US20130087340A1 - Chemomechanical treatment fluids and methods of use - Google Patents

Chemomechanical treatment fluids and methods of use Download PDF

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US20130087340A1
US20130087340A1 US13/330,040 US201113330040A US2013087340A1 US 20130087340 A1 US20130087340 A1 US 20130087340A1 US 201113330040 A US201113330040 A US 201113330040A US 2013087340 A1 US2013087340 A1 US 2013087340A1
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surfactant
fluid
subterranean formation
chemomechanical
formation
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US13/330,040
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II Robert Charles Choens
Gangerico G. Ramos
Carl T. Montgomery
Jeremy Johnson
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ConocoPhillips Co
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    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25Methods for stimulating production
    • E21B43/26Methods for stimulating production by forming crevices or fractures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584Compositions 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/66Compositions based on water or polar solvents
    • C09K8/68Compositions based on water or polar solvents containing organic compounds
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25Methods for stimulating production
    • E21B43/26Methods for stimulating production by forming crevices or fractures
    • E21B43/27Methods for stimulating production by forming crevices or fractures by use of eroding chemicals, e.g. acids

Definitions

  • the present invention relates generally to methods and systems for treating subterranean formations. More particularly, but not by way of limitation, embodiments of the present invention include methods and systems for favorably altering the chemomechanical properties of subterranean formations with treatment fluids comprising surfactants and halide salts.
  • Hydrocarbons occupy pore spaces in subterranean formations such as, in sandstone and limestone formations.
  • the pore spaces are often interconnected and have a certain permeability, which is a measure of the ability of the rock to transmit fluid flow. Maximizing production from low permeability reservoirs remains a continuing challenge in the hydrocarbon producing industry.
  • a variety of conventional methods have been used to improve the permeability of formations to enhance hydrocarbon recovery.
  • Examples of such treatment methods include stimulation operations such as fracturing and acid stimulation operations.
  • Hydraulic fracturing is a process by which a fluid under high pressure is injected into the formation to create and/or extend fractures that penetrate into the formation. These fractures can create flow channels to improve well productivity. Propping agents of various kinds, chemical or physical, may be used to hold the fractures open and to prevent the healing of the fractures after the fracturing pressure is released.
  • Acid stimulation is a chemical stimulation method that involves the injection of acid solutions that create porous channels throughout the formation to improve the permeability and porosity of the formation.
  • ROP drilling operations rate-of-penetration
  • the present invention relates generally to methods and systems for treating subterranean formations. More particularly, but not by way of limitation, embodiments of the present invention include methods and systems for favorably altering the chemomechanical properties of subterranean formations with treatment fluids comprising surfactants and halide salts.
  • One example of a method for treating a subterranean formation comprises: (a) providing a chemomechanical treatment fluid comprising a base fluid, a nonamphoteric surfactant, and a halide salt, wherein the nonamphoteric surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration; (b) introducing the chemomechanical treatment fluid under pressure into the subterranean formation, the subterranean formation having a plurality of fractures, tensile strengths, compressive strengths, and a fracture toughness, wherein each fracture has one or more fracture tips; (c) substantially ceasing the introduction of the chemomechanical treatment fluid; (d) allowing the chemomechanical treatment fluid to saturate the fracture tips; (e) allowing the chemomechanical treatment fluid to interact with the subterranean formation to decrease the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation; and (f) introducing additional chemomechanical treatment fluid after step
  • One example of a method for treating a subterranean formation comprises: (a) providing a chemomechanical treatment fluid comprising a base fluid, an amphoteric surfactant, and a halide salt, wherein the amphoteric surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration; (b) introducing the chemomechanical treatment fluid into the subterranean formation; (c) allowing the chemomechanical treatment fluid to interact with the subterranean formation to increase the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation to form a treated portion of the subterranean formation; and (d) drilling a portion of a well bore in the treated portion of the subterranean formation.
  • an enhanced hydrocarbon recovery method comprises: providing a chemomechanical treatment fluid comprising an aqueous base fluid, a surfactant, and a halide salt, wherein the surfactant is dissolved in the aqueous base fluid at a concentration below its critical micelle concentration; introducing the chemomechanical treatment fluid into the subterranean formation by way of an injection well; allowing the chemomechanical treatment fluid to interact with the subterranean formation to decrease the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation; and sweeping hydrocarbons towards a production well using the chemomechanical treatment fluid as a driving fluid for motivating the hydrocarbons towards the production well.
  • a chemomechanical treating fluid for treating subterranean formations comprises: an aqueous base fluid wherein the aqueous base fluid comprises water and an alcohol; a nonamphoteric surfactant wherein the nonamphoteric surfactant is dissolved in the aqueous base fluid at a concentration below its critical micelle concentration; and a halide salt.
  • FIG. 1 compares tensile strengths of carbonate-rich rock samples soaked in various surfactants.
  • FIG. 2 shows average tensile strengths results of the rock samples of FIG. 1 for each of the surfactants.
  • FIG. 3 compares tensile strengths of quartz-rich sandstone rock samples both dry and soaked in various surfactants.
  • FIG. 4 shows average tensile strengths results of the rock samples of FIG. 3 for each of the surfactants.
  • FIG. 5 compares fracture toughness of carbonate-rich rock samples both dry and soaked in various surfactants.
  • FIG. 6 compares the rock sample fracture toughness results of FIG. 5 for each of the surfactants to that of dry rock.
  • FIG. 7 compares the rock sample fracture toughness of the Eagle Ford Shales under dry and wet conditions.
  • FIG. 8 shows each of the Eagle Ford tests of FIG. 7 compared to the dry sample.
  • the present invention relates generally to methods and systems for treating subterranean formations. More particularly, but not by way of limitation, embodiments of the present invention include methods and systems for favorably altering the chemomechanical properties of subterranean formations with treatment fluids comprising surfactants and halide salts.
  • methods for treating subterranean formations comprise the steps of introducing a chemomechanical treatment fluid into the subterranean formation and allowing the chemomechanical treatment fluid to interact with the subterranean formation to alter its petrochemical properties in various ways.
  • the chemomechanical treatment fluid may comprise a base fluid, a halide salt and an amphoteric or nonamphoteric surfactant where the surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration.
  • Applications of use involving the chemomechanical treatment fluids include treatment operations, secondary recovery operations, drilling operations, and any other operation that would benefit from the formation property modifications described herein.
  • Subterranean formation properties that may to be varied by the chemomechanical treatment fluid include, but are not limited to, fracture toughness, tensile strength, or a combination thereof. Other enhancements of the methods are described further below.
  • chemomechanical treatment fluids may comprise a base fluid, a halide salt, and a surfactant.
  • the chemomechanical treatment fluid may advantageously modify certain properties of the formation, such as the fracture toughness.
  • concentrations of and the types of halide salts and surfactants employed in the chemomechanical treatment fluid influence the interaction of the chemomechanical treatment fluid and the formation.
  • a plurality of halide salts and/or surfactants may be employed as desired or as particular applications warrant.
  • chemomechanical treatment fluids employed depend on a number of factors, including, but not limited to, desired application, formation lithology, cementation, mineralogy, virgin pore pressure, formation temperature, acidity, or pH, secondary porosity, and the presence of discontinuities (e.g. fractures, bugs, and bedding).
  • the surfactant may comprise an amphoteric surfactant or a nonamphoteric surfactant depending on the desired application. In certain embodiments, a plurality of surfactants may be used.
  • nonamphoteric surfactants may be employed where a weakening of the formation is desired, whereas amphoteric surfactants may be employed where a strengthening of the formation is desired.
  • suitable nonamphoteric and amphoteric surfactants for use with the present invention include, but are not limited to, ammonium laurel sulfate, sodium lauryl sulfate, sodium dodecyl sulfate, fluorinated surfactants, cationic fluorinated surfactants, or any combination thereof. Under some conditions, various surfactants will act as a nonamphoteric surfactant or an amphoteric surfactant.
  • suitable concentrations of surfactants include concentrations from about 100 ppm to about 250 ppm.
  • the concentration of surfactant is below its critical micelle concentration (CMC).
  • CMC critical micelle concentration
  • the critical micelle concentration (CMC) is the concentration of surfactants above which micelles are spontaneously formed. Above the CMC, surfactants start aggregating into micelles, thus again decreasing the system's free energy by decreasing the contact area of hydrophobic parts of the surfactant with water. Upon reaching CMC, any further addition of surfactants will just increase the number of micelles (in the ideal case).
  • CMC is an important characteristic of a surfactant. Before reaching the CMC, the surface tension changes strongly with the concentration of the surfactant. After reaching the CMC, the surface tension remains more constant.
  • the halide salt may comprise any halide salt capable of assisting the modification of formation properties, including weakening or strengthening the formation as desired.
  • suitable halide salts for use with the present invention include, but are limited to, chloride salts, iodide, salts, bromide salts, fluoride salts, halide salts of potassium, or any combination thereof.
  • the addition of halide salts provides beneficial petrophysical and petrochemical interactions with the formation and may enhance the effects of the surfactants in the chemomechanical treatment fluid.
  • the base fluid of the chemomechanical treatment fluid may comprise any aqueous fluid.
  • the base fluid comprises water.
  • the water may be from any source including, but not limited to fresh water, sea water, naturally-occurring formation water, artificially-injected formation water, or any combination thereof.
  • the base fluid may comprise an alcohol as desired.
  • chemomechanical treatment fluids of the present invention include, but are not limited to, stimulation enhancement, fluid loss prevention during drilling applications, prevention of disintegration or prevention of weakening of the formation being drilled or stimulated, strengthening of the formation being drilled or stimulated, enhancement of secondary operations, and enhancement of hydrocarbon recovery operations.
  • One example of a method for stimulation enhancement comprises treating a subterranean formation with a chemomechanical treatment fluid to enhance a stimulation operation such as a fracturing operation.
  • the chemomechanical treatment fluid may be introduced into a subterranean formation to create a plurality of first fractures.
  • the chemomechanical treatment fluid may be introduced into a subterranean formation that already possesses a plurality of first fractures.
  • the operator may cease introducing chemomechanical treatment fluid into the subterranean formation and allow the chemomechanical treatment fluid to saturate the fracture tips of the existing fractures in the subterranean formation.
  • interaction of the chemomechanical treatment fluid with the formation may cause a weakening of the formation or a reduction in the fracture toughness of the formation.
  • the surfactants of chemomechanical treatment fluids may alter the free surface energy of the crack face and reduce the work required to propagate a fracture.
  • chemomechanical treatment fluids of the present invention may change the tensile strength and fracture toughness of the rocks by altering the work needed to propagate microscopic cracks.
  • Molecules at the surface of a grain have higher bond energy than internal molecules, so, to propagate a crack in a grain and create new surface area, work must be done to break the bonds of an internal molecule and crate higher energy bonds of surface grains.
  • Surface acting agents such as surfactants and inorganic salts adsorb and weakly bond with the surface molecules, lowering the bond energy and reducing the work needed to propagate a crack. Because some surface acting agents work better than others, these principles can be used to either increase or reduce the tensile strength and fracture toughness in the rock of interest.
  • pressure may be maintained in the formation or allowed to reduce, depending on the conditions of the system.
  • the time period of saturation may vary from about 15 minutes to about half an hour to about two hours. In certain embodiments, this delay (between saturation of the fracture tips and subsequent introduction of additional chemomechanical treatment fluid) allows lagging fluids sufficient time to catch up with the tip of the propagating fractions. This process may be repeated two or more times if desired. This process may be referred to as the “hesitation” method, because some fluids are left behind the tip of the fracture and require some time for them to travel towards the moving end.
  • additional chemomechanical treatment fluid may be introduced under pressure to bifurcate the fracture tips so as to form multiple fractures from each first fracture.
  • the saturation of the fracture tips allows the fluid to act as a “wedge” when additional chemomechanical treatment fluid is reintroduced into the formation.
  • the cyclical introduction of the chemomechanical treatment fluid allows a wedge-splitting effect to occur so as to enhance the fracture tip birfurcations.
  • These cyclical introductions of the chemomechanical treatment fluid may be repeated a plurality of times as desired. The subsequent reintroductions of chemomechanical treatment fluid should be sufficient to increase the pressure above the fracturing pressure.
  • any rate of injection will be suitable if the injection rate imparts a downhole pressure that is near or above the parting pressure of the formation being treated (e.g. between about 500 psi and about 5,000 psi).
  • the fractures may extend radially at least about 10 feet from the well bore into the formation.
  • the stimulation enhancement methods described herein may have particular suitability in limestone formations, sandstone formations, low permeability formations, or any combination thereof.
  • the applications described herein may have particular advantage in formations having low permeabilities of less than about 100 mD.
  • chemomechanical treatment fluids described herein include treatment of subterranean formations in anticipation of drilling. Alternatively or additionally, treatment operations may also be performed simultaneously while drilling.
  • the chemomechanical treatment fluids may interact with the subterranean formation around the wellbore to increase the fracture toughness of the formation.
  • Increasing the fracture toughness of the formation may be advantageous in certain embodiments by preventing washouts or fluid loss during certain drilling or treatment operations.
  • Increasing fracture toughness may also aid in preventing well collapse.
  • chemomechanical treatment fluids may be included as one component of a drilling mud or other completion fluid.
  • chemomechanical treatment fluids of the present invention include using chemomechanical treatment fluids to enhance secondary operations such as water flood sweeps.
  • chemomechanical treatment fluids may be used as a water flood to enhance recovery of hydrocarbons by “sweeping” any hydrocarbons remaining in place towards a production well.
  • the chemomechanical treatment fluid may also act to beneficially modify the properties of the subterranean formation so as to increase the permeability of the formation.
  • the chemomechanical treatment fluid may also act to change the fracture toughness of the formation in anticipation of a treatment operation, a stimulation operation, or a drilling operation.
  • chemomechanical treatment fluids may be designed to more efficiently target one or more zones of a subterranean formation.
  • Some embodiments of chemomechanical treatment fluids may include multiple types of surfactants and/or halide salts as desired. Where multiple surfactants and/or halide salts are used, one or more of each may be coated in a time-delay release encapsulation for delayed activation or delivery of the chemical agent.
  • a reservoir layer may be bounded above and below by adjacent barrier layers.
  • one may wish to increase the fracture toughness of the barrier layers while simultaneously decreasing the fracture toughness of the reservoir layer.
  • one chemomechanical treatment fluid may have differing effects on differing geological adjacent layers, under some circumstances, an operator may be able to advantageously increase the fracture toughness of one geological layer while simultaneously decreasing the fracture toughness of another geological layer.
  • FIG. 1 compares tensile strengths of carbonate-rich rock samples soaked in various surfactants. As shown in FIG. 1 , the chloride-rich fluid (KCl) was not as effective as the other fluids (or surfactants).
  • FIG. 2 shows average tensile strengths results of the rock samples of FIG. 1 for each of the surfactants.
  • FIG. 3 compares tensile strengths of quartz-rich sandstone rock samples both dry and soaked in various surfactants.
  • the same type of tensile strength was employed to test rock specimens from a quartz-rich sandstone formation called the “Tensleep” formation.
  • FIG. 3 shows the results of each specimen with no fluid (dry), and saturated with fluid such as a chloride (KCl) or surfactant (FS 50 and TLF 10652).
  • FIG. 4 shows average tensile strengths results of the rock samples of FIG. 3 for each of the surfactants.
  • the average for each fluid-group for the Tensleep tests are given in FIG. 4 where the average tensile strength with the chloride fluid (KCl) is only slightly lower than the average dry strength but those with the surfactants are lower by as much as 18%.
  • FIG. 5 shows the results for the Tensleep sandstone's fracture toughness, comparing the effects of 3 fluids and the dry rock.
  • the fracture toughness of carbonate-rich rock samples is compared for both dry and soaked in various surfactants.
  • FIG. 6 compares the rock sample fracture toughness results of FIG. 5 in terms of percent-reduction of toughness relative to the average dry fracture toughness.
  • the chloride-rich fluid and the surfactant TLF 10652 have the most weakening effect relative to dry rock.
  • FIG. 8 shows each of the Eagle Ford tests compared to the dry sample, where fluids lower the strength, relative to the dry condition, by 27% to 41%.

Abstract

Methods and systems are provided for favorably altering the chemomechanical properties of subterranean formations using treatment fluids comprising surfactants and halide salts. Methods for treating formations comprise the steps of introducing a chemomechanical treatment fluid into the formation and allowing the treatment fluid to interact with the formation to alter its petrochemical properties in various ways. Depending on the application, the chemomechanical treatment fluid may comprise a base fluid, a halide salt and an amphoteric or nonamphoteric surfactant where the surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration. Applications of use involving the chemomechanical treatment fluids include treatment operations, secondary recovery operations, drilling operations, and any other operation that would benefit from the formation property modifications described herein. Subterranean formation properties that may to be varied by the chemomechanical treatment fluid include fracture toughness, compressive strength, and tensile strength.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a non-provisional application which claims the benefit of and priority to U.S. Provisional Application Ser. No. 61/432,495 filed Jan. 13, 2011, entitled “Chemomechanical Treatment Fluids and Methods of Use,” which is hereby incorporated by reference in its entirety.
  • FIELD OF THE INVENTION
  • The present invention relates generally to methods and systems for treating subterranean formations. More particularly, but not by way of limitation, embodiments of the present invention include methods and systems for favorably altering the chemomechanical properties of subterranean formations with treatment fluids comprising surfactants and halide salts.
  • BACKGROUND
  • Hydrocarbons occupy pore spaces in subterranean formations such as, in sandstone and limestone formations. The pore spaces are often interconnected and have a certain permeability, which is a measure of the ability of the rock to transmit fluid flow. Maximizing production from low permeability reservoirs remains a continuing challenge in the hydrocarbon producing industry.
  • A variety of conventional methods have been used to improve the permeability of formations to enhance hydrocarbon recovery. Examples of such treatment methods include stimulation operations such as fracturing and acid stimulation operations.
  • Hydraulic fracturing is a process by which a fluid under high pressure is injected into the formation to create and/or extend fractures that penetrate into the formation. These fractures can create flow channels to improve well productivity. Propping agents of various kinds, chemical or physical, may be used to hold the fractures open and to prevent the healing of the fractures after the fracturing pressure is released. Acid stimulation, on the other hand, is a chemical stimulation method that involves the injection of acid solutions that create porous channels throughout the formation to improve the permeability and porosity of the formation.
  • While conventional methods are typically effective at improving the hydrocarbon producing characteristics of a formation, at least in the short term, operators continually seek to enhance reservoir productivity.
  • Other applications that may benefit from altering the petrochemical properties of hydrocarbon reservoirs include enhanced treatment fluids or completion fluids used prior to or simultaneously with drilling operations. For example, any treatment operation that increases a drilling operations rate-of-penetration (ROP) is usually desirable. At the same time, preventing a phenomenon referred to as washouts or loss of drilling mud or completion fluids is also desirable during some operations such as completion operations. Therefore, treating a subterranean formation so as to alter its petrochemical properties to achieve improved production characteristics continues to evoke high interest in the industry.
  • SUMMARY
  • The present invention relates generally to methods and systems for treating subterranean formations. More particularly, but not by way of limitation, embodiments of the present invention include methods and systems for favorably altering the chemomechanical properties of subterranean formations with treatment fluids comprising surfactants and halide salts.
  • One example of a method for treating a subterranean formation comprises: (a) providing a chemomechanical treatment fluid comprising a base fluid, a nonamphoteric surfactant, and a halide salt, wherein the nonamphoteric surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration; (b) introducing the chemomechanical treatment fluid under pressure into the subterranean formation, the subterranean formation having a plurality of fractures, tensile strengths, compressive strengths, and a fracture toughness, wherein each fracture has one or more fracture tips; (c) substantially ceasing the introduction of the chemomechanical treatment fluid; (d) allowing the chemomechanical treatment fluid to saturate the fracture tips; (e) allowing the chemomechanical treatment fluid to interact with the subterranean formation to decrease the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation; and (f) introducing additional chemomechanical treatment fluid after step (d) under pressure to bifurcate the fracture tips so as to from multiple fractures from each fracture.
  • One example of a method for treating a subterranean formation comprises: (a) providing a chemomechanical treatment fluid comprising a base fluid, an amphoteric surfactant, and a halide salt, wherein the amphoteric surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration; (b) introducing the chemomechanical treatment fluid into the subterranean formation; (c) allowing the chemomechanical treatment fluid to interact with the subterranean formation to increase the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation to form a treated portion of the subterranean formation; and (d) drilling a portion of a well bore in the treated portion of the subterranean formation.
  • One example of an enhanced hydrocarbon recovery method comprises: providing a chemomechanical treatment fluid comprising an aqueous base fluid, a surfactant, and a halide salt, wherein the surfactant is dissolved in the aqueous base fluid at a concentration below its critical micelle concentration; introducing the chemomechanical treatment fluid into the subterranean formation by way of an injection well; allowing the chemomechanical treatment fluid to interact with the subterranean formation to decrease the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation; and sweeping hydrocarbons towards a production well using the chemomechanical treatment fluid as a driving fluid for motivating the hydrocarbons towards the production well.
  • One example of a chemomechanical treating fluid for treating subterranean formations comprises: an aqueous base fluid wherein the aqueous base fluid comprises water and an alcohol; a nonamphoteric surfactant wherein the nonamphoteric surfactant is dissolved in the aqueous base fluid at a concentration below its critical micelle concentration; and a halide salt.
  • The features and advantages of the present invention will be apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • A more complete understanding of the present disclosure and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying figures, wherein:
  • FIG. 1 compares tensile strengths of carbonate-rich rock samples soaked in various surfactants.
  • FIG. 2 shows average tensile strengths results of the rock samples of FIG. 1 for each of the surfactants.
  • FIG. 3 compares tensile strengths of quartz-rich sandstone rock samples both dry and soaked in various surfactants.
  • FIG. 4 shows average tensile strengths results of the rock samples of FIG. 3 for each of the surfactants.
  • FIG. 5 compares fracture toughness of carbonate-rich rock samples both dry and soaked in various surfactants.
  • FIG. 6 compares the rock sample fracture toughness results of FIG. 5 for each of the surfactants to that of dry rock.
  • FIG. 7 compares the rock sample fracture toughness of the Eagle Ford Shales under dry and wet conditions.
  • FIG. 8 shows each of the Eagle Ford tests of FIG. 7 compared to the dry sample.
  • While the present invention is susceptible to various modifications and alternative forms, specific exemplary embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
  • DETAILED DESCRIPTION
  • The present invention relates generally to methods and systems for treating subterranean formations. More particularly, but not by way of limitation, embodiments of the present invention include methods and systems for favorably altering the chemomechanical properties of subterranean formations with treatment fluids comprising surfactants and halide salts.
  • In certain embodiments, methods for treating subterranean formations comprise the steps of introducing a chemomechanical treatment fluid into the subterranean formation and allowing the chemomechanical treatment fluid to interact with the subterranean formation to alter its petrochemical properties in various ways. Depending on the desired application, the chemomechanical treatment fluid may comprise a base fluid, a halide salt and an amphoteric or nonamphoteric surfactant where the surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration. Applications of use involving the chemomechanical treatment fluids include treatment operations, secondary recovery operations, drilling operations, and any other operation that would benefit from the formation property modifications described herein. Subterranean formation properties that may to be varied by the chemomechanical treatment fluid include, but are not limited to, fracture toughness, tensile strength, or a combination thereof. Other enhancements of the methods are described further below.
  • Reference will now be made in detail to embodiments of the invention, one or more examples of which are illustrated in the accompanying drawings. Each example is provided by way of explanation of the invention, not as a limitation of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment can be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention cover such modifications and variations that come within the scope of the invention.
  • In certain embodiments, chemomechanical treatment fluids may comprise a base fluid, a halide salt, and a surfactant. The chemomechanical treatment fluid may advantageously modify certain properties of the formation, such as the fracture toughness. The concentrations of and the types of halide salts and surfactants employed in the chemomechanical treatment fluid influence the interaction of the chemomechanical treatment fluid and the formation. In certain embodiments, a plurality of halide salts and/or surfactants may be employed as desired or as particular applications warrant. The specific concentrations and types of chemomechanical treatment fluids employed depend on a number of factors, including, but not limited to, desired application, formation lithology, cementation, mineralogy, virgin pore pressure, formation temperature, acidity, or pH, secondary porosity, and the presence of discontinuities (e.g. fractures, bugs, and bedding).
  • The surfactant may comprise an amphoteric surfactant or a nonamphoteric surfactant depending on the desired application. In certain embodiments, a plurality of surfactants may be used.
  • Generally, nonamphoteric surfactants may be employed where a weakening of the formation is desired, whereas amphoteric surfactants may be employed where a strengthening of the formation is desired. Examples of suitable nonamphoteric and amphoteric surfactants for use with the present invention include, but are not limited to, ammonium laurel sulfate, sodium lauryl sulfate, sodium dodecyl sulfate, fluorinated surfactants, cationic fluorinated surfactants, or any combination thereof. Under some conditions, various surfactants will act as a nonamphoteric surfactant or an amphoteric surfactant.
  • In certain embodiments, suitable concentrations of surfactants include concentrations from about 100 ppm to about 250 ppm. In certain embodiments, the concentration of surfactant is below its critical micelle concentration (CMC). The critical micelle concentration (CMC) is the concentration of surfactants above which micelles are spontaneously formed. Above the CMC, surfactants start aggregating into micelles, thus again decreasing the system's free energy by decreasing the contact area of hydrophobic parts of the surfactant with water. Upon reaching CMC, any further addition of surfactants will just increase the number of micelles (in the ideal case). CMC is an important characteristic of a surfactant. Before reaching the CMC, the surface tension changes strongly with the concentration of the surfactant. After reaching the CMC, the surface tension remains more constant.
  • The halide salt may comprise any halide salt capable of assisting the modification of formation properties, including weakening or strengthening the formation as desired. Examples of suitable halide salts for use with the present invention include, but are limited to, chloride salts, iodide, salts, bromide salts, fluoride salts, halide salts of potassium, or any combination thereof. In certain embodiments, the addition of halide salts provides beneficial petrophysical and petrochemical interactions with the formation and may enhance the effects of the surfactants in the chemomechanical treatment fluid.
  • The base fluid of the chemomechanical treatment fluid may comprise any aqueous fluid. In certain embodiments, the base fluid comprises water. The water may be from any source including, but not limited to fresh water, sea water, naturally-occurring formation water, artificially-injected formation water, or any combination thereof. In certain embodiments, the base fluid may comprise an alcohol as desired.
  • Various Methods of Use and Application
  • Useful applications of chemomechanical treatment fluids of the present invention include, but are not limited to, stimulation enhancement, fluid loss prevention during drilling applications, prevention of disintegration or prevention of weakening of the formation being drilled or stimulated, strengthening of the formation being drilled or stimulated, enhancement of secondary operations, and enhancement of hydrocarbon recovery operations.
  • One example of a method for stimulation enhancement comprises treating a subterranean formation with a chemomechanical treatment fluid to enhance a stimulation operation such as a fracturing operation. In this example, the chemomechanical treatment fluid may be introduced into a subterranean formation to create a plurality of first fractures. Alternatively or additionally, the chemomechanical treatment fluid may be introduced into a subterranean formation that already possesses a plurality of first fractures.
  • After introduction of the chemomechanical treatment fluid into the subterranean formation, the operator may cease introducing chemomechanical treatment fluid into the subterranean formation and allow the chemomechanical treatment fluid to saturate the fracture tips of the existing fractures in the subterranean formation. As mentioned previously, interaction of the chemomechanical treatment fluid with the formation may cause a weakening of the formation or a reduction in the fracture toughness of the formation. During the saturation period, the surfactants of chemomechanical treatment fluids may alter the free surface energy of the crack face and reduce the work required to propagate a fracture. That is, chemomechanical treatment fluids of the present invention may change the tensile strength and fracture toughness of the rocks by altering the work needed to propagate microscopic cracks. Molecules at the surface of a grain have higher bond energy than internal molecules, so, to propagate a crack in a grain and create new surface area, work must be done to break the bonds of an internal molecule and crate higher energy bonds of surface grains. Surface acting agents such as surfactants and inorganic salts adsorb and weakly bond with the surface molecules, lowering the bond energy and reducing the work needed to propagate a crack. Because some surface acting agents work better than others, these principles can be used to either increase or reduce the tensile strength and fracture toughness in the rock of interest.
  • During the period of saturation, pressure may be maintained in the formation or allowed to reduce, depending on the conditions of the system. In certain embodiments, the time period of saturation may vary from about 15 minutes to about half an hour to about two hours. In certain embodiments, this delay (between saturation of the fracture tips and subsequent introduction of additional chemomechanical treatment fluid) allows lagging fluids sufficient time to catch up with the tip of the propagating fractions. This process may be repeated two or more times if desired. This process may be referred to as the “hesitation” method, because some fluids are left behind the tip of the fracture and require some time for them to travel towards the moving end.
  • Upon sufficient saturation of the fracture tips, additional chemomechanical treatment fluid may be introduced under pressure to bifurcate the fracture tips so as to form multiple fractures from each first fracture. In certain embodiments, the saturation of the fracture tips allows the fluid to act as a “wedge” when additional chemomechanical treatment fluid is reintroduced into the formation. Thus, the cyclical introduction of the chemomechanical treatment fluid allows a wedge-splitting effect to occur so as to enhance the fracture tip birfurcations. These cyclical introductions of the chemomechanical treatment fluid may be repeated a plurality of times as desired. The subsequent reintroductions of chemomechanical treatment fluid should be sufficient to increase the pressure above the fracturing pressure. For most reservoirs, any rate of injection will be suitable if the injection rate imparts a downhole pressure that is near or above the parting pressure of the formation being treated (e.g. between about 500 psi and about 5,000 psi). In general, the fractures may extend radially at least about 10 feet from the well bore into the formation.
  • The stimulation enhancement methods described herein may have particular suitability in limestone formations, sandstone formations, low permeability formations, or any combination thereof. In certain embodiments, the applications described herein may have particular advantage in formations having low permeabilities of less than about 100 mD.
  • Another useful application of the chemomechanical treatment fluids described herein include treatment of subterranean formations in anticipation of drilling. Alternatively or additionally, treatment operations may also be performed simultaneously while drilling.
  • In such drilling applications, the chemomechanical treatment fluids may interact with the subterranean formation around the wellbore to increase the fracture toughness of the formation. Increasing the fracture toughness of the formation may be advantageous in certain embodiments by preventing washouts or fluid loss during certain drilling or treatment operations. Increasing fracture toughness may also aid in preventing well collapse.
  • In certain situations, decreasing the fracture toughness may be desired to increase the rate of penetration of drilling. Thus, if desired, the composition of the chemomechanical treatment fluids will be chosen to decrease rather than increase the fracture toughness of the subterranean formation. In some cases, chemomechanical treatment fluids may be included as one component of a drilling mud or other completion fluid.
  • Other beneficial applications of chemomechanical treatment fluids of the present invention include using chemomechanical treatment fluids to enhance secondary operations such as water flood sweeps. In this way, chemomechanical treatment fluids may be used as a water flood to enhance recovery of hydrocarbons by “sweeping” any hydrocarbons remaining in place towards a production well. In addition to the chemomechanical treatment fluid functioning as a water flood, the chemomechanical treatment fluid may also act to beneficially modify the properties of the subterranean formation so as to increase the permeability of the formation. Additionally or alternatively, the chemomechanical treatment fluid may also act to change the fracture toughness of the formation in anticipation of a treatment operation, a stimulation operation, or a drilling operation.
  • All or a portion of the surfactants and the halide salts may be encapsulated in a time-delay encapsulation material. Any encapsulation method known in the art may be used including, but not limited to, those encapsulating materials which degrade based on chemical or thermal conditions. In this way, chemomechanical treatment fluids may be designed to more efficiently target one or more zones of a subterranean formation. Some embodiments of chemomechanical treatment fluids may include multiple types of surfactants and/or halide salts as desired. Where multiple surfactants and/or halide salts are used, one or more of each may be coated in a time-delay release encapsulation for delayed activation or delivery of the chemical agent.
  • Where multiple geological subterranean zones are present next to one another, operators may wish to target each subterranean zone with an eye towards modifying the properties of each subterranean zone in a different way. For example, a reservoir layer may be bounded above and below by adjacent barrier layers. In certain embodiments, one may wish to increase the fracture toughness of the barrier layers while simultaneously decreasing the fracture toughness of the reservoir layer. Because one chemomechanical treatment fluid may have differing effects on differing geological adjacent layers, under some circumstances, an operator may be able to advantageously increase the fracture toughness of one geological layer while simultaneously decreasing the fracture toughness of another geological layer.
  • It is explicitly recognized that any of the elements and features of each of the methods described herein are capable of use with any of the other methods described herein with no limitation. Furthermore, it is explicitly recognized that the steps of the methods herein may be performed in any order except unless explicitly stated otherwise or inherently required otherwise by the particular method.
  • To facilitate a better understanding of the present invention, the following examples of certain embodiments are given. In no way should the following examples be read to limit, or define, the scope of the invention.
  • EXAMPLES
  • In one test, we measured the tensile strength of carbonate-rich rock samples from the Eagle Ford Reservoir, that were soaked in various chemical additives. FIG. 1 compares tensile strengths of carbonate-rich rock samples soaked in various surfactants. As shown in FIG. 1, the chloride-rich fluid (KCl) was not as effective as the other fluids (or surfactants).
  • FIG. 2 shows average tensile strengths results of the rock samples of FIG. 1 for each of the surfactants.
  • FIG. 3 compares tensile strengths of quartz-rich sandstone rock samples both dry and soaked in various surfactants. Here, the same type of tensile strength was employed to test rock specimens from a quartz-rich sandstone formation called the “Tensleep” formation. FIG. 3 shows the results of each specimen with no fluid (dry), and saturated with fluid such as a chloride (KCl) or surfactant (FS 50 and TLF 10652). FIG. 4 shows average tensile strengths results of the rock samples of FIG. 3 for each of the surfactants. The average for each fluid-group for the Tensleep tests (in FIG. 3) are given in FIG. 4 where the average tensile strength with the chloride fluid (KCl) is only slightly lower than the average dry strength but those with the surfactants are lower by as much as 18%.
  • We also measured a strength called “Fracture Toughness”, the resistance of a material to propagate a tensile fracture. FIG. 5 shows the results for the Tensleep sandstone's fracture toughness, comparing the effects of 3 fluids and the dry rock. In this Figure, the fracture toughness of carbonate-rich rock samples is compared for both dry and soaked in various surfactants.
  • FIG. 6 compares the rock sample fracture toughness results of FIG. 5 in terms of percent-reduction of toughness relative to the average dry fracture toughness. The chloride-rich fluid and the surfactant TLF 10652 have the most weakening effect relative to dry rock.
  • For the Eagle Ford carbonate-rich shales, the same fracture toughness experiments shown in FIG. 7 for wet samples and one dry sample with dry toughness of 1,240 psi-square-root of (inch). FIG. 8 shows each of the Eagle Ford tests compared to the dry sample, where fluids lower the strength, relative to the dry condition, by 27% to 41%.
  • Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations and equivalents are considered within the scope and spirit of the present invention.

Claims (31)

What is claimed is:
1. A method for treating a subterranean formation comprising:
(a) providing a chemomechanical treatment fluid comprising a base fluid, a nonamphoteric surfactant, and a halide salt, wherein the nonamphoteric surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration;
(b) introducing the chemomechanical treatment fluid under pressure into the subterranean formation, the subterranean formation having a plurality of fractures, tensile strengths, compressive strengths, and a fracture toughness, wherein each fracture has one or more fracture tips;
(c) substantially ceasing the introduction of the chemomechanical treatment fluid;
(d) allowing the chemomechanical treatment fluid to saturate the fracture tips;
(e) allowing the chemomechanical treatment fluid to interact with the subterranean formation to decrease the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation; and
(f) introducing additional chemomechanical treatment fluid after step (d) under pressure to bifurcate the fracture tips so as to from multiple fractures from each fracture.
2. The method of claim 1 wherein the base fluid comprises an aqueous fluid and wherein the nonamphoteric surfactant comprises quaternary ammonium cation surfactant.
3. The method of claim 1 wherein the base fluid comprises an aqueous fluid and wherein the nonamphoteric surfactant is ammonium laurel sulfate, sodium lauryl sulfate, or sodium dodecyl sulfate.
4. The method of claim 1 wherein the base fluid comprises water and an alcohol and wherein the nonamphoteric surfactant comprises a cationic fluorinated surfactant.
5. The method of claim 2 wherein the concentration of the quaternary ammonium cation surfactant in base fluid is from about 100 ppm to about 250 ppm.
6. The method of claim 5 wherein the subterranean formation comprises a limestone or a sandstone formation.
7. The method of claim 6 wherein the subterranean formation is a low permeability formation, having a permeability of less than about 100 mD before step (b).
8. The method of claim 7 wherein the halide salt is a chloride salt or a bromide salt.
9. The method of claim 8 wherein step (f) follows step (d) with a minimum time delay of at least about 1 hour between steps (f) and (d).
10. The method of claim 1 wherein the base fluid comprises an aqueous fluid, wherein the nonamphoteric surfactant comprises a fluorinated surfactant.
11. The method of claim 1 wherein the halide salt is a chloride salt or a bromide salt.
12. The method of claim 1 further comprising repeating steps (b) through (f) a plurality of times.
13. A method for treating a subterranean formation comprising:
(a) providing a chemomechanical treatment fluid comprising a base fluid, an amphoteric surfactant, and a halide salt, wherein the amphoteric surfactant is dissolved in the base fluid at a concentration below its critical micelle concentration;
(b) introducing the chemomechanical treatment fluid into the subterranean formation;
(c) allowing the chemomechanical treatment fluid to interact with the subterranean formation to increase the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation to form a treated portion of the subterranean formation; and
(d) drilling a portion of a well bore in the treated portion of the subterranean formation.
14. The method of claim 13 wherein the base fluid comprises an aqueous fluid and wherein the amphoteric surfactant comprises an amphoteric flourinated surfactant.
15. The method of claim 14 wherein the concentration of the amphoteric flourinated surfactant in the base fluid comprises is from about 100 ppm to about 250 ppm.
16. The method of claim 13 wherein the step (b) further comprises introducing the chemomechanical treatment fluid into the well bore.
17. The method of claim 15 wherein the subterranean formation comprises a limestone or a sandstone formation.
18. The method of claim 13 wherein the subterranean formation is a low permeability formation, having a permeability of less than about 100 mD before step (b).
19. The method of claim 17 wherein the halide salt is a chloride salt or a bromide salt.
20. The method of claim 19 wherein step (f) follows step (d) with a minimum time delay of at least about 1 hour between steps (f) and (d).
21. The method of claim 19 wherein step (f) follows step (d) with a minimum time delay of from about 15 minutes to about 1 hour between steps (f) and (d).
22. The method of claim 13 wherein the base fluid comprises an aqueous fluid and wherein the amphoteric surfactant comprises a fluorinated surfactant.
23. The method of claim 13 wherein the halide salt is a chloride salt or a bromide salt.
24. An enhanced hydrocarbon recovery method comprising:
providing a chemomechanical treatment fluid comprising an aqueous base fluid, a surfactant, and a halide salt, wherein the surfactant is dissolved in the aqueous base fluid at a concentration below its critical micelle concentration;
introducing the chemomechanical treatment fluid into the subterranean formation by way of an injection well;
allowing the chemomechanical treatment fluid to interact with the subterranean formation to decrease the tensile strengths, compressive strengths, and fracture toughness of the subterranean formation; and
sweeping hydrocarbons towards a production well using the chemomechanical treatment fluid as a driving fluid for motivating the hydrocarbons towards the production well.
25. The method of claim 24 wherein the surfactant is an amphoteric surfactant and wherein the halide salt comprises an iodide salt.
26. The method of claim 24 wherein the subterranean formation is a limestone or a sandstone formation.
27. A chemomechanical treating fluid for treating subterranean formations comprising:
an aqueous base fluid wherein the aqueous base fluid comprises water and an alcohol;
a nonamphoteric surfactant wherein the nonamphoteric surfactant is dissolved in the aqueous base fluid at a concentration below its critical micelle concentration; and
a halide salt.
28. The method of claim 27 wherein the nonamphoteric surfactant comprises a nonionic fluorinated surfactant.
29. The method of claim 28 wherein the nonamphoteric surfactant comprises an amine oxide based fluorinated surfactant.
30. The method of claim 29 wherein the concentration of ammonium laurel sulfate in the base fluid is from about 100 ppm to about 250 ppm.
31. The method of claim 30 wherein the halide salt is a chloride salt or a bromide salt.
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