - 0.287 0.296 2 Blend I9.5 lhs/gal 0.052 0.029 3 Blend I10.0 lbs/gal 0.023 0.025
4 lend I10.5 lbs/gal 0.005 0.005 Blend I11.0 lbs/gal 0.005 0.004 6 Blend III - 0.029 0.019 7 Blend III 9.5 lbs/gal 0.009 0.013 8 Blend III 10.0 lbs/gal 0.003 0.009 9 Blend III 10.5 lbs~gal 0.003 0.002 Blend III 11.0 lbs/gal 0.002 0.002 Table II shows that the composition of the invention effectively reduced iron corrosion.
EXAMPLE II
In order to demonstrate the corrosion inhibiting ability of the composition of the invention, various samples of a 10 percent by volume acetic acid were prepared with various salts. The density of the samples was ten pounds per gallon of sample. Tests 4 through 6 and 8 contained Blend I as an inhibitor. The composition of this Blend is the same as dis-closed in Example I. Tests 1 through 3 and 7 utilized MBA
29 as an inhibitor. MBA 29 contained, as ingredients, 50 percent by volume crude quaternized quinoline and S0 percent by volume methyl butynol.
A coupon of API rrype ~-80 steel was placed in the acidic f composition for a period of six hours at 200F. All tests were carried out under atmospheric conditions. The corro-sion loss was calculated as in Example I.
The results of these tests are shown in Tahle III.
TABLE III
Volume - Surface Area Ratio - 25 cc./in.
___ Inhibitor Corrosion Loss Test Salt 1% v/v _ lbs/ft _ 1 AlC13 MBA29 0.004 2 NaBr MBA29 0.004 3 NH4I MBA29 0.003 4 AlC13 Blend I 0.009 NaBr Blend I 0.018 6 N~I Blend I 0.005 7 - MBA29 0.150 8 - Blend I 0.287 Table III shows that the composition of the invention reduced iron corrosion.
EXAMPLE III
In order to compare the corrosion inhibiting ability of the composition of the invention, a composition which had a density of 19.2 pounds per gallon was prepared. The salt u-tilized in preparing the composition was a mixture of zinc brcmide and calcium bromlde. A coupon of API Type N-80 steel was placed in the composition for a period of seven days at 26~F. All tests were carried out under atmospheric condi-tions.
Blend III was made up of the same componen-ts as de-scribed in Example I. Blend II was made up of pure g propargyl alcohol, crude propargyl alcohol, ethyl oc-tynol, alkyl pyridines and diacetone alcohol.
Test 9 could not be accurately calculated due to con-tamination of the sample during the test.
Results of these tests are shown in Table IV.
TABLE IV
~Jolume - Surface Area Ratio 25 cc./in.
Inhibitor Corrosion2Loss Test l V/V lbs/ft 1 - 0.102 2 Propargyl alcohol 0.058 3 Methyl butynol 0.019 4 Me-thyl pentynol 0.056 50 percent by volume hexynol0.026 6 Ethyloctynol and 10 percent by volume 0.098 of lS moles of ethylene oxide adduct of nonyl phenol 7 50 percent by volume propargyl alcohol 0.013 & 50 percent by volume quaternary quinollne 8 50 percent by volume methyl butynol 0.011 50 percent by volume quaternary quinoline 9 50 percent by volume methyl pentynol 0.105 & 50 percent by volume quaternary quinoline 50 percent by volume propargyl alcohol 0.044 & 50 percent by volume pyridine 11 mixture of acetylenic alcohol, cyclic 0.052 amine and linear amines 12 mixture of acetylenic alcohol, cyclic 0.050 amine and llnear amines 13 mixture of acetylenic alcohol, cylcic 0.048 amine and linear amines 14 mixture of acetylenic alcohol, cylcic 0.048 amine and linear amines 31end II 0.005 16 Blend II~ 0.007 Table IV shows that tne composition of the invention effectively reduced iron corrosion.
While certain embodiments of the invention have been described for illustrative purposes, the invention is not limited thereto. Various other modifications or embodiments of the invention will be apparent to those skilled in the art in view of this disclosure. Such modifications or embodi-ments are within the spirit and scope of the disclosure.
hat is claimed is:
EXAMPLE II
In order to demonstrate the corrosion inhibiting ability of the composition of the invention, various samples of a 10 percent by volume acetic acid were prepared with various salts. The density of the samples was ten pounds per gallon of sample. Tests 4 through 6 and 8 contained Blend I as an inhibitor. The composition of this Blend is the same as dis-closed in Example I. Tests 1 through 3 and 7 utilized MBA
29 as an inhibitor. MBA 29 contained, as ingredients, 50 percent by volume crude quaternized quinoline and S0 percent by volume methyl butynol.
A coupon of API rrype ~-80 steel was placed in the acidic f composition for a period of six hours at 200F. All tests were carried out under atmospheric conditions. The corro-sion loss was calculated as in Example I.
The results of these tests are shown in Tahle III.
TABLE III
Volume - Surface Area Ratio - 25 cc./in.
___ Inhibitor Corrosion Loss Test Salt 1% v/v _ lbs/ft _ 1 AlC13 MBA29 0.004 2 NaBr MBA29 0.004 3 NH4I MBA29 0.003 4 AlC13 Blend I 0.009 NaBr Blend I 0.018 6 N~I Blend I 0.005 7 - MBA29 0.150 8 - Blend I 0.287 Table III shows that the composition of the invention reduced iron corrosion.
EXAMPLE III
In order to compare the corrosion inhibiting ability of the composition of the invention, a composition which had a density of 19.2 pounds per gallon was prepared. The salt u-tilized in preparing the composition was a mixture of zinc brcmide and calcium bromlde. A coupon of API Type N-80 steel was placed in the composition for a period of seven days at 26~F. All tests were carried out under atmospheric condi-tions.
Blend III was made up of the same componen-ts as de-scribed in Example I. Blend II was made up of pure g propargyl alcohol, crude propargyl alcohol, ethyl oc-tynol, alkyl pyridines and diacetone alcohol.
Test 9 could not be accurately calculated due to con-tamination of the sample during the test.
Results of these tests are shown in Table IV.
TABLE IV
~Jolume - Surface Area Ratio 25 cc./in.
Inhibitor Corrosion2Loss Test l V/V lbs/ft 1 - 0.102 2 Propargyl alcohol 0.058 3 Methyl butynol 0.019 4 Me-thyl pentynol 0.056 50 percent by volume hexynol0.026 6 Ethyloctynol and 10 percent by volume 0.098 of lS moles of ethylene oxide adduct of nonyl phenol 7 50 percent by volume propargyl alcohol 0.013 & 50 percent by volume quaternary quinollne 8 50 percent by volume methyl butynol 0.011 50 percent by volume quaternary quinoline 9 50 percent by volume methyl pentynol 0.105 & 50 percent by volume quaternary quinoline 50 percent by volume propargyl alcohol 0.044 & 50 percent by volume pyridine 11 mixture of acetylenic alcohol, cyclic 0.052 amine and linear amines 12 mixture of acetylenic alcohol, cyclic 0.050 amine and llnear amines 13 mixture of acetylenic alcohol, cylcic 0.048 amine and linear amines 14 mixture of acetylenic alcohol, cylcic 0.048 amine and linear amines 31end II 0.005 16 Blend II~ 0.007 Table IV shows that tne composition of the invention effectively reduced iron corrosion.
While certain embodiments of the invention have been described for illustrative purposes, the invention is not limited thereto. Various other modifications or embodiments of the invention will be apparent to those skilled in the art in view of this disclosure. Such modifications or embodi-ments are within the spirit and scope of the disclosure.
hat is claimed is:
Claims (24)
1. A composition for use as a well completion and work-over operation comprising:
(a) water (b) a salt selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, ammonium chloride, ammonium bromide, ammonium iodide, sodium chloride, sodium bro-mide, sodium iodide, potassium chloride, potas-sium bromide, potassium iodide, calcium chlor-ide, calcium bromide, calcium iodide, zinc chloride, zinc bromide, zinc iodide and mix-tures thereof; and, (c) a compound selected from the group consist-ing of acetylenic alcohols having the gen-eral formula wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said composition has a density of about 9.0 pounds to about 21.5 pounds per gallon of composition.
(a) water (b) a salt selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, ammonium chloride, ammonium bromide, ammonium iodide, sodium chloride, sodium bro-mide, sodium iodide, potassium chloride, potas-sium bromide, potassium iodide, calcium chlor-ide, calcium bromide, calcium iodide, zinc chloride, zinc bromide, zinc iodide and mix-tures thereof; and, (c) a compound selected from the group consist-ing of acetylenic alcohols having the gen-eral formula wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said composition has a density of about 9.0 pounds to about 21.5 pounds per gallon of composition.
2. The composition recited in claim 1 further compris-ing an organic amine selected from the group consisting of mono, di and tri-alkyl amines having from about two to about six carbon atoms in each alkyl moiety, six membered N-hetero-cyclic amines, quinolines and quaternized derivatives of quinolines, quaternized derivatives of pyridines, alkyl pyridines having from one to five nuclear alkyl substituents per pyridine moiety wherein said alkyl substituents have from one to 12 carbon atoms and mixtures thereof.
3. The composition recited in claims 1 further comprising an acid selected from the group consisting of formic acid, acetic acid, proprionic acid, butyric acid, glycolic acid, and mixtures thereof and said acid is present in said composition in the range of from about .2 to about 40 volume percent of said compostion.
4. The composition recited in claims 1, 2 or 3 wherein said salt is calcium chloride.
5. The composition recited in claim 2 wherein said amine is selected from the group consisting of pyridines and quinolines.
6. The composition recited in claims 3 or 5 wherein said acid is acetic acid.
7. The composition recited in claims 1, 2 or 3 wherein said density of said composition is about 16.5 pounds to about 21.5 pounds per gallon of said composition.
19 3. The composition recited in claims 1 or 2 wherein said acetylenic alcohol is selected from the group consist-ing of methylbutynol, ethyloctynol, methylpentynol, 3, 4 dihydroxy 1-butyne, 1-ethynylcyclohexanol, 3-methyl-1-nonyn-3-ol, 2-methyl-3-butyn-2-ol, 1-propyn-3-ol, 1-butyn-3-ol, 1-pentyn-3-ol, 1-heptyn-e-ol, 1-octyn-3-ol, 1-nonyl-3-ol, 1-decyn-3-ol, 3-(2, 4, 6-trimethyl-3-cyclohexenyl)-1-propyne-3-ol and mixtures thereof.
9. The composition recited in claim 1 wherein the acetylenic alcohol is present in the range of from about 0.2 to 5.0 percent by volume of said composition.
10. A method of completing a well penetrating a sub-terranean formation comprising:
contacting said well at sufficient hydrostatic pres-sure to control the well a composition comprising (a) water (b) a salt selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, ammonium chloride, ammonium bromide, ammonium iodide, sodium chloride, sodium bro-mide, sodium iodide, potassium chloride, potas-sium bromide, potassium iodide, calcium chlor-ide, calcium bromide, calcium iodide, zinc chloride, zinc bromide, zinc iodide and mix-tures thereof; and, (c) a compound selected from the group consisting of acetylenic alcohols having the general formula wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said composition has a density of about 9.0 pounds to about 21.5 pounds per gallon of composition.
contacting said well at sufficient hydrostatic pres-sure to control the well a composition comprising (a) water (b) a salt selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, ammonium chloride, ammonium bromide, ammonium iodide, sodium chloride, sodium bro-mide, sodium iodide, potassium chloride, potas-sium bromide, potassium iodide, calcium chlor-ide, calcium bromide, calcium iodide, zinc chloride, zinc bromide, zinc iodide and mix-tures thereof; and, (c) a compound selected from the group consisting of acetylenic alcohols having the general formula wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said composition has a density of about 9.0 pounds to about 21.5 pounds per gallon of composition.
11. The method recited in claim 10 wherein said compo-sition further comprises an organic amine selected from the group consisting of mono, di and tri-alkyl amines hav-ing from about two to about six carbon atoms in each alkyl moiety, six membered N-heterocyclic amines, quinolines and quaternized derivatives of quinolines, quaternized deriva-tives of pyridines, alkyl pyridines having from one to five nuclear alkyl substituents per pyridine moiety wherein said alkyl substituents have from one to 12 carbon atoms and mixtures thereof.
12. The method recited in claim 11 wherein said compo-sition further comprises an acid selected from the group consisting of formic acid, acetic acid, glycolic acid, proprionic acid, butyric acid and mixtures thereof and said acid is present in said composition in the range of from about .2 to about 40 volume percent of said composi-tion.
13. The method recited in claims 10, 11 or 12 wherein said salt is calcium chloride.
14. The method recited in claim 11 wherein said amine is selected from the group consisting of pyridines and quinolines.
15. The method recited in claim 10 wherein said acid is acetic acid.
16. The method recited in claims 10, 11 or 12 wherein said density of said composition is about 16.5 pounds to about 21.5 pounds per gallon of composition.
17. The method recited in claims 10, 11 or 12 wherein the acetylenic alcohol is present in the range of from about 0.2 to 5.0 percent by volume of said composition.
18. The method recited in claims 10 or 11 wherein said acetylenic alcohol is selected from the group consist-ing of methylbutynol, ethyloctynol, methylpentynol, 3, 4 dehydroxy 1-butyne, 1-ethynylcyclohexanol, 3-methyl-1-nonyn-3-ol, 2-methyl-3-butyn-2-ol, 1-propyn-3-ol, 1-butyn-3-ol, 1-pentyn-3-ol, 1-heptyn-3-ol, 1-octyn-3-ol, 1-nonyl-3-ol, 1-decyn-3-ol, 3-(2, 4, 6-trimethyl-3-cyclohexenyl)-1-propyne-3-ol and mixtures thereof.
19. A method of inhibiting the corrosion of a iron sur-face in contact with an aqueous salt fluid said fluid con-taining salts selected from the group consisting of aluminum chloride, aluminum bromide, aluminum iodide, ammonium chlor-ide, ammonium bromide, ammonium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, zinc chloride, zinc bromide and zinc iodide and mixtures thereof comprising incorporating into said fluid a composition selected from the group consisting of acetylenic alcohols having the general formula:
wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said fluid has a density of about 9.0 pounds to about 21.5 pounds per gallon of composition.
wherein R is H, alkyl, phenyl, substituted phenyl, or hydroxy-alkyl radical wherein said fluid has a density of about 9.0 pounds to about 21.5 pounds per gallon of composition.
20. The method recited in claim 19, wherein said fluid further comprises an organic amine selected from the group consisting of mono, di and tri-alkyl amines having from about two to about six carbon atoms in each alkyl moiety, six membered N-heterocyclic amines, quinolines and quater-nized derivatives of quinolines, alkyl pyridines having from one to five nuclear alkyl substituents per pyridine moiety wherein said alkyl substituents have from one to 12 carbon atoms and mixtures thereof.
21. The method recited in claims 19 or 20, wherein said salt is calcium chloride.
22. The method recited in claim 20, wherein said amine is selected from the group consisting of pyridines and quinolines.
23. The method recited in claims 10, 19 or 20, wherein the acetylenic alcohol is present in the range of from about 0.2 to 5.0 percent by volume of said composition.
24. The method recited in claims 19 and 20, wherein said acetylenic alcohol is selected from the group consisting of methylbutynol, ethyloctynol, methylpentynol, 3, 4 dehydroxy 1-butyne, 1-ethynylcyclohexanol, 3-methyl-1-nonyn-3-ol, 2-methyl-3-butyn-2-ol, 1-propyn-3-ol, 1-butyn-3-ol, 1-pentyn-3-ol, 1-heptyn-3-ol, 1-octyn-3-ol, 1-nonyl-3-ol, 1-decyn-3-ol, 3-(2, 4, 6-trimethyl-2-cyclohexenyl)-1-propyne-3-ol and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33622081A | 1981-12-31 | 1981-12-31 | |
| US336,220 | 1981-12-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1201282A true CA1201282A (en) | 1986-03-04 |
Family
ID=23315093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416810A Expired CA1201282A (en) | 1981-12-31 | 1982-12-01 | Well completion fluid compositions |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA1201282A (en) |
| DE (1) | DE3247872A1 (en) |
| GB (1) | GB2112836A (en) |
| NL (1) | NL8204996A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1210928A (en) * | 1982-09-20 | 1986-09-09 | Arnold M. Singer | Process for removing contaminates from a well fluid and well system |
| US4552672A (en) * | 1984-06-21 | 1985-11-12 | Halliburton Company | Method and composition for acidizing subterranean formations |
| AU3404695A (en) * | 1994-07-27 | 1996-02-22 | Baker Hughes Incorporated | Drilling fluid additives for improved shale stabilization, the drilling fluid formed therefrom and method of using same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3126950A (en) * | 1964-03-31 | Steel coupons in | ||
| US3107221A (en) * | 1958-04-18 | 1963-10-15 | Dow Chemical Co | Corrosion inhibitor composition |
| US4304677A (en) * | 1978-09-05 | 1981-12-08 | The Dow Chemical Company | Method of servicing wellbores |
| US4292183A (en) * | 1978-12-13 | 1981-09-29 | Great Lakes Chemical Corporation | High-density fluid compositions |
-
1982
- 1982-12-01 CA CA000416810A patent/CA1201282A/en not_active Expired
- 1982-12-01 GB GB08234302A patent/GB2112836A/en not_active Withdrawn
- 1982-12-23 DE DE19823247872 patent/DE3247872A1/en not_active Ceased
- 1982-12-27 NL NL8204996A patent/NL8204996A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3247872A1 (en) | 1983-07-07 |
| NL8204996A (en) | 1983-07-18 |
| GB2112836A (en) | 1983-07-27 |
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