WO2001023703A1 - A method of improving the permeability of an underground petroleum-containing formation - Google Patents

A method of improving the permeability of an underground petroleum-containing formation Download PDF

Info

Publication number
WO2001023703A1
WO2001023703A1 PCT/US2000/025483 US0025483W WO0123703A1 WO 2001023703 A1 WO2001023703 A1 WO 2001023703A1 US 0025483 W US0025483 W US 0025483W WO 0123703 A1 WO0123703 A1 WO 0123703A1
Authority
WO
WIPO (PCT)
Prior art keywords
moles
composition
group
alkyl
ethoxylated
Prior art date
Application number
PCT/US2000/025483
Other languages
French (fr)
Inventor
Alberto Slikta
James F. Gadberry
Andress K. Johnson
Original Assignee
Akzo Nobel N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to BRPI0014244-1A priority Critical patent/BR0014244B1/en
Priority to GB0206718A priority patent/GB2371823B/en
Priority to AU74955/00A priority patent/AU773820C/en
Priority to CA002385605A priority patent/CA2385605C/en
Priority to MXPA02003135A priority patent/MXPA02003135A/en
Priority to US10/088,962 priority patent/US6972274B1/en
Publication of WO2001023703A1 publication Critical patent/WO2001023703A1/en
Priority to NO20021414A priority patent/NO322161B1/en

Links

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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • 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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L19/00—Joints in which sealing surfaces are pressed together by means of a member, e.g. a swivel nut, screwed on or into one of the joint parts

Definitions

  • the present invention generally relates to compositions and methods for improving the mjectivity of water injection wells thereby restoring permeability to the formation and enhancing the recovery of oil by the waterflood process.
  • Petroleum is generally recovered from subterranean formations by penetrating the formation and establishing fluid communication with one or more wells and pumping or permitting the petroleum to flow to the surface.
  • This method of recovery called primary recovery ordinarily recovers only 20-30% of the petroleum existing in the formation.
  • Secondary recovery is accomplished by penetrating the formation with an injection well and establishing fluid communication. Water or steam is then forced into the injection well and petroleum and water are recovered at the recovery well. Petroleum recovery in water-wells is, however, inherently low. More particularly, in a porous subterranean oil-containing formation, the pores in the area adjacent to the well bore have a tendency to become clogged with synthetic and biological matter which restricts the flow of aqueous fluids such as drive fluids into the injection well in a petroleum recovery process. With time, the accumulation of plugging materials becomes sufficient to substantially reduce the permeability of the formation fact to the drive fluid which greatly impairs petroleum recovery.
  • U.S. patent No. 4,690,217 describes a method for improving the injectivity of water injection wells which comprises the injection of an aqueous fluid containing an effective amount of a surface-active agent into the well.
  • the surfactants employed by this document are anionic.
  • U.S. Patent No. 4,464,268 discloses a method for restoring the permeability of injection wells which have been plugged by polymer residue and or organic debris. The method includes treating the well for a period of time with an aqueous solution containing hydrogen peroxide, and acid selected from the group consisting of hydrochloric, hydrofluoric and acetic, and optionally a surfactant.
  • U.S. Patent No. 5,374,361 discloses a composition for well bore cleaning which comprises an alkyl polyglucoside and a cosurfactant which is selected from a linear alkyl ethoxylate or an alkyl phenyl ethoxylate, and caustic.
  • U.S. Patent No. 5,830,831 discloses a composition for well bore cleanout which consists essentially of a first surfactant which is an alkyl polyglucoside and a second surfactant consisting essentially of at least one alkyl polyglucoside and a linear ethoxylated alcohol.
  • U.S. Patent No. 4,514, 310 discloses a method for well bore treatment with a composition containing in major part, a nonaqueous solvent containing at least 50% by weight of N-methyl-2-pyrrolidone.
  • U.S. Patent No. 4,668,408 discloses a composition for treatment of well bores containing parraffin. The composition comprises a liquid mixture of a water-soluble ethoxylated alkyl phenol and an alcohol containing one to four carbon atoms.
  • U.S. Patent No. 5,501 ,276 discloses a method and composition for removing gelled and dehydrated drilling fluid and filter cake from the walls of well bores.
  • the composition comprises an aqueous solution of a sugar selected from mono-, di-, and triglycerides and mixtures thereof.
  • U.S. Patent No. 5,678,631 discloses a chemical additive for cleaning well bores which comprises an ether amine, alkene alcohol and water.
  • the object of the present method is to provide an improved and environmentally friendly method of restoring the permeability to injection wells that are plugged by various biological and synthetic organic debris and for improving the overall recovery rate of secondary recovery methods. This and other objects are realized by the method and composition of the present invention.
  • the present invention generally relates to a method of restoring the permeability of a porous subterranean petroleum-containing formation thereby improving the improving the injectivity of water injection wells leading to enhanced oil recovery.
  • the method generally comprises treating said formation with a composition which comprises a combination of at least one nonionic surfactant with at least one cationic surfactant in a ratio and in a concentration effective to restore permeability to the formation.
  • the method and composition of the present invention is useful for removing drilling residues, sludge, muds, paraffin, mud solids, biological or synthetic solids and the like from the formation area adjacent to the well bore of an injection well thus restoring permeability to a subterranean formation.
  • the method generally comprises treating the formation with a composition, which comprises a combination of at least one nonionic surfactant with at least one cationic surfactant in a specific ratio such that the permeability of a porous subterranean oil-containing formation is improved thereby enhancing oil recovery.
  • the composition of the present invention is also effective in clearing partially blocked or plugged well bores.
  • the nonionic surfactant of the present composition is preferably selected from the group consisting of alkanolamides, alkoxylated alcohols, alkoxylated amines, alkyl phenyl polyethoxylates, lecithin, hydroxylated lecithin, fatty acid esters, glycerol esters and their ethoxylates, glycol esters and their ethoxylates, esters of propylene glycol, sorbitan, ethoxylated sorbitan, polyglycosides and the like, and mixtures thereof.
  • Alkoxylated alcohols, preferably ethoxylated alcohols, optionally in combination with (alkyl)polyglycosides are the most preferred nonionic surfactants.
  • the ethoxylated alcohol useful in the context of the present invention is preferably an ethoxylated linear or branched alcohol having from 8 to 18 carbon atoms reacted with 2 to 12 moles of ethylene oxide.
  • Ethoxylated alcohols of the following general alcohol are particularly preferred:
  • R-O-(CH 2 CH 2 O) z -H (I) wherein R is a C 8 -C 30 saturated or unsaturated, branched or straight chain alkyl group, or an alkylphenyl group of the formula A - ⁇ ° / - O(CH 2 CH 2 O) z , wherein A is a C 8 -C 3 o saturated or unsaturated, branched or straight chain alkyl, preferably a Cg-C- ⁇ 2 linear or branched alkyl, and z is an integer of from 1 to 30.
  • the following alcohols are particularly preferred: laury alcohol ethoxylated with 3 moles of ethylene oxide(EO), coco alcohol ethoxylated with 3 moles of EO, stearyl alcohol ethoxylated with 5 moles of EO, mixed C 12 -C 15 alcohol ethoxylated with 7 moles EO, mixed secondary C 11 -C 15 alcohol ethoxylated with 7 moles EO, mixed C 9 -Cn linear alcohol ethoxylated with 6 moles EO, a Cg-C-n alcohol ethoxylated with 4 moles EO, and the like. Narrow range, less dispersed ethoxylates are particularly preferred.
  • the nonionic surfactant component of the present invention can be prepared by various methods in the prior art know those skilled in the art. Alternatively, many nonionics useful in the context of the present invention are commercially available.
  • the preferred (poly) alkyl glucoside nonionic surfactant is represented by formulae III or IV, below:
  • R 4 (CH 2 ) y - O - G x H (III) wherein R 4 is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5.
  • R 4 (CHCH 2 ) y - O - G x H wherein R is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, R 5 is hydrogen or a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5.
  • the cationic surfactants of the present are preferably selected from primary, secondary and tertiary amines, ester amines, amido amines, quaternary ammonium salts, ester containing quaternary ammonium compounds, amido amine quaternary ammonium compounds, alkyl pyridinium salts, and the like.
  • the most preferred cationic surfactant is a quaternary ammonium compound.
  • a class of quaternary ammonium compounds usefully employed in the context of the present invention is represented by the general formula:
  • Ri is an saturated or unsaturated, branched or straight chain alkyl group having 8-22 carbon atoms, preferably, cocoalkyl
  • R 2 is a C-, to C 8 alkyl group, 2- ethylhexyl, hydroxyethyl, hydroxypropyl, preferably methyl, ethyl or propyl
  • R 3 is selected from Ri, R 2 , or a group of the formula:
  • Preferred anions include but are not limited to Cl " and methylsulfate (MeSO ), acetate and the like.
  • the cationic surfactant component of the present invention is preferably a bis(ethoxylated) quaternary ammonium compounds including but are not limited to: stearyl methyl bis(ethoxy) ammonium chloride (12 moles EO), stearyl ethyl bis(ethoxy) ammonium ethyl sulfate (15 moles EO), tallow methyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), tallow ethyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), hydrogenated tallow methyl bis(ethoxy) ammonium chloride (15 moles EO), coco methyl bis (ethoxy) ammonium chloride (20 moles EO), and the like.
  • stearyl methyl bis(ethoxy) ammonium chloride (12 moles EO)
  • the amount of ethoxylation is the total ethoxylation for the molecule.
  • the ammonium compounds of the present invention preferably have an HLB of from 14.00 to 22.00 and are hydrophilic.
  • a particularly preferred cationic surfactant component is cocomethyl bis[ethoxylated] (15)-quatemary ammonium chloride available from Akzo Nobel Chemicals, Inc. under the trademark Ethoquad® C/25.
  • a solvent, or mixtures of solvents may optionally be employed with the composition of the present invention.
  • a solvent is preferably selected from the group which includes, but is not limited to water, lower alcohols such as methanol, ethanol, 1-propanol, 2-propanol and the like, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polyethylene glycol block copolymers, and the like, and glycol ethers such as 2- methoxyethanol, diethylene glycol monomethylether, and the like.
  • composition of the present invention may also contain various optional ingredients such as corrosion inhibitors, scale inhibitors, biocides, and the like.
  • the ratio of said at least one nonionic surfactant to said at least one cationic surfactant is generally in the range of 4:1 to 1 :4, more preferably, 3:1 to 1 :3 by weight.
  • the present invention relates to a method for improving the permeability of an oil-containing formation which comprises treating said formation with a composition which comprises 20-80% of an ethoxylated alcohol, 10-60% of quaternary ammonium compound and optionally, up to 30% of an alkyl glycoside, and optionally a solvent.
  • the present invention contemplates a method for improving the permeability of an oil-containing formation which comprises treating said formation with a composition which comprises 25-65% of an ethoxylated alcohol, 20-60% of quaternary ammonium compound and optionally, up to 30% of an alkyl glycoside, and optionally a solvent.
  • the invention relates to a method of cleaning a porous formation and adjacent well bore from synthetic and oil-based contaminants which comprises said formation and well bore with a composition which comprises at least one ethoxylated linear or branched alcohol having from 8 to 18 carbon atoms reacted with 2 to 12 moles of ethylene oxide, at least one quaternary ammonium compound and optionally, at least one APG.
  • the invention also relates to the various compositions utilized to restore the permeability of oil-containing formations and to clean well bore of injection wells.
  • An effective concentration of the surfactant composition of the present invention in the injected solution will vary between about 0.1 % to 10% by weight of the aqueous fluid and surfactant composition, preferably between about 0.1 % and 5% by weight.
  • the amount of injected solution necessary to sweep the plugging materials from the area of he formation near the well bore can readily be determined by those of ordinary skill in the art.
  • the volume of injected solution will normally be less than 1 per cent of the oil- containing reservoir pore space volume between the injection well and the production wells.
  • sufficient solution should be used to fill the well bore and to fill the porous formation with a solution to a distance of about one foot to about twenty feet or more from the formation face. Typically, treating a porous formation from a distance of from about one to about four feet is sufficient to obtain good results.
  • the well is allowed to stand for about 2 hours up to about 96 hours or more. Typically, 10 to about 36 hours is enough time to allow the composition of the present invention to diffuse into the pores of the formation and remove the plugging materials.
  • the well can then be either backflowed to remove the composition of the invention and displaced plugging material or injection fluid can be used to dislodge and/or displace the plugging materials.
  • the well can be treated in a continuous flow method by circulating the composition of the present invention down the tubing of the well bore and out the annulus for a period of time sufficient for the treating composition to diffuse into the formation to react with and displace the plugging materials.
  • the treating flow is typically circulated for about 2 hours up to about 96 hours or more, preferably from about 10 to about 36 hours. This is typically enough time to allow the composition of the present invention to diffuse into the pores of the formation and remove the plugging materials although one of ordinary skill in the art will recognize that this time can vary greatly depending on the formation and the variety of plugging materials.
  • the well is then either backflowed to remove the composition of the invention and displaced plugging material or injection fluid can be used to dislodge and/or displace the plugging materials.
  • injection can be resumed and petroleum and aqueous fluids are recovered at the production well.
  • the composition of the present invention can be intermittently or continuously circulated in the well bore to dissolve and disperse unwanted accumulations and to treat the surfaces to prevent future accumulations.
  • a well bore cleaning effective amount of the composition of the present invention to be used in the well bore varies depending on the amount of debris to be removed, the amount of parrafins, etc. in the crude, the production rate, the temperature of the well bore, and other factors which are readily apparent to those of ordinary skill in the art.
  • the composition of the present invention can be circulated in the formation at an approximate rate of 50 to 500 parts per million based on oil production. Circulation of the composition can be achieved by pumping it through the casing exterior of the production pipe.
  • the composition of the invention can be added at a rate of 1 -5 gallons every 5-10 days.
  • the circulation can occur either during injection or while production is stopped.
  • compositions of the present invention are within the knowledge of one of ordinary skill in the art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mechanical Engineering (AREA)
  • Detergent Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention generally relates to a method and a composition useful in restoring the permeability of a porous underground petroleum-containing formation. Restoring permeability to the formation enhances the injectivity thereby accelerating petroleum recovery. The method of the invention comprises treating said formation with a composition which comprises a combination of at least one nonionic compound, preferably an alkoxylated alcohol, with at least one cationic compound, preferably a quaternary ammonium compound, in an amount effective to improve the permeability of the formation. The composition may also optionally contain an alkyl glycoside.

Description

A Method Of Improving The Permeability Of an Underground Petroleum- Containing Formation
The present application claims priority of U.S. provisional patent application No. 60/155,983 filed on September 24, 1999.
Field of The Invention
The present invention generally relates to compositions and methods for improving the mjectivity of water injection wells thereby restoring permeability to the formation and enhancing the recovery of oil by the waterflood process.
Background of The Invention
Petroleum is generally recovered from subterranean formations by penetrating the formation and establishing fluid communication with one or more wells and pumping or permitting the petroleum to flow to the surface. This method of recovery called primary recovery ordinarily recovers only 20-30% of the petroleum existing in the formation.
Once primary recovery has ceased, secondary recovery methods such as water flooding techniques are often called for. Secondary recovery is accomplished by penetrating the formation with an injection well and establishing fluid communication. Water or steam is then forced into the injection well and petroleum and water are recovered at the recovery well. Petroleum recovery in water-wells is, however, inherently low. More particularly, in a porous subterranean oil-containing formation, the pores in the area adjacent to the well bore have a tendency to become clogged with synthetic and biological matter which restricts the flow of aqueous fluids such as drive fluids into the injection well in a petroleum recovery process. With time, the accumulation of plugging materials becomes sufficient to substantially reduce the permeability of the formation fact to the drive fluid which greatly impairs petroleum recovery. Various methods have been suggested for improving the injectivity of water injection wells to be used in certain waterflood processes where there is low formation permeability to water compared to the formation absolute permeability due to the presence of residual oil in the formation pore spaces. For example, U.S. patent No. 4,690,217 describes a method for improving the injectivity of water injection wells which comprises the injection of an aqueous fluid containing an effective amount of a surface-active agent into the well. The surfactants employed by this document are anionic.
U.S. Patent No. 4,464,268 discloses a method for restoring the permeability of injection wells which have been plugged by polymer residue and or organic debris. The method includes treating the well for a period of time with an aqueous solution containing hydrogen peroxide, and acid selected from the group consisting of hydrochloric, hydrofluoric and acetic, and optionally a surfactant.
U.S. Patent No. 5,374,361 discloses a composition for well bore cleaning which comprises an alkyl polyglucoside and a cosurfactant which is selected from a linear alkyl ethoxylate or an alkyl phenyl ethoxylate, and caustic.
U.S. Patent No. 5,830,831 discloses a composition for well bore cleanout which consists essentially of a first surfactant which is an alkyl polyglucoside and a second surfactant consisting essentially of at least one alkyl polyglucoside and a linear ethoxylated alcohol.
U.S. Patent No. 4,514, 310 discloses a method for well bore treatment with a composition containing in major part, a nonaqueous solvent containing at least 50% by weight of N-methyl-2-pyrrolidone. U.S. Patent No. 4,668,408 discloses a composition for treatment of well bores containing parraffin. The composition comprises a liquid mixture of a water-soluble ethoxylated alkyl phenol and an alcohol containing one to four carbon atoms.
U.S. Patent No. 5,501 ,276 discloses a method and composition for removing gelled and dehydrated drilling fluid and filter cake from the walls of well bores. The composition comprises an aqueous solution of a sugar selected from mono-, di-, and triglycerides and mixtures thereof.
Finally, U.S. Patent No. 5,678,631 discloses a chemical additive for cleaning well bores which comprises an ether amine, alkene alcohol and water.
The object of the present method is to provide an improved and environmentally friendly method of restoring the permeability to injection wells that are plugged by various biological and synthetic organic debris and for improving the overall recovery rate of secondary recovery methods. This and other objects are realized by the method and composition of the present invention.
Summary of the Invention
The present invention generally relates to a method of restoring the permeability of a porous subterranean petroleum-containing formation thereby improving the improving the injectivity of water injection wells leading to enhanced oil recovery. The method generally comprises treating said formation with a composition which comprises a combination of at least one nonionic surfactant with at least one cationic surfactant in a ratio and in a concentration effective to restore permeability to the formation. Detailed Description of The Invention
The method and composition of the present invention is useful for removing drilling residues, sludge, muds, paraffin, mud solids, biological or synthetic solids and the like from the formation area adjacent to the well bore of an injection well thus restoring permeability to a subterranean formation. The method generally comprises treating the formation with a composition, which comprises a combination of at least one nonionic surfactant with at least one cationic surfactant in a specific ratio such that the permeability of a porous subterranean oil-containing formation is improved thereby enhancing oil recovery. The composition of the present invention is also effective in clearing partially blocked or plugged well bores.
The nonionic surfactant of the present composition is preferably selected from the group consisting of alkanolamides, alkoxylated alcohols, alkoxylated amines, alkyl phenyl polyethoxylates, lecithin, hydroxylated lecithin, fatty acid esters, glycerol esters and their ethoxylates, glycol esters and their ethoxylates, esters of propylene glycol, sorbitan, ethoxylated sorbitan, polyglycosides and the like, and mixtures thereof. Alkoxylated alcohols, preferably ethoxylated alcohols, optionally in combination with (alkyl)polyglycosides are the most preferred nonionic surfactants.
The ethoxylated alcohol useful in the context of the present invention is preferably an ethoxylated linear or branched alcohol having from 8 to 18 carbon atoms reacted with 2 to 12 moles of ethylene oxide. Ethoxylated alcohols of the following general alcohol are particularly preferred:
R-O-(CH2CH2O)z-H (I) wherein R is a C8-C30 saturated or unsaturated, branched or straight chain alkyl group, or an alkylphenyl group of the formula A -\ ° / - O(CH2CH2O)z , wherein A is a C8-C3o saturated or unsaturated, branched or straight chain alkyl, preferably a Cg-C-ι2 linear or branched alkyl, and z is an integer of from 1 to 30. The following alcohols are particularly preferred: laury alcohol ethoxylated with 3 moles of ethylene oxide(EO), coco alcohol ethoxylated with 3 moles of EO, stearyl alcohol ethoxylated with 5 moles of EO, mixed C12-C15 alcohol ethoxylated with 7 moles EO, mixed secondary C11-C15 alcohol ethoxylated with 7 moles EO, mixed C9-Cn linear alcohol ethoxylated with 6 moles EO, a Cg-C-n alcohol ethoxylated with 4 moles EO, and the like. Narrow range, less dispersed ethoxylates are particularly preferred. The nonionic surfactant component of the present invention can be prepared by various methods in the prior art know those skilled in the art. Alternatively, many nonionics useful in the context of the present invention are commercially available.
The preferred (poly) alkyl glucoside nonionic surfactant is represented by formulae III or IV, below:
R4 (CH2)y - O - Gx H (III) wherein R4 is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5.
R5
I (IV) R4 (CHCH2)y - O - Gx H wherein R is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, R5 is hydrogen or a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5.
The cationic surfactants of the present are preferably selected from primary, secondary and tertiary amines, ester amines, amido amines, quaternary ammonium salts, ester containing quaternary ammonium compounds, amido amine quaternary ammonium compounds, alkyl pyridinium salts, and the like. The most preferred cationic surfactant is a quaternary ammonium compound. A class of quaternary ammonium compounds usefully employed in the context of the present invention is represented by the general formula:
Figure imgf000007_0001
wherein Ri is an saturated or unsaturated, branched or straight chain alkyl group having 8-22 carbon atoms, preferably, cocoalkyl; R2 is a C-, to C8 alkyl group, 2- ethylhexyl, hydroxyethyl, hydroxypropyl, preferably methyl, ethyl or propyl; R3 is selected from Ri, R2, or a group of the formula:
Figure imgf000007_0002
I I
(CH2CHO)m (CH2CHO)n H wherein R5 and R6 independently selected from hydrogen or a C1 to C6 alkyl group, and m + n is an integer of from 2-80; R is selected from R2 or R3 ; and X" is an anion.
Preferred anions include but are not limited to Cl" and methylsulfate (MeSO ), acetate and the like.
The cationic surfactant component of the present invention is preferably a bis(ethoxylated) quaternary ammonium compounds including but are not limited to: stearyl methyl bis(ethoxy) ammonium chloride (12 moles EO), stearyl ethyl bis(ethoxy) ammonium ethyl sulfate (15 moles EO), tallow methyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), tallow ethyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), hydrogenated tallow methyl bis(ethoxy) ammonium chloride (15 moles EO), coco methyl bis (ethoxy) ammonium chloride (20 moles EO), and the like. Mixtures of these compounds can also be used in the context of the present invention. Additionally, in the above description, the amount of ethoxylation is the total ethoxylation for the molecule. One of ordinary skill in the art will recognize that these values can be varied while remaining within the spirit and scope of the present invention. Additionally, one of ordinary skill in the art will recognize that the values m and n can be varied, but their combined total has a profound affect on HLB. The ammonium compounds of the present invention preferably have an HLB of from 14.00 to 22.00 and are hydrophilic. A particularly preferred cationic surfactant component is cocomethyl bis[ethoxylated] (15)-quatemary ammonium chloride available from Akzo Nobel Chemicals, Inc. under the trademark Ethoquad® C/25.
A solvent, or mixtures of solvents may optionally be employed with the composition of the present invention. If a solvent is employed, it is preferably selected from the group which includes, but is not limited to water, lower alcohols such as methanol, ethanol, 1-propanol, 2-propanol and the like, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polyethylene glycol block copolymers, and the like, and glycol ethers such as 2- methoxyethanol, diethylene glycol monomethylether, and the like.
The composition of the present invention may also contain various optional ingredients such as corrosion inhibitors, scale inhibitors, biocides, and the like.
The ratio of said at least one nonionic surfactant to said at least one cationic surfactant is generally in the range of 4:1 to 1 :4, more preferably, 3:1 to 1 :3 by weight. In one embodiment, the present invention relates to a method for improving the permeability of an oil-containing formation which comprises treating said formation with a composition which comprises 20-80% of an ethoxylated alcohol, 10-60% of quaternary ammonium compound and optionally, up to 30% of an alkyl glycoside, and optionally a solvent.
In another embodiment, the present invention contemplates a method for improving the permeability of an oil-containing formation which comprises treating said formation with a composition which comprises 25-65% of an ethoxylated alcohol, 20-60% of quaternary ammonium compound and optionally, up to 30% of an alkyl glycoside, and optionally a solvent.
In still a further embodiment, the invention relates to a method of cleaning a porous formation and adjacent well bore from synthetic and oil-based contaminants which comprises said formation and well bore with a composition which comprises at least one ethoxylated linear or branched alcohol having from 8 to 18 carbon atoms reacted with 2 to 12 moles of ethylene oxide, at least one quaternary ammonium compound and optionally, at least one APG.
The invention also relates to the various compositions utilized to restore the permeability of oil-containing formations and to clean well bore of injection wells.
An effective concentration of the surfactant composition of the present invention in the injected solution will vary between about 0.1 % to 10% by weight of the aqueous fluid and surfactant composition, preferably between about 0.1 % and 5% by weight. The amount of injected solution necessary to sweep the plugging materials from the area of he formation near the well bore can readily be determined by those of ordinary skill in the art. Typically, however, the volume of injected solution will normally be less than 1 per cent of the oil- containing reservoir pore space volume between the injection well and the production wells.
In treating a well in accordance with the present invention, sufficient solution should be used to fill the well bore and to fill the porous formation with a solution to a distance of about one foot to about twenty feet or more from the formation face. Typically, treating a porous formation from a distance of from about one to about four feet is sufficient to obtain good results. Once the well is injected with the composition of the present invention, the well is allowed to stand for about 2 hours up to about 96 hours or more. Typically, 10 to about 36 hours is enough time to allow the composition of the present invention to diffuse into the pores of the formation and remove the plugging materials. The well can then be either backflowed to remove the composition of the invention and displaced plugging material or injection fluid can be used to dislodge and/or displace the plugging materials.
Alternatively, the well can be treated in a continuous flow method by circulating the composition of the present invention down the tubing of the well bore and out the annulus for a period of time sufficient for the treating composition to diffuse into the formation to react with and displace the plugging materials. The treating flow is typically circulated for about 2 hours up to about 96 hours or more, preferably from about 10 to about 36 hours. This is typically enough time to allow the composition of the present invention to diffuse into the pores of the formation and remove the plugging materials although one of ordinary skill in the art will recognize that this time can vary greatly depending on the formation and the variety of plugging materials. As previously mentioned, the well is then either backflowed to remove the composition of the invention and displaced plugging material or injection fluid can be used to dislodge and/or displace the plugging materials. After treatment, injection can be resumed and petroleum and aqueous fluids are recovered at the production well.
To utilize the composition of the present invention for the treatment of the well bores of injection wells, the composition can be intermittently or continuously circulated in the well bore to dissolve and disperse unwanted accumulations and to treat the surfaces to prevent future accumulations. A well bore cleaning effective amount of the composition of the present invention to be used in the well bore varies depending on the amount of debris to be removed, the amount of parrafins, etc. in the crude, the production rate, the temperature of the well bore, and other factors which are readily apparent to those of ordinary skill in the art.
For continuous treatment of well bores, the composition of the present invention can be circulated in the formation at an approximate rate of 50 to 500 parts per million based on oil production. Circulation of the composition can be achieved by pumping it through the casing exterior of the production pipe.
For batch treatment, the composition of the invention can be added at a rate of 1 -5 gallons every 5-10 days. The circulation can occur either during injection or while production is stopped.
Other methods for improving the permeability of underground formations and treating well bores with the compositions of the present invention are within the knowledge of one of ordinary skill in the art.

Claims

We claim:
1. A method for improving the permeability of a petroleum-containing formation, said method comprising treating said formation with a composition which comprises at least one nonionic surfactant and at least one cationic surfactant in an amount and a concentration effective to improve the permeability of said formation.
2. The method of claim 1 wherein said at least one nonionic surfactant is selected from the group consisting of alkanolamides, alkoxylated alcohols, alkoxylated amines, alkyl phenyl polyethoxylates, lecithin, hydroxylated lecithin, fatty acid esters, glycerol esters and their ethoxylates, glycol esters and their ethoxylates, esters of propylene glycol, sorbitan, ethoxylated sorbitan polyglycosides and mixtures thereof.
3. The method of claim 2 wherein said at least one nonionic surfactant is an ethoxylated linear or or branched alcohol of the formula:
R-O-(CH2CH2O)z-H (I)
wherein R is a C8-C30 saturated or unsaturated, branched or straight chain alkyl, or alkylphenyl group of the formula A -ζθ - O(CH2CH2O)Zι , wherein A is a C8- C30 saturated or unsaturated, branched or straight chain alkyl, preferably a C9- C12 linear or branched alkyl, and z is an integer of from 1 to 30.
4. The method of claim 3 wherein wherein A is a saturated or unsaturated, branched or straight chain C9-C12 alkyl.
5. The method of claim 3 wherein said ethoxylated alcohol is selected from the group consisting of laury alcohol ethoxylated with 3 moles of ethylene oxide(EO), coco alcohol ethoxylated with 3 moles of EO, stearyl alcohol ethoxylated with 5 moles of EO, mixed C12-C15 alcohol ethoxylated with 7 moles EO, mixed secondary C11-C15 alcohol ethoxylated with 7 moles EO, mixed C9- C11 linear alcohol ethoxylated with 6 moles EO, a Cg-C-n alcohol ethoxylated with 4 moles EO, and mixtures thereof.
6. The method of claim 1 wherein said at least one cationic surfactant is selected from the group consisting of primary, secondary and tertiary amines, quaternary ammonium compounds, alkyl pyridinium salts and mixtures thereof.
7. The method of claim 6 wherein said at least one cationic surfactant is a quaternary ammonium compound of the general formula:
Figure imgf000013_0001
wherein R-i is an saturated or unsaturated, branched or straight chain alkyl group having 8-22 carbon atoms, preferably, cocoalkyl; R2 is a C-, to C6 alkyl group, 2- ethylhexyl, hydroxyethyl, hydroxypropyl, preferably methyl, ethyl or propyl; R3 is selected from Ri , R2 or a group of the formula:
Figure imgf000013_0002
I I
(CH2CHO)m (CH2CHO)n H wherein R5 and R6 independently selected from hydrogen or a Ci to C6 alkyl group, and m + n is an integer of from 2-80; R4 is selected from R2 or R3 ; and X" is an anion.
8. The method of claim 1 wherein said composition comprises a combination of (i) at least one ethoxylated linear or branched alcohol having from 8 to 18 carbon atoms reacted with 2 to 12 moles of ethylene oxide;
(ϋ) at least one quaternary ammonium compound of the general formula:
Figure imgf000014_0001
wherein Ri is an saturated or unsaturated, branched or straight chain alkyl group having 8-22 carbon atoms, preferably, cocoalkyl; R2 is a Ci to C6 alkyl group, 2- ethylhexyl, hydroxyethyl, hydroxypropyl; R3 is selected from R-,, R2 or a group of the formula:
R5 R6
(CH2CHO)m (CH2CHO)n H wherein R5 and Re independently selected from hydrogen or a Ci to C& alkyl group, and m + n is an integer of from 2-80; R4 is selected from R2 or R3 ; and X" is an anion, and
(iii) up to 30% by weight of at least one (poly) alkyl glucoside.
9. The method of claim 8 wherein said ethoxylated alcohol is selected from the group consisting of.lauryl alcohol ethoxylated with 3 moles of ethylene oxide(EO), coco alcohol ethoxylated with 3 moles of EO, stearyl alcohol ethoxylated with 5 moles of EO, mixed C-12-C-15 alcohol ethoxylated with 7 moles EO, mixed secondary C11-C15 alcohol ethoxylated with 7 moles EO, mixed Cg- C11 linear alcohol ethoxylated with 6 moles EO, a Cg-Cn alcohol ethoxylated with 4 moles EO, and mixtures thereof.
10. The method of claim 8 wherein R-i is coco alkyl, m+n = 15, R2 is methyl, R3 is H and X" is CI" or methylsulfate.
11. The method of claim 8 wherein said quaternary ammonium compound is selected from the group consisting of stearyl methyl bis(ethoxy) ammonium chloride (12 moles EO), stearyl ethyl bis(ethoxy) ammonium ethyl sulfate (15 moles EO), tallow methyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), tallow ethyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), hydrogenated tallow methyl bis(ethoxy) ammonium chloride (15 moles EO), coco methyl bis (ethoxy) ammonium chloride (20 moles EO), and mixtures thereof.
12. The method of claim 8 wherein the HLB of the quaternary ammonium compound is from about 14.00 to 22.00.
13. The method of claim 8 wherein said composition additionally comprises up to 30% of a (poly) alkyl glycoside of formulae III or IV:
R4 (CH2)y - O - Gx H (HI)
wherein R4 is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5; R5 (iv)
I R (CHCH2)y - O - Gx H wherein R4 is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, R5 is hydrogen or a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5.
14. The method of claim 1 wherein said composition additionally comprises one or more solvents.
15. The method of claim 14 wherein said solvent is selected from the group consisting of water, lower alcohols, glycol ethers and mixtures thereof.
16. The method of claim 15 wherein said solvent is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol and the like, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polyethylene glycol block copolymers, and mixtures thereof.
17. The method of claim 1 wherein the ratio of said at least one nonionic surfactant to said at least one cationic surfactant is in the range of 4:1 to 1 :4.
18. The method of claim 17 wherein said composition comprising said at least one nonionic surfactant to said at least one cationic surfactant is diluted to a concentration of from about 0.1 % to about 10% by weight prior to injection into the formation.
19. An aqueous composition for use in restoring the permeability of a subterranean petroleum containing formation which comprises: (i) at least one nonionic surfactant which is a ethoxylated linear or branched alcohol having from 8 to 18 carbon atoms reacted with 2 to 12 moles of ethylene oxide;
(ii) at least one cationic surfactant which is a quaternary ammonium compound of the general formula:
Figure imgf000017_0001
wherein Ri is an saturated or unsaturated, branched or straight chain alkyl group having 8-22 carbon atoms, preferably, cocoalkyl; R2 is a d to C6 alkyl group, 2- ethylhexyl, hydroxyethyl, hydroxypropyl; R3 is selected from Ri, R2 or a group of the formula:
R5 Re
(CH2CHO)m (CH2CHO)n H wherein R5 and Re independently selected from hydrogen or a Ci to C6 alkyl group, and m + n is an integer of from 2-80; R is selected from R2 or R3 ; and X" is an anion, and
(iii) optionally, at least one (poly) alkyl glucoside.
20. The composition of claim 19 wherein said ethoxylated linear or branched alcohol is of the formula:
R-O-(CH2CH2O)z-H (I) wherein R is a C8-C30 saturated or unsaturated, branched or straight chain alkyl, or alkylphenyl group of the formula A -\ ° / - O(CH2CH2O)z, , wherein A is a C8-C30 saturated or unsaturated, branched or straight chain alkyl, preferably a C -Ci2 linear or branched alkyl, and z is an integer of from 1 to 30.
21. The composition of claim 20 wherein wherein A is a saturated or unsaturated, branched or straight chain C9-C-ι2 alkyl.
22. The composition of claim 20 wherein said ethoxylated alcohol is selected from the group consisting of.laury alcohol ethoxylated with 3 moles of ethylene oxide(EO), coco alcohol ethoxylated with 3 moles of EO, stearyl alcohol ethoxylated with 5 moles of EO, mixed C12-C-15 alcohol ethoxylated with 7 moles EO, mixed secondary C11-C15 alcohol ethoxylated with 7 moles EO, mixed C9- C11 linear alcohol ethoxylated with 6 moles EO, a Cg-C-n alcohol ethoxylated with 4 moles EO, 15 mole ethoxylate of coco alkyl amine and mixtures thereof.
23. The composition of claim 19 wherein Ri is coco alkyl, m+n = 15, R2 is methyl, R3 is H and X" is CI" or methylsulfate.
24. The composition of claim 19 wherein said quaternary ammonium compound is selected from the group consisting of stearyl methyl bis(ethoxy) ammonium chloride (12 moles EO), stearyl ethyl bis(ethoxy) ammonium ethyl sulfate (15 moles EO), tallow methyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), tallow ethyl bis(ethoxy) ammonium methyl sulfate (15 moles EO), hydrogenated tallow methyl bis(ethoxy) ammonium chloride (15 moles EO), coco methyl bis (ethoxy) ammonium chloride (20 moles EO), andmixtures thereof.
25. The composition of claim 19 wherein the HLB of the quaternary ammonium compound is from about 14.00 to 22.00.
26. The composition of claim 19 wherein said composition optionally comprises a (poly) alkyl glycoside of formulae III or IV:
R4 (CH2)y - O - Gx H (III) wherein R is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5;
R5 (iv)
I R4 (CHCH2)y - O - Gx H wherein R is a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, R5 is hydrogen or a straight or branched chain alkyl or alkenyl group having from 8 to 21 carbon atoms, G is a monosaccharide residue and x and y are selected from a number of from 1 to 5.
27. The composition of claim 19 wherein said composition additionally comprises one or more solvents selected from the group consisting of water, methanol, ethanol, 1-propanol, 2-propanol and the like, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polyethylene glycol block copolymers, and mixtures thereof.
28. The composition of claim 19 wherein the ratio of said at least one nonionic surfactant to said at least one cationic surfactant is in the range of 4:1 to 1 :4.
29. The composition of claim 19 wherein said composition comprising said at least one nonionic surfactant to said at least one cationic surfactant is diluted to a concentration of from about 0.1 % to about 10% by weight prior to injection into the formation.
PCT/US2000/025483 1999-09-24 2000-09-15 A method of improving the permeability of an underground petroleum-containing formation WO2001023703A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BRPI0014244-1A BR0014244B1 (en) 1999-09-24 2000-09-15 aqueous composition for use in restoring the permeability of an underground petroleum containing formation.
GB0206718A GB2371823B (en) 1999-09-24 2000-09-15 A method of improving the permeability of an underground petroleum-containing formation
AU74955/00A AU773820C (en) 1999-09-24 2000-09-15 A method of improving the permeability of an underground petroleum-containing formation
CA002385605A CA2385605C (en) 1999-09-24 2000-09-15 A method of improving the permeability of an underground petroleum-containing formation
MXPA02003135A MXPA02003135A (en) 1999-09-24 2000-09-15 A method of improving the permeability of an underground petroleum containing formation.
US10/088,962 US6972274B1 (en) 1999-09-24 2000-09-15 Method of improving the permeability of an underground petroleum-containing formation
NO20021414A NO322161B1 (en) 1999-09-24 2002-03-21 Method for improving the permeability of a petroleum-containing subsurface formation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15598399P 1999-09-24 1999-09-24
US60/155,593 1999-09-24

Publications (1)

Publication Number Publication Date
WO2001023703A1 true WO2001023703A1 (en) 2001-04-05

Family

ID=22557587

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/025483 WO2001023703A1 (en) 1999-09-24 2000-09-15 A method of improving the permeability of an underground petroleum-containing formation

Country Status (8)

Country Link
CN (1) CN1266369C (en)
AR (1) AR025758A1 (en)
AU (1) AU773820C (en)
BR (1) BR0014244B1 (en)
MX (1) MXPA02003135A (en)
NO (1) NO322161B1 (en)
RU (1) RU2249682C2 (en)
WO (1) WO2001023703A1 (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7115547B2 (en) * 2003-09-30 2006-10-03 Wolfco Group, Inc. Additive for enhanced treatment of oil well contaminants
CN100355838C (en) * 2006-05-24 2007-12-19 西南石油大学 Hydrophobic oleophilic self-cementing sand and its preparation method
EP2232256A2 (en) * 2007-11-30 2010-09-29 M-I Llc Methods of cleaning wellbores and analyzing wellbore fluids
EP2232003A2 (en) * 2007-11-30 2010-09-29 M-I Llc Breaker fluids and methods of using the same
RU2443677C1 (en) * 2010-10-28 2012-02-27 Учреждение Российской академии наук Институт органической и физической химии им. А.Е. Арбузова Казанского научного центра РАН Poly[nonylphenoxypoly(ethyleneoxy)carbonylmethylammonium] polychlorides, having epoxy polymer hydrophilising modifier properties
US8273693B2 (en) 2001-12-12 2012-09-25 Clearwater International Llc Polymeric gel system and methods for making and using same in hydrocarbon recovery
WO2017070272A1 (en) * 2015-10-20 2017-04-27 M-I L.L.C. Non-emulsifier for completion brines to prevent emulsion from forming
WO2017070271A1 (en) * 2015-10-20 2017-04-27 M-I L.L.C. Emulsion preventer for completion brines
WO2018111229A1 (en) * 2016-12-13 2018-06-21 Halliburton Energy Services, Inc. Surfactant flowback aids for use in subterranean formation operations
WO2018144711A1 (en) * 2017-02-03 2018-08-09 Saudi Arabian Oil Company Drilling fluid compositions with enhanced rheology and methods of using same
IT201800007438A1 (en) * 2018-07-23 2020-01-23 LOW ECOTOXICOLOGICAL IMPACT FOAMING ADDITIVE FOR THE CONDITIONING OF THE SOIL IN THE PRESENCE OF MECHANIZED EXCAVATION

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100400618C (en) * 2006-05-24 2008-07-09 西南石油大学 Oil well surrounding stratum hyphobic lipophilic treating additive and its preparing method
CN101693829B (en) * 2009-10-28 2012-09-05 中联煤层气国家工程研究中心有限责任公司 Pulverized coal dispersing agent and active water fracturing fluid for fracturing of coal bed gas well
US8763705B2 (en) * 2011-03-25 2014-07-01 Schlumberger Technology Corporation Compositions and methods for cleaning a wellbore prior to cementing
CN103573231B (en) * 2012-07-23 2017-09-08 中国石油化工股份有限公司 The method for improving recovery ratio of sensitive heavy oil reservoir
CA2889606C (en) * 2013-01-14 2019-01-22 Basf Se Method of fracturing subterranean formations
CN104650841B (en) * 2013-11-22 2018-10-16 中国石油天然气股份有限公司 A kind of zwitterion compound surfactant oil displacement agent
CN105368428B (en) * 2014-08-27 2019-12-10 中国石油化工股份有限公司 Anionic-nonionic mixed oil-displacing surfactant and preparation method and application thereof
CN106590595B (en) * 2015-10-20 2020-02-07 中国石油化工股份有限公司 Oil displacement composition suitable for low-calcium magnesium oil reservoir and preparation method thereof
CN109989727A (en) * 2017-12-29 2019-07-09 新疆中核天山铀业有限公司 A kind of ground-dipping uranium extraction drilling de-plugging anatonosis technique
CN111088016B (en) * 2018-10-23 2022-04-05 中国石油化工股份有限公司 Non-alkylphenol surfactant yin-yang compound composition for chemical flooding and preparation method and application thereof
CN109880607A (en) * 2019-03-25 2019-06-14 大庆华理生物技术有限公司 A kind of binary displacement oil agent and its application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3323593A (en) * 1964-03-16 1967-06-06 Dow Chemical Co Method of treating an oil-bearing formation
US4120356A (en) * 1976-09-30 1978-10-17 Phillips Petroleum Company Well-cleaning process using viscosified surfactant solutions
US4669544A (en) * 1986-04-17 1987-06-02 Dowell Schlumberger Incorporated Reducing paraffin deposits on paraffin contaminated surfaces
US5830831A (en) * 1995-05-11 1998-11-03 Atlantic Richfield Company Surfactant blends for well operations
US5977032A (en) * 1998-09-26 1999-11-02 Atlantic Richfield Company Acidic surfactant composition and method for cleaning wellbore and flowline surfaces using the surfactant composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3323593A (en) * 1964-03-16 1967-06-06 Dow Chemical Co Method of treating an oil-bearing formation
US4120356A (en) * 1976-09-30 1978-10-17 Phillips Petroleum Company Well-cleaning process using viscosified surfactant solutions
US4669544A (en) * 1986-04-17 1987-06-02 Dowell Schlumberger Incorporated Reducing paraffin deposits on paraffin contaminated surfaces
US5830831A (en) * 1995-05-11 1998-11-03 Atlantic Richfield Company Surfactant blends for well operations
US5977032A (en) * 1998-09-26 1999-11-02 Atlantic Richfield Company Acidic surfactant composition and method for cleaning wellbore and flowline surfaces using the surfactant composition

Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8273693B2 (en) 2001-12-12 2012-09-25 Clearwater International Llc Polymeric gel system and methods for making and using same in hydrocarbon recovery
US7115547B2 (en) * 2003-09-30 2006-10-03 Wolfco Group, Inc. Additive for enhanced treatment of oil well contaminants
CN100355838C (en) * 2006-05-24 2007-12-19 西南石油大学 Hydrophobic oleophilic self-cementing sand and its preparation method
EP2232256A4 (en) * 2007-11-30 2011-10-12 Mi Llc Methods of cleaning wellbores and analyzing wellbore fluids
EP2232003A2 (en) * 2007-11-30 2010-09-29 M-I Llc Breaker fluids and methods of using the same
EP2232003A4 (en) * 2007-11-30 2011-10-19 Mi Llc Breaker fluids and methods of using the same
US8227382B2 (en) 2007-11-30 2012-07-24 M-I L.L.C. Breaker fluids and methods of using the same
EP2232256A2 (en) * 2007-11-30 2010-09-29 M-I Llc Methods of cleaning wellbores and analyzing wellbore fluids
US8950481B2 (en) 2007-11-30 2015-02-10 M-I Llc Methods of cleaning wellbores and analyzing wellbore fluids
RU2443677C1 (en) * 2010-10-28 2012-02-27 Учреждение Российской академии наук Институт органической и физической химии им. А.Е. Арбузова Казанского научного центра РАН Poly[nonylphenoxypoly(ethyleneoxy)carbonylmethylammonium] polychlorides, having epoxy polymer hydrophilising modifier properties
WO2017070272A1 (en) * 2015-10-20 2017-04-27 M-I L.L.C. Non-emulsifier for completion brines to prevent emulsion from forming
WO2017070271A1 (en) * 2015-10-20 2017-04-27 M-I L.L.C. Emulsion preventer for completion brines
US10214435B2 (en) 2015-10-20 2019-02-26 M-I L.L.C. Non-emulsifier for completion brines to prevent emulsion from forming
US10537829B2 (en) 2015-10-20 2020-01-21 M-I L.L.C. Emulsion preventer for completion brines
WO2018111229A1 (en) * 2016-12-13 2018-06-21 Halliburton Energy Services, Inc. Surfactant flowback aids for use in subterranean formation operations
US10995261B2 (en) 2016-12-13 2021-05-04 Halliburton Energy Services, Inc. Surfactant flowback aids for use in subterranean formation operations
US10494559B2 (en) 2017-02-03 2019-12-03 Saudi Arabian Oil Company Cement slurries, cured cement and methods of making and use thereof
US10683447B2 (en) 2017-02-03 2020-06-16 Saudi Arabian Oil Company Invert emulsion based drilling fluid and methods of using same
US10351750B2 (en) 2017-02-03 2019-07-16 Saudi Arabian Oil Company Drilling fluid compositions with enhanced rheology and methods of using same
US10377939B2 (en) 2017-02-03 2019-08-13 Saudi Arabian Oil Company Development of anti-bit balling fluids
US10392550B2 (en) 2017-02-03 2019-08-27 Saudi Arabian Oil Company Spacer fluid compositions, methods, and systems for aqueous based drilling mud removal
US10487254B2 (en) 2017-02-03 2019-11-26 Saudi Arabian Oil Company Enhanced filtration control packages, wellbore servicing fluids utilizing the same, and methods of maintaining the structure of a wellbore
US10494560B2 (en) 2017-02-03 2019-12-03 Saudi Arabian Oil Company Development of anti-bit balling fluids
US10287477B2 (en) 2017-02-03 2019-05-14 Saudi Arabian Oil Company Dispersant in cement formulations for oil and gas wells
US10526520B2 (en) 2017-02-03 2020-01-07 Saudi Arabian Oil Company Anti-bit balling drilling fluids, and methods of making and use thereof
US10266745B2 (en) 2017-02-03 2019-04-23 Saudi Arabian Oil Company Anti-bit balling drilling fluids, and methods of making and use thereof
US10538692B2 (en) 2017-02-03 2020-01-21 Saudi Arabian Oil Company Development of anti-bit balling fluids
US11365339B2 (en) 2017-02-03 2022-06-21 Saudi Arabian Oil Company Development of retarded acid system
US10563110B2 (en) 2017-02-03 2020-02-18 Saudi Arabian Oil Company Methods of using drilling fluid compositions with enhanced rheology
US10570324B2 (en) 2017-02-03 2020-02-25 Saudi Arabian Oil Company Emulsifier compositions for invert emulsion fluids and methods of using the same
US10590325B2 (en) 2017-02-03 2020-03-17 Saudi Arabian Oil Company Spacer fluid compositions that include surfactants
US10640695B2 (en) 2017-02-03 2020-05-05 Saudi Arabian Oil Company Dispersant in cement formulations for oil and gas wells
US10662363B2 (en) 2017-02-03 2020-05-26 Saudi Arabian Oil Company Lubricants for water-based drilling fluids
US10287476B2 (en) 2017-02-03 2019-05-14 Saudi Arabian Oil Company Cement slurries, cured cements and methods of making and use thereof
US10703957B2 (en) 2017-02-03 2020-07-07 Saudi Arabian Oil Company Development of retarded acid system
US10822534B2 (en) 2017-02-03 2020-11-03 Saudi Arabian Oil Company Retarded acid systems, emulsions, and methods for using in acidizing carbonate formations
US10844266B2 (en) 2017-02-03 2020-11-24 Saudi Arabian Oil Company Spacer fluids and cement slurries that include surfactants
US10851281B2 (en) 2017-02-03 2020-12-01 Saudi Arabian Oil Company Development of anti-bit balling fluids
US10876028B2 (en) 2017-02-03 2020-12-29 Saudi Arabian Oil Company Enhanced filtration control packages, wellbore servicing fluids utilizing the same, and methods of maintaining the structure of a wellbore
US10961426B2 (en) 2017-02-03 2021-03-30 Saudi Arabian Oil Company Development of anti-bit balling fluids
WO2018144711A1 (en) * 2017-02-03 2018-08-09 Saudi Arabian Oil Company Drilling fluid compositions with enhanced rheology and methods of using same
US11015104B2 (en) 2017-02-03 2021-05-25 Saudi Arabian Oil Company Cement slurries, cured cements and methods of making and use thereof
US11015105B2 (en) 2017-02-03 2021-05-25 Saudi Arabian Oil Company Cement slurries, cured cements and methods of making and use thereof
US11034875B2 (en) 2017-02-03 2021-06-15 Saudi Arabian Oil Company Enhanced filtration control packages, wellbore servicing fluids utilizing the same, and methods of maintaining the structure of a wellbore
US11078396B2 (en) 2017-02-03 2021-08-03 Saudi Arabian Oil Company Spacer fluid compositions, methods, and systems for aqueous based drilling mud removal
US11078397B2 (en) 2017-02-03 2021-08-03 Saudi Arabian Oil Company Spacer fluid compositions, methods, and systems for aqueous based drilling mud removal
US11098231B2 (en) 2017-02-03 2021-08-24 Saudi Arabian Oil Company Spacer fluid compositions that include surfactants
US11098232B2 (en) 2017-02-03 2021-08-24 Saudi Arabian Oil Company Lubricants for water-based drilling fluids
US11248157B2 (en) 2017-02-03 2022-02-15 Saudi Arabian Oil Company Emulsifier compositions for invert emulsion fluids and methods of using the same
IT201800007438A1 (en) * 2018-07-23 2020-01-23 LOW ECOTOXICOLOGICAL IMPACT FOAMING ADDITIVE FOR THE CONDITIONING OF THE SOIL IN THE PRESENCE OF MECHANIZED EXCAVATION

Also Published As

Publication number Publication date
NO20021414D0 (en) 2002-03-21
AR025758A1 (en) 2002-12-11
BR0014244B1 (en) 2012-09-04
NO20021414L (en) 2002-05-21
NO322161B1 (en) 2006-08-21
MXPA02003135A (en) 2002-09-30
AU7495500A (en) 2001-04-30
CN1266369C (en) 2006-07-26
BR0014244A (en) 2002-08-27
AU773820B2 (en) 2004-06-10
RU2249682C2 (en) 2005-04-10
AU773820C (en) 2005-02-17
CN1433499A (en) 2003-07-30

Similar Documents

Publication Publication Date Title
CA2385605C (en) A method of improving the permeability of an underground petroleum-containing formation
AU773820C (en) A method of improving the permeability of an underground petroleum-containing formation
RU2598959C2 (en) Thickened viscoelastic fluid media and their application
EP0569484B1 (en) Well cleanout using caustic alkyl polyglycoside compositions
EP2561035B1 (en) Process for the removal of deposits from an oil or gas well, and/or from the surface structures, and/or from the equipment connected therewith, and/or from hydrocarbon bearing formations
US20120208726A1 (en) Composition and method for removing filter cake
EP2831195B1 (en) Microemulsion flowback aid composition and method of using same
US8584760B2 (en) Cleaning agents for wellbore cleaning and methods of use thereof
EP3363876B1 (en) Process for the cleaning of oil and gas wellbores
US11084968B2 (en) Compositions and methods for treating oil and gas wells
US7115547B2 (en) Additive for enhanced treatment of oil well contaminants
US5773390A (en) Chemical additive for removing solids from a well drilling system
CN117987120A (en) Chemical agent for releasing water lock of oil and gas reservoir, and preparation method and application thereof
EP0765429A1 (en) A chemical additive and process for removing solids from a well drilling system

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2385605

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 00813085X

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 200206718

Country of ref document: GB

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/2002/003135

Country of ref document: MX

Ref document number: 74955/00

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2002 2002110813

Country of ref document: RU

Kind code of ref document: A

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
WWE Wipo information: entry into national phase

Ref document number: 10088962

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: JP

WWG Wipo information: grant in national office

Ref document number: 74955/00

Country of ref document: AU