[go: up one dir, main page]

WO2014193697A1 - Billes dégradables pour utilisation dans des applications souterraines - Google Patents

Billes dégradables pour utilisation dans des applications souterraines Download PDF

Info

Publication number
WO2014193697A1
WO2014193697A1 PCT/US2014/038739 US2014038739W WO2014193697A1 WO 2014193697 A1 WO2014193697 A1 WO 2014193697A1 US 2014038739 W US2014038739 W US 2014038739W WO 2014193697 A1 WO2014193697 A1 WO 2014193697A1
Authority
WO
WIPO (PCT)
Prior art keywords
degradable
wellbore
ball
degradable ball
compliant
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2014/038739
Other languages
English (en)
Inventor
Zachary Ryan Murphree
Michael Linley Fripp
Zachary William Walton
Feng Liang
Dwight Fulton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Halliburton Energy Services Inc
Original Assignee
Halliburton Energy Services Inc
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
Priority claimed from US13/907,336 external-priority patent/US9260935B2/en
Application filed by Halliburton Energy Services Inc filed Critical Halliburton Energy Services Inc
Priority to GB1516827.1A priority Critical patent/GB2528798B/en
Priority to MX2015014127A priority patent/MX2015014127A/es
Priority to AU2014271873A priority patent/AU2014271873B2/en
Priority to CA2907934A priority patent/CA2907934C/fr
Publication of WO2014193697A1 publication Critical patent/WO2014193697A1/fr
Priority to NO20151248A priority patent/NO20151248A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/12—Packers; Plugs
    • E21B33/128—Packers; Plugs with a member expanded radially by axial pressure
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B34/00—Valve arrangements for boreholes or wells
    • E21B34/06—Valve arrangements for boreholes or wells in wells
    • E21B34/14—Valve arrangements for boreholes or wells in wells operated by movement of tools, e.g. sleeve valves operated by pistons or wire line tools
    • E21B34/142—Valve arrangements for boreholes or wells in wells operated by movement of tools, e.g. sleeve valves operated by pistons or wire line tools unsupported or free-falling elements, e.g. balls, plugs, darts or pistons
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
    • E21B33/138—Plastering the borehole wall; Injecting into the formation
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
    • E21B33/14—Methods or devices for cementing, for plugging holes, crevices or the like for cementing casings into boreholes

Definitions

  • the embodiments disclosed herein relate to degradable balls, methods for their manufacture and methods for use in temporarily sealing perforations in wellbores, isolating segments of wellbores, and actuating wellbore tools.
  • Ball sealers are typically solid materials useful in sealing portions of a wellbore, subterranean formation, or both during completion operations.
  • ball sealers (sometimes referred to as perforation balls) may be used to seal a perforation in a wellbore to at least substantially reduce flow therethrough into the subterranean formation.
  • ball sealers may be used in conjunction with a baffle disposed along and within the wellbore to at least substantially reduce flow through the baffle, thereby defining upper and lower segments of the wellbore.
  • ball sealers are typically spherical with a hard, solid core made from nylon, phenolic, or aluminum .
  • the solid cores may be covered with rubber to protect them from solvents and to enhance their sealing capabilities.
  • the ball sealer should be removed from the sealing location so as to return fluid flow between to the portion of the wellbore and/or formation that was previously blocked by the sealer.
  • the density of the ball sealer is used to achieve removal . That is, ball sealers with a density greater than the fluids disposed within the wellbore (sometimes referred to as "sinkers”) may sink and accumulate at the bottom of the wellbore where they are out of the way of further operations. However, bottom hole accumulation can inhibit further wellbore operations. In other instances, ball sealers with a density less than the fluids disposed within the wellbore (sometimes referred to as "floaters”) may be flowed back to the surface and potentially reused .
  • this clean-up activity may be undesirable as it can delay further operations at the well and adds complications to the well treatment process. It is desirable to avoid either of these processes and would be desirable for the ball sealers to degrade downhole in such a manner as to not form undesirable products that may negatively affect any subsequent operations. More particularly, it is desirable that such balls degrade in a predictable manner, typically within a few hours or days.
  • degradable ball sealers also suffer from a limited useful temperature range.
  • the degradable sealers are generally made from polyvinyl alcohol (“PVA”) and/or polyvinyl acetate (“PVAC”) .
  • PVA polyvinyl alcohol
  • PVAC polyvinyl acetate
  • balls may be made from blends of polyethylene oxide (“PEO”), poly(propylene oxide) (“PPO”), and polylactic acid (“PLA”) (also referred to as polylactide).
  • PEO polyethylene oxide
  • PPO poly(propylene oxide)
  • PLA polylactic acid
  • degradable ball sealers made from any of these materials may soften and deform in use, thereby losing their sealing capability.
  • the embodiments disclosed herein relate to degradable balls, methods for their manufacture and methods for use in temporarily sealing perforations in wellbores, isolating segments of wellbores, and actuating wellbore tools.
  • One embodiment of the present invention provides for a degradable ball for downhole use, the degradable ball including an incompliant degradable polymer and a compliant filler material, the incompliant degradable polymer having an elastic modulus of about 2 GPa or greater, and the compliant filler material having an elastic modulus of less than about 2 GPa .
  • a degradable ball for downhole use, the degradable ball including a core and at least one shell disposed about the core, wherein the core includes a first incompliant degradable polymer having an elastic modulus of about 2 GPa or greater; and wherein the shell includes at least one selected from the group consisting of a degradable compliant polymer; a second incompliant degradable polymer and a compliant filler; a second incompliant degradable polymer and a degradable compliant polymer; and any combination thereof, the compliant filler material and the degradable compliant polymer each having an elastic modulus of less than about 2 GPa, and the second and third incompliant degradable polymers each having an elastic modulus of about 2 GPa or greater.
  • Yet another embodiment of the present invention provides for a method that involves introducing a degradable ball according to either of the preceding embodiments into a wellbore penetrating a subterranean formation; seating the degradable ball in a baffle arranged within the wellbore, and thereby reducing a fluid flow through the baffle and defining an upper segment of the wellbore and a lower segment of the wellbore; treating the upper segment of the wellbore; and degrading the degradable ball and thereby returning fluid connectivity between the upper segment of the wellbore and the lower segment of the wellbore.
  • Another embodiment of the present invention provides for a method that involves introducing a degradable ball according to either of the preceding embodiments into a wellbore penetrating a subterranean formation and having a wellbore tool arranged therein, wherein the wellbore tool is configured to receive the degradable ball; seating the degradable ball on the wellbore tool and thereby reducing the fluid flow through at least a portion of the wellbore tool; applying a differential pressure across the degradable ball seated on the wellbore tool and thereby actuating the wellbore tool; and degrading the degradable ball .
  • FIG. 1 relates to the dissolution of a % inches (about 2.22 cm) ball made of sebacic acid .
  • FIG. 2 illustrates the hypothetical flow of examples of certain embodiments of degradable balls described herein in a downhole environment to seal perforations.
  • FIG. 3 illustrates a degradable ball described herein seated on a baffle in a downhole environment to seal segments of the wellbore.
  • FIG. 4 illustrates two degradable balls described herein seated on baffles in a downhole environment to seal segments of the wellbore.
  • FIG. 5A illustrates a degradable ball described herein prior to seating on a wellbore tool.
  • FIG. 5B illustrates a degradable ball described herein seated on and having actuated a wellbore tool .
  • the embodiments disclosed herein relate to degradable balls, methods for their manufacture and methods for use in temporarily sealing perforations in wellbores, isolating segments of wellbores, and actuating wellbore tools.
  • ball sealers capable of withstanding high pressures and temperatures while exposed to gases and solvents.
  • the ball sealers must also resist changes in density to ensure satisfactory sealing efficiency during a wellbore operation .
  • these degradable balls may be used in subterranean applications involving temperature ranges of up to 250°F ( 121°C) or more, depending on the particular composition employed . Some of the disclosed materials have higher melting temperatures and may be used in even higher temperature applications, for example, up to 400°F (204°C) or more. As will be appreciated, the temperature limitations of the system may depend on the melting points of the degradable material forming the degradable balls described herein. Additionally, these degradable balls may exhibit sufficient strength at these temperature ranges to withstand the differential pressures present in the wellbore (e.g.
  • the degradable balls described herein should not leave an undesirable residue in the formation that could reduce the permeability of the formation.
  • carrier fluid refers to oil or water based fluids.
  • carrier fluids that are comprised of gases such as carbon dioxide or nitrogen in large or small concentrations.
  • gases such as carbon dioxide or nitrogen in large or small concentrations.
  • Such fluids may be used to transport materials, such as degradable balls or proppant particulates, downhole.
  • introducing includes pumping, injecting, pouring, releasing, displacing, spotting, circulating, or otherwise placing a fluid or material within a well, wellbore, or subterranean formation using any suitable manner known in the art.
  • degradable means that a degradable ball is degradable due to, inter alia, both the two relatively extreme cases of hydrolytic degradation that the degradable material may undergo (i. e. , heterogeneous (or bulk erosion) and homogeneous (or surface erosion)) and any stage of degradation in between these two.
  • degradation or “degradable” refer to the conversion of materials into smaller components, intermediates, or end products by the result of solubilization, hydrolytic degradation, biologically formed entities (e.g., bacteria or enzymes), chemical reactions, thermal reactions, reactions induced by radiation, or any other suitable mechanism .
  • the term "incompliant" refers to materials having an elastic modulus of about 2 GPa or greater.
  • the elastic modulus of a polymer may be measured by ASTM D638- 10.
  • the term "compliant" refers to materials having an elastic modulus of less than about 2 GPa .
  • splitting agent means and refers generally to an agent that functions to prevent, either temporarily or permanently, the flow of a fluid into a particular location, usually located in a subterranean formation, wherein the agent serves to seal the location and thereby cause the fluid to flow to a different location.
  • treatment refers to any wellbore or subterranean operation performed in conjunction with a desired function and/or for a desired purpose. It should be noted, however, that the term “treatment,” or “treating,” does not imply any particular action.
  • treatment fluid refers generally to any fluid that may be used in a subterranean application in conjunction with a desired function and/or for a desired purpose. It should be noted, however, that the term “treatment fluid” does not imply any particular action by the fluid or any component thereof.
  • stimulation refers to productivity improvement or restoration operations on a well as a result of a hydraulic fracturing, acid fracturing, matrix acidizing, sand treatment, or other type of treatment intended to increase and/or maximize the well's production rate or its longevity, often by creating highly conductive reservoir flow paths.
  • soluble means capable of being at least partially dissolved upon exposure to a suitable solvent, such as wellbore fluids, at subterranean formation conditions.
  • deformable means capable of being deformed or put out of shape.
  • a ball may be deformed when its shape is no longer spherical, such as when it deforms to assume the shape of a perforation opening or a baffle ⁇ i.e. , a ball seat) .
  • the deformation can be due at least in part to the differential pressure experienced by the degradable ball between the wellbore and the formation or between segments of a wellbore. It is an indication that the ball shape is flexible.
  • substantially plug and “seal,” as used herein, mean to occlude ⁇ i. e. seal or plug) an opening by about 95% or more. In some instances, this can be estimated in a lab environment by placing a ball sealer in a temperature controlled pressure chamber against an opening representing a perforation tunnel, ball seat, or the like and applying a flow rate, then measuring the differential pressure held by the ball as it seals against the opening and stops flow. Or by running the test and testing the difference between the unsealed flow and the sealed flow in the case of less than 100% occlusion. Also, visual tests in a lab environment can be used to estimate that no fluid, or only a small amount of fluid, flows through a perforation, ball seat, or the like.
  • compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. When “comprising” is used in a claim, it is to be understood as an open-ended term.
  • the degradable balls described herein should be able to withstand the impact force experienced when seating the ball and withstand the pressure differentials subsequently applied while still comprising materials that allow for degradation of the ball .
  • the degradation product produced may include molecule, compounds, or particulates that are small enough to travel back to the surface without significantly interacting with or plugging portions of the subterranean formation or wellbore.
  • a degradable ball may comprise compliant filler materials (e.g. , rubber particulates) dispersed in an incompliant degradable polymer ⁇ e.g. , like poly(glycolic acid) ("PGA"), also referred to as polyglycolide) and yield degradation products that include the compliant filler materials and degraded PGA.
  • the PGA may provide for degradation and the strength needed to withstand the applied pressure differentials, and the compliant filler material may mitigate breaking or cracking of the degradable ball during seating .
  • the degradable balls described herein may comprise an incompliant degradable polymer and a compliant filler material . In some embodiments, the degradable balls described herein may comprise an incompliant degradable polymer and a compliant degradable polymer. In some embodiments, the degradable balls described herein may comprise an incompliant degradable polymer, a compliant filler material, and a compliant degradable polymer.
  • polymer encompasses homopolymer and copolymers, which may be linear or branched .
  • copolymer encompasses polymers with two or more different monomeric units arranged as random copolymers, block copolymers, graft copolymers, star- or hyper-branched copolymers, and the like.
  • Suitable examples of incompliant degradable polymers may include, but are not limited to, PGA, crystalline PLA, semi-crystalline PLA having an elastic modulus of about 2 GPa or greater, polyhydroxyalkonates with an elastic modulus greater than about 2 GPa or greater (e.g. , poly- hydroxybutyrates), aliphatic polyesters with an elastic modulus greater of about 2 GPa or greater, poly(etheresters) with an elastic modulus greater of about 2 GPa or greater, polyamides with an elastic modulus greater of about 2 GPa or greater, polycarbonates, aliphatic polycarbonates, polyorthoesters, polyethylene terephthalate, and the like, copolymers thereof, blends thereof.
  • poly(lactide)-co-poly(glycolide) copolymers may be suitable for use as an incompliant degradable polymer.
  • PLA/ PGA poly(lactide)-co-poly(glycolide) copolymers
  • the elastic modulus of a polymer may depend on, inter alia, the crystallinity of the polymer, the molecular weight of the polymer, derivatization of the polymer, degree of branching of the polymer, and the like.
  • compliant filler materials may include, but are not limited to, vulcanized rubber particles, rubber fibers, thermoplastic particles, thermoplastic fibers, hollow glass spheres, hollow ceramic spheres, hollow metal spheres, hollow thermoplastic spheres, particles comprising the compliant degradable polymers described herein, and the like, and any combination thereof.
  • compliant thermoplastic materials suitable for particulates or fibers may include, but are not limited to, low-density polyethlyene, high density polyethylene, polypropylene, polyethlyene oxide, polypropylene oxide, polytetrafluoroethylene, and the like.
  • the surface of the compliant filler materials may be modified, which may enhance compatibility with and incorporation into the incompliant degradable polymer.
  • surface modifications may include, but are not limited to, surface oxidation, surface functionalization with moieties miscible with the incompliant degradable polymer, surface functionalization with oligomers of the incompliant degradable polymer, and the like, and any combination thereof.
  • hollow glass beads may be functionalized with silane compounds (e.g. , trialkoxysilane, thiols, and the like) compatible with the incompliant degradable polymer (e.g. , silane-based polyethylene glycol).
  • Compliant particles may be included in the degradable balls in an amount ranging from a lower limit of about 0.5%, 1%, 5%, or 10% by weight of the degradable balls to an upper limit of about 50%, 40%, 30%, 20%, or 10% by weight of the degradable balls, and wherein the amount may range from any lower limit to any upper limit and encompasses any subset therebetween .
  • the compliant particles may have an average diameter ranging from a lower limit of about 50 nm, 100 nm, 250 nm, 500 nm, 1 micron, 10 microns, 50 microns, or 100 microns to an upper limit of about 5 mm, 2.5 mm, 1 mm, 500 microns, 250 microns, 100 microns, 50 microns, 10 microns, 1 micron, or 500 nm, and wherein the average diameter may range from any lower limit to any upper limit and encompasses any subset therebetween.
  • Suitable examples of compliant degradable polymers may include, but are not limited to, polysaccharides (e.g.
  • dextran or cellulose dextran or cellulose
  • chitin chitosan
  • proteins aliphatic polyesters having an elastic modulus of less than about 2 GPa, amorphous PLA, semi-crystalline PLA having an elastic modulus of less than about 2 GPa, polyhydroxyalkonates with an elastic modulus greater of less than about 2 GPa, poly(£-caprolactone), poly(amino acids), poly(phosphazenes), poly(anhydrides), poly(ethylene oxide), polyester amides, and the like, and any combination thereof.
  • Polyanhydrides are another type of particularly suitable degradable polymers useful in the present invention .
  • suitable polyanhydrides include poly(adipic anhydride), poly(suberic anhydride), poly(sebacic anhydride), poly(dodecanedioic anhydride), and the like, and any combination thereof.
  • Other suitable examples include, but are not limited to, poly(maleic anhydride), poly(benzoic anhydride), and the like, and any combination thereof. Combinations of the foregoing polymers may also be suitable.
  • the degradable balls may be substantially homogeneous throughout (e.g. , compliant filler materials dispersed in the incompliant degradable polymers or incompliant degradable polymers blended with compliant degradable polymers).
  • the degradable balls may be a core-shell structure.
  • a core-shell structure provides for a core and at least one shell with a composition different than that of the core.
  • Suitable core compositions may include, but are not limited to, the incompliant degradable polymers, the incompliant degradable polymers in combination with compliant filler materials, incompliant degradable polymers blended with compliant degradable polymers, and the like.
  • Suitable shell compositions may include, but are not limited to, compliant degradable polymers, the incompliant degradable polymers in combination with compliant filler materials, incompliant degradable polymers blended with compliant degradable polymers, and the like.
  • the degradable balls may be a layered structure. It should be noted that a layered structure provides for adjacent layers to be made of different compositions. Suitable layers may include, but are not limited to, the incompliant degradable polymers, the incompliant degradable polymers in combination with compliant filler materials, compliant degradable polymers, incompliant degradable polymers blended with compliant degradable polymers, and the like.
  • the degradable balls described herein may optionally further comprise at least one additive of degradation accelerators, degradable materials, plasticizers, filler materials, and the like, and any combination thereof.
  • at least one additive of degradation accelerators, degradable materials, plasticizers, filler materials, and the like may be substantially homogeneous throughout the degradable ball, within the core and/or at least one shell of the degradable ball, or within at least one layer of the degradable ball .
  • each of the additives may independently be included in the degradable balls in an amount ranging from a lower limit of about 0.1%, 0.5%, or 1% by weight of the degradable balls to an upper limit of about 10%, 5%, or 2% by weight of the degradable balls, and wherein the amount may range from any lower limit to any upper limit and encompasses any subset therebetween.
  • an additive may be useful at a concentration outside these preferred ranges based on the desired properties of the degradable balls.
  • degradation accelerator refers to material (e.g. , particles or polymers) that accelerate the rate of degradation of the degradable material.
  • degradation accelerators may degrade to form acidic or basic degradation products that, in turn, enhance the rate of degradation of the degradable polymer of the degradable balls.
  • degradation accelerators may be highly soluble in water and dissolve quickly, thereby increasing the surface area or porosity of the degradable polymer of the degradable ball, which increases the degradation rate.
  • Suitable examples of degradation accelerators may include, but are not limited to, salts (e.g.
  • Suitable dehydrated compounds are those materials that will degrade over time when rehydrated.
  • a particulate solid dehydrated salt or a particulate solid anhydrous borate material that degrades over time may be suitable.
  • Specific examples of particulate solid anhydrous borate materials that may be used include but are not limited to anhydrous sodium tetraborate (also known as anhydrous borax), and anhydrous boric acid . These anhydrous borate materials are only slightly soluble in water. However, with time and heat in a subterranean environment, the anhydrous borate materials react with the surrounding aqueous fluid and are hydrated . The resulting hydrated borate materials are substantially soluble in water as compared to anhydrous borate materials and, as a result degrade in the aqueous fluid .
  • Blends of certain degradable materials and other compounds may also be suitable.
  • a suitable blend of materials is a mixture of poly(lactic acid) and sodium borate where the mixing of an acid and base could result in a neutral solution where this is desirable.
  • Another example would include a blend of poly(lactic acid) and boric oxide.
  • lactides have been found to be suitable for lower temperature wells, including those within the range of 60°F to 150°F (16°C to 66°C), and polylactides have been found to be suitable for wellbore temperatures above this range.
  • Poly(lactic acid) and dehydrated salts may be suitable for higher temperature wells.
  • a preferable result is achieved if the degradable material degrades slowly over time as opposed to instantaneously. In some embodiments, it may be desirable when the degradable material does not substantially degrade until after the degradable material has been substantially placed in a desired location within a subterranean formation .
  • the carboxylic acids that are suitable for use in the degradable balls described herein include, but are not limited to, such carboxylic acids as: sebacic acid (also known as dedanedioic acid, which is believed to have a melting point ("M . P.") of about 133°C (271°F) and is insoluble in water at room temperature); stearic acid (also known as octadecanoic acid, which has a M. P. of 156°C (313°F), and is a slightly dissolvable fatty acid); phthalic acid (which has a M .P. of 210°C (410°F), and is slightly soluble in water at room temperature); isophthalic acid (which has a M . P.
  • sebacic acid also known as dedanedioic acid, which is believed to have a melting point ("M . P."
  • stearic acid also known as octadecanoic acid, which has a M. P. of 156
  • adipic acid which has a M .P. of 152°C (306°F) and is slightly soluble in water at room temperature
  • pamoic acid which has a M .P. greater than 300°C (572°F) and is insoluble in water at room temperature
  • suberic acid which has a M . P. of 143°C (289°F), and is slightly soluble in water at room temperature
  • succinic acid which has a M. P. of 187°C (369°F), and is moderately soluble in water at room temperature
  • traumatic acid which has a M .P.
  • the carboxylic acids may also include, as examples: azelaic acid (HOOC— (CH 2 ) 7 — COOH, M. P. 107°C (225°F), moderately soluble in water); camphoric acid (CioHi 6 0 4 , M . P.
  • Suitable fatty alcohols and fatty esters and that may be used in the degradable balls described herein include, but are not limited to, such fatty alcohols and esters as: montanyl alcohol (which has a M .P. of 83°C (171°F); tert-butylhydroquinone (which has a M .P. of 128°C (262°F), and is insoluble in water); cholesterol (which has a M .P. of 149°C (300°F), and has a solubility of 0.095 mg/L of water at 30°C (86°F)); cholesteryl nonanoate (which has a M .P.
  • montanyl alcohol which has a M .P. of 83°C (171°F
  • tert-butylhydroquinone which has a M .P. of 128°C (262°F), and is insoluble in water
  • cholesterol which has a M .P. of 149°C (300°
  • the fatty alcohols may also include, as examples: camphor (Ci 0 Hi 6 O, with a M . P. of about 180°C (356°F), slightly soluble in water); cholecalciferol (a . k.a ., vitamin D3, C2 7 H 44 O, with a M. P.
  • the described esters are generally reaction product of alcohols and acids. Examples include but are not limited to prednisolone acetate (C2 6 H 3 6 0 6 , M . P. 233°C (451°F), slightly soluble in water), cellobiose tetraacetate (slightly soluble in water), terephthalic acid dimethyl ester, (Ci 0 H 10 O 4 , M .P. 140°C (284°F), slightly soluble in water) .
  • ester waxes such as Carnauba wax and Ouricouri wax.
  • Carnauba wax contains ceryl palmitate, myricyl ceretate, myricyl alcohol (C 30 H 6 iOH) along with other high molecular weight esters and alcohols.
  • Olho wax is a pure whitish gray carnauba wax obtained from young leaves. Refined olho wax is called flora wax.
  • Palha wax is a brownish wax obtained from older leaves. Palha wax can be emulsified with water to form chalky wax.
  • Castor wax like compound obtained by the controlled hydrogenation of pure castor oil .
  • the principle constituent is glycerol tris 12-hydroxystearate, also known as opalwax with a melting point in the range from about 78°C (172°F) to about 85°C (185°F).
  • Prolamins may also be used in the present invention.
  • Prolamins are a group of plant storage proteins having a high proline and glutamine content and found in the seeds of cereal grains.
  • the prolamins that are suitable for use in the degradable balls described herein include, but are not limited to, such prolamins as : gliadin, hordein, secalin, zein and avenin .
  • Prolamins are generally soluble only in strong alcohol solutions and have a melting point in the range from about 160°C (320°F) to about 200°C (392°F) .
  • fatty acid salts that are suitable for use in the degradable perforation balls described herein include, but are not limited to, such fatty acid salts as: sucrose distearate, calcium stearate, glyceryl monostearate, zinc stearate and magnesium stearate which is a hydrophobic substance with a melting point of 88°C ( 190°F).
  • plasticizers may be included in the degradable balls described herein.
  • the plasticizers may be present in an amount sufficient to provide the desired characteristics, for example, increased compatibility of the melt blend components, improved processing characteristics during the blending and processing steps, and control and regulation of the sensitivity and degradation of the polymer by moisture.
  • the density of the degradable balls described herein may be tailored with the use of filler materials.
  • Filler materials in accordance with some embodiments, refers to a broad range of finely powdered materials or fibrous materials that are substantially non-reactive in a downhole, subterranean environment, and typically have a size ranging from a lower limit of about 635 mesh, 600 mesh, 500 mesh, 400 mesh, 350 mesh, 325 mesh, or 250 mesh to an upper limit of about 10 mesh, 50 mesh, 100 mesh, or 200 mesh, and wherein the size may range from any lower limit to any upper limit and encompasses any subset therebetween .
  • suitable filler materials include, but are not limited to, natural organic materials, inorganic minerals, silica materials and powders, ceramic materials, metallic materials and powders, synthetic organic materials and powders, mixtures thereof, and the like.
  • Typical examples of such finely graded filler materials suitable for use herein include, but are not limited to, sodium chloride, sugar, silica flour (such as 325 mesh Silica Flour commercially- available from Santrol of Fresno, Texas, USA), calcium carbonate fillers (such as that available in a variety of mesh sizes from Vulcan Minerals Inc. of Newfoundland, California, USA), fumed silica (such as that available from PT Hutchins Co., Ltd . of Los Angeles, California, USA), and the like and any combination thereof.
  • silica flour such as 325 mesh Silica Flour commercially- available from Santrol of Fresno, Texas, USA
  • calcium carbonate fillers such as that available in a variety of mesh sizes from Vulcan Minerals Inc. of Newfoundl
  • Natural organic materials suitable for use as filler materials may include, but are not limited to, finely ground nut shells such as walnut, brazil nut, and macadamia nut, as well as finely ground fruit pits such as peach pits, apricot pits, or olive pits, and any resin impregnated or resin coated version of these.
  • Silica materials and powders suitable for use as filler materials may include, but are not limited to, glass spheres and glass microspheres, glass beads, glass fibers, silica quartz sand, sintered Bauxite, silica flour, silica fibers, and sands of all types such as white or brown, silicate minerals, and combinations thereof.
  • Typical silica sands suitable for use include Northern White Sands (Fairmount Minerals, Chardon, Ohio), Ottawa, Jordan, Brady, Hickory, Ariz., St. Peter, Wonowoc, and Chalfort.
  • the fibers can be straight, curved, crimped, or spiral shaped, and can be of any grade, such as E-grade, S-grade, and A -grade.
  • Typical silicate minerals suitable for use herein include the clay minerals of the Kaolinite group (kaolinite, dickite, and nacrite), the Montmorillonite/smectite group (including pyrophyllite, talc, vermiculite, sauconite, saponite, nontronite, and montmorillonite), and the Illite (or clay-mica) group (including muscovite and illite), as well as combinations of such clay minerals.
  • Ceramic materials suitable for use as filler materials may include, but are not limited to, ceramic beads; ceramic fibers; clay powders; finely crushed spent fluid-cracking catalysts (FCC) such as those described in U .S. Pat. No. 6,372,378; finely crushed ultra-lightweight porous ceramics; finely crushed economy lightweight ceramics; finely crushed lightweight ceramics; finely crushed intermediate strength ceramics.
  • FCC spent fluid-cracking catalysts
  • Metallic materials and powders suitable for use as filler materials may include, but are not limited to, transition metal powders, transition metal dust, and the like.
  • Synthetic organic materials and powders suitable for use as filler materials may include, but are not limited to, plastic particles, beads or powders, nylon beads, nylon fibers, nylon pellets, nylon powder, SDVB (styrene divinyl benzene) beads, SDVB fibers, TEFLON® fibers, carbon fibers such as PANEXTM carbon fibers from Zoltek Corporation (Van Nuys, Calif.) and KYNOLTM carbon fibers from American Kynol, Inc.
  • the properties of the degradable balls described herein should typically be so chosen that the degradable balls have a density ranging from a lower limit of about 0.70 g/cc, 0.75 g/cc, 0.80 g/cc, 0.85 g/cc, 0.90 g/cc, 0.95 g/cc, or 1.0 g/cc to an upper limit of about 1.5 g/cc, 1.4 g/cc, 1.3 g/cc, 1.2 g/cc, 1.1, g/cc or 1.0 g/cc, and wherein the density may range from any lower limit to any upper limit and encompasses any subset therebetween .
  • the degradable balls described herein may have a diameter in the range of about 0.625 inches (about 1.58 cm) to about 1.25 inches (about 3.18 cm) with densities ranging from about 0.7 g/cc to 1.5 g/cc. In some embodiments, the degradable balls described herein may have a diameter in the range of about 1 inch (about 2.54 cm) to about 4 inches (about 10.16 cm) with densities ranging from about 0.7 g/cc to 1.5 g/cc.
  • size and density combinations outside these preferred ranges may be applicable depending on the application .
  • degradable balls described herein may, in some embodiments, be useful in subterranean formations for controlling fluid flow between wellbore segments and/or portions of the wellbore and the subterranean formation . Degradable balls then degrade over time, and generally do not require an additional step of retrieving them from the wellbore, thereby returning fluid flow between the sealed segments, portions, or intervals of the wellbore and/or subterranean formation following a prescribed amount of time.
  • the degradable balls described herein may be useful in fluid diversion in one or more intervals of a subterranean formation having varying permeability and/or injectivity during a stimulation operation. Specifically, the degradable balls described herein become seated in the perforations of the wellbore casing and deflect the treating fluid to unsealed perforations in the wellbore casing. Referring now to FIG. 2, one or more degradable balls 200 described herein may flow through wellbore 202 lined with casing 204 to a zone of interest 206 while being pushed through workstring 208 into the perforations 210.
  • Some embodiments may involve introducing a plurality of degradable balls described herein into a wellbore penetrating a subterranean formation, wherein the wellbore comprises a plurality of perforations that fluidly connect the wellbore to the subterranean formation; seating the degradable balls in one or more of the perforations, thereby reducing the fluid flow through the one or more perforations and providing a sealed portion of the subterranean formation and a fluidly connected portion of the subterranean formation; treating the fluidly connected portion of the subterranean formation; and degrading the degradable balls, thereby returning fluid connectivity between the wellbore and the sealed portion of the subterranean formation.
  • treating the fluidly connected portion of the subterranean formation may involve hydraulic fracturing by introducing a treatment fluid at a pressure sufficient to create or extend at least one fracture in the fluidly connected portion of the subterranean formation .
  • treating the fluidly connected portion of the subterranean formation may involve matrix acidizing with a treatment fluid comprising a reactive fluid (e.g., HCI, HCI in combination with HF, and the like) at a pressure below that required to create or extend at least one fracture in the fluidly connected portion of the subterranean formation.
  • a reactive fluid e.g., HCI, HCI in combination with HF, and the like
  • the degradable balls described herein may be useful in a downhole environment to seal off segments of the wellbore.
  • degradable ball 300 that may be configured to flow through wellbore 302 lined with casing 304.
  • Degradable ball 300 may be configured to locate and land on baffle 312 defined or otherwise arranged within casing 304.
  • Baffle 312 may serve to generally separate upper and lower portions of wellbore 302, thereby defining upper segment 302a and lower segment 302b of wellbore 302. It should be noted that the terms “upper,” “lower,” “middle,” “intermediate,” and the like are used for clarity and should not be considered to be limiting as to the scope of the embodiments described herein.
  • Some embodiments may involve introducing a degradable ball described herein into a wellbore penetrating a subterranean formation, wherein the wellbore comprises a baffle configured to receive the degradable ball; seating the degradable ball in a baffle arranged within the wellbore, and thereby reducing a fluid flow through the baffle and defining an upper segment of the wellbore and a lower segment of the wellbore; treating the upper segment of the wellbore; and degrading the degradable ball and thereby returning fluid connectivity between the upper segment of the wellbore and the lower segment of the wellbore.
  • treating the upper segment of the wellbore may involve hydraulic fracturing by introducing a treatment fluid at a pressure sufficient to create or extend at least one fracture in the upper segment of the wellbore.
  • treating the upper segment of the wellbore may involve matrix acidizing the upper segment of the wellbore with a treatment fluid comprising a reactive fluid (e.g. , an acid like HCI, HCI in combination with HF, and the like) at a pressure below that required to create or extend at least one fracture in the upper segment of the wellbore.
  • a reactive fluid e.g., an acid like HCI, HCI in combination with HF, and the like
  • multiple degradable balls 400a, 400b may be useful in a downhole environment to seal off multiple segments 402a,402b,402c of wellbore 402 when seated in corresponding first and second baffles 412a,412b.
  • second degradable ball 400b which has smaller diameter than first degradable ball 400a and is smaller than the opening in first baffle 412a, may be introduced into the wellbore, pass through first baffle 412a, and become seated in second baffle 412b.
  • first degradable ball 400a may be introduced into wellbore 402 and become seated in first baffle 412a.
  • the first and second degradable balls 400a, 400b seated in the first and second baffles 412a, 412b respectively, define three axially adjacent segments 402a,402b,402c in wellbore 402.
  • Some embodiments may involve introducing a first degradable ball into a wellbore penetrating a subterranean formation, the wellbore providing a first baffle and a second baffle arranged uphole from the first baffle, wherein the second baffle is configured to allow the first degradable ball to pass therethrough and locate the first baffle; seating the first degradable ball in the first baffle and thereby reducing a fluid flow through the first baffle;
  • Some embodiments may further involve treating a third wellbore segment defined downhole from the first baffle.
  • treating any of the first, second, and third wellbore segments may involve hydraulic fracturing by introducing a treatment fluid at a pressure sufficient to create or extend at least one fracture in the upper segment of the wellbore.
  • treating any of the first, second, and third wellbore segments may involve matrix acidizing the upper segment of the wellbore with a treatment fluid comprising a reactive fluid ⁇ e.g., an acid like HCI, HCI in combination with HF, and the like) at a pressure below that required to create or extend at least one fracture in the upper segment of the wellbore.
  • a reactive fluid ⁇ e.g., an acid like HCI, HCI in combination with HF, and the like
  • FIGS. 5A and 5B illustrated is expandable packer assembly 514.
  • Assembly 514 may be extended into wellbore 502 on conveyance 526.
  • wellbore 502 may be lined with casing 504 or the like.
  • Assembly 514 may include one or more packing elements 520 configured to expand and contact inner wall 528 of casing 504 upon proper actuation .
  • FIG. 5A assembly 514 is depicted in its run-in configuration 516.
  • FIG. 5B depicts assembly 514 in its actuated configuration 518, or otherwise after packing elements 520 have been expanded .
  • degradable ball 500 In order to expand packing elements 520, degradable ball 500, such as one of those described herein, may be introduced into conveyance 526 and conveyed to assembly 514. At assembly 514, degradable ball 500 may be configured to locate and be seated within seat 522. Biasing device 524 (e.g., a spring) may be configured to bias degradable ball 500 in the uphole direction . Upon pressurizing conveyance 526, however, the hydraulic pressure within conveyance 526 overcomes the force of biasing device 524 and forces degradable ball 500 against seat 522, thereby substantially sealing conduit 530 extending below seat 522.
  • Biasing device 524 e.g., a spring
  • Increasing the pressure in the conveyance 526 may serve to force degradable ball 500 even harder against seat 522, which serves to axially compress corresponding wedges 532 on either side of packing elements 520.
  • compressing wedges 532 serves to also compress packing elements 520, thereby forcing packing elements 520 to expand radially outward and into contact with inner wall 528 of the casing 504.
  • Some embodiments may involve introducing a degradable ball according to embodiments described herein into a wellbore penetrating a subterranean formation, wherein the wellbore comprises a wellbore tool (e.g. , a packer, a sliding sleeve, a perforated sliding sleeve, a collet assembly, a crossover tool, and the like, wherein the wellbore tool is configured to receive the degradable ball; seating the degradable ball in the wellbore tool, thereby reducing the fluid flow through at least a portion of the wellbore tool; applying a differential pressure across the degradable ball seated on the wellbore tool, so as to actuate the wellbore tool; and degrading the degradable ball .
  • a wellbore tool e.g. , a packer, a sliding sleeve, a perforated sliding sleeve, a collet assembly, a crossover tool, and the like
  • actuating a packer may involve engaging packer elements of the packer with the casing of the wellbore, as described above.
  • actuating a sliding sleeve may involve axially moving the sliding sleeve within the wellbore.
  • actuating the crossover tool may involve opening or closing at least one flow path across the crossover tool (e.g. , a flow path that extends from the internal flow path of the crossover tool string into the annulus area to be packed in a gravel packing operation) .
  • the degradable balls described herein may be degradable by aqueous based fluids under acidic, neutral, or basic pH environments, depending on the chemical composition of the degradable balls.
  • acidic pH it is meant that the environment surrounding the degradable balls (e.g., the treating fluid) has a pH less than about 7, while by “neutral pH” it is meant that the environment surrounding the degradable balls has a pH of about 7, and “basic pH” means a pH of above about 7.
  • degrading a degradable ball may involve contacting the degradable ball with a degrading fluid (e.g. , an appropriately acidic, neutral, or basic aqueous fluid).
  • the degradable balls may degrade in the wellbore and/or subterranean formation without the need for introduction of an additional fluid (e.g., as a result of temperature, exposure to fluids from the formation, a previous treatment, or used in introducing the degradable ball) .
  • degrading a degradable ball may involve allowing the degradable ball to degrade.
  • the degradation rate of the degradable ball can be tailored or otherwise varied based on the compositions and configuration/structure of the degradable ball .
  • the degradable balls described herein can be manufactured using a number of processes, including melting and molding, hot press and the like. Solvent-based techniques may be suitable as well . Such processes allow the degradable balls described herein to have any number of desired three- dimensional geometric shapes, including polygonal, spherical, or more complex shapes like darts and wipers. In some instances, the degradable balls described herein may preferably be substantially spherical in shape. However, it will be apparent to those of skill in the art that any of the commonly used shapes for use in oil field tubular pipes can be used in accordance with the present invention .
  • the various components of the degradable balls can be added before injection molding (e.g. , mixed before heating or compounded as a polymer melt).
  • injection molding e.g. , mixed before heating or compounded as a polymer melt.
  • the process of the invention is practiced in a conventional injection molding machine.
  • the mixture in particulate form is tumble blended with the master-batch until homogeneous.
  • the blend is charged to the hopper of an injection molding machine which melts the resin under heat and pressure, thereby converting it to a flowable thermoplastic mass.
  • two or more blends may be produced for each of the portions of the degradable ball .
  • the nozzle of the injection molding machine is in liquid flow communication with a mold whose mold cavity or cavities is of substantially the same dimension as the final core.
  • the molds are water cooled to a temperature of about 0°C (32°F) to about 18°C (65°F) and preferably to a temperature of about 2°C (35°F) to about 7°C (45°F) which is necessary to form a skin on the surface of the polymeric mass injected into the mold.
  • the mold is continuously cooled with water in order to maintain the mold cavity surface at the low temperature.
  • thermoplastic mass is held in the mold until a spherical mass of adequate strength is formed so that upon removal of the spherical mass from the mold, the mass does not collapse.
  • the sprue is cut with a small excess above the surface of the sphere to allow for shrinkage, and the formed ball core is placed in a water immersion bath at about 0°C (32°F) to about 18°C (65°F), and more preferably, at about 2°C (35°F) to about 7°C (45°F), for a period of time to substantially quench the ball.
  • the minimum period of quenching time in the water bath is about 15 minutes. If the ball is not sufficiently cooled in the water bath, it does not shrink and an oversized product is obtained .
  • the balls are placed on a rack at ambient temperature.
  • the degradable balls described herein may be formed from the above process to have dimensions substantially the same as the mold cavity, and such cores can be produced within tolerances of plus or minus 0.1% deviation in circumference and plus or minus 0.6% deviation in weight.
  • the ball is typically characterized by a substantially smooth surface and a substantially spherical shape, although other polygonal shapes can be used.
  • Embodiments disclosed herein include, but are not limited to :
  • Embodiment A A degradable ball for downhole use, the degradable ball including an incompliant degradable polymer and a compliant filler material, the incompliant degradable polymer having an elastic modulus of about 2 GPa or greater, and the compliant filler material having an elastic modulus of less than about 2 GPa.
  • Embodiment B A degradable ball for downhole use, the degradable ball including a core and at least one shell disposed about the core, wherein the core includes a first incompliant degradable polymer having an elastic modulus of about 2 GPa or greater; and wherein the shell includes at least one selected from the group consisting of a degradable compliant polymer; a second incompliant degradable polymer and a compliant filler; a second incompliant degradable polymer and a degradable compliant polymer; and any combination thereof, the compliant filler material and the degradable compliant polymer each having an elastic modulus of less than about 2 GPa, and the second and third incompliant degradable polymers each having an elastic modulus of about 2 GPa or greater.
  • each of embodiments A and B may have one or more of the following additional elements in any combination :
  • Element 1 any one of the incompliant degradable polymers comprising at least one selected from the group consisting of poly(glycolic acid), crystalline poly(lactic acid), semi- crystalline poly(lactic acid), a polyhydroxyalkonate, poly(hydroxybutyrate), an aliphatic polyester, a polycarbonate, an aliphatic polycarbonate, a polyorthoester, polyethylene terephthalate, a copolymer thereof, and a blend thereof;
  • Element 2 any one of the compliant filler materials comprising at least one selected from the group consisting of a vulcanized rubber particle, a rubber fiber, a thermoplastic particle, a thermoplastic fiber, a hollow glass sphere, a hollow ceramic sphere, a hollow metal sphere, a hollow thermoplastic sphere, a particulate of a compliant degradable polymer, and any combination thereof;
  • Element 3 any one of the
  • Element 4 any one of the compliant filler materials comprising a plurality of particulates having an average diameter of about 50 nm to about 500 nm;
  • Element 5 any one of the compliant filler materials comprising a plurality of particulates having an average diameter of about 0.5 microns to about 1 mm;
  • Element 6 any one of the compliant filler materials comprising a plurality of particulates having a surface modification;
  • Element 7 any one of the compliant filler materials being present in an amount of about 0.5% to about 50%
  • exemplary combinations applicable to A and B include: Elements 1 and 2; Elements 1 and 3; Elements 1, 2, and 3; any of the foregoing in combination with Element 4 or Element 5; Element 6 in combination with at least one of Elements 2, 4, or 5; Element 1 in combination with the foregoing; at least one of Elements 7-10 in combination with at least one of the foregoing; at least two of Elements 7-10 in combination, and so on.
  • Embodiment C Introducing a degradable ball according to Embodiment A or B (with any combination of the optional elements as described herein) into a wellbore penetrating a subterranean formation; seating the degradable ball in a baffle arranged within the wellbore, and thereby reducing a fluid flow through the baffle and defining an upper segment of the wellbore and a lower segment of the wellbore; treating the upper segment of the wellbore; and degrading the degradable ball and thereby returning fluid connectivity between the upper segment of the wellbore and the lower segment of the wellbore; and
  • Embodiment D Introducing a degradable ball according to Embodiment A or B (with any combination of the optional elements as described herein) into a wellbore penetrating a subterranean formation and having a wellbore tool arranged therein, wherein the wellbore tool is configured to receive the degradable ball; seating the degradable ball on the wellbore tool and thereby reducing the fluid flow through at least a portion of the wellbore tool; applying a differential pressure across the degradable ball seated on the wellbore tool and thereby actuating the wellbore tool; and degrading the degradable ball.
  • Embodiment C may have the following additional elements: Element 11 : wherein treating the upper segment of the wellbore comprises introducing a treatment fluid at a pressure sufficient to create or extend at least one fracture in the subterranean formation adjacent the upper segment of the wellbore; and Element 12 : wherein treating the upper segment of the wellbore comprises matrix acidizing the upper segment of the wellbore with a treatment fluid comprising a reactive fluid at a pressure below that required to create or extend at least one fracture in the subterranean formation adjacent the upper segment of the wellbore.
  • Embodiment D may have the following additional elements : Element 13 : wherein the wellbore tool is a packer assembly and actuating the wellbore tool comprises engaging one or more packer elements of the packer assembly with an inner wall of the wellbore; Element 14 : wherein the wellbore tool is a sliding sleeve and actuating the wellbore tool comprises axially moving the sliding sleeve within the wellbore; and Element 15 : wherein the wellbore tool is a crossover tool and actuating the wellbore tool comprises opening or closing at least one flow path across the crossover tool .
  • sebacic powder is melted and molded into a
  • FIG . 1 relates to the dissolution of a % inches (about 2.22 cm) ball made of sebacic acid .
  • the ball weighs 6.47 grams and sank in water.
  • the ball remains hard up to 200°F (93°C).
  • the ball dissolves in hot water in the temperature range of about 180°F to 210°F (82°C to 99°C) with the dissolution rate increasing with temperature.
  • 200°F (93°C) water the ball's diameter decreases to 0.8 inches (about 2.03 cm) in 0.5 hours and 0.5 inches (about 1.27 cm) in about 2 hours.
  • the dissolution rate at 180°F (82°C) is considerably slower, with little diameter change in 1 hour. It is believed that such a degradable perforation ball would be useful in subterranean applications involving about 75°F to about 550°F (24°C to 288°C).
  • suberic acid and adipic acid made from melting their respective powders will dissolve in about 2 to about 3 hours at 175°F (79°C) while maintaining mechanical strength.
  • compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Mining & Mineral Resources (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des billes dégradables d'utilisation en fond de trou pouvant comprendre un polymère dégradable non souple et un matériau de charge souple, le polymère dégradable non souple ayant un module d'élasticité d'environ 2 GPa, ou plus, et la matière de charge souple ayant un module d'élasticité inférieur à environ 2 GPa. Ces billes dégradables peuvent être utiles lors du scellement de segments d'un puits de forage et de la commande d'outils de puits de forage.
PCT/US2014/038739 2013-05-31 2014-05-20 Billes dégradables pour utilisation dans des applications souterraines Ceased WO2014193697A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB1516827.1A GB2528798B (en) 2013-05-31 2014-05-20 Degradable balls for use in subterranean applications
MX2015014127A MX2015014127A (es) 2013-05-31 2014-05-20 Esferas degradables para utilizar en aplicaciones subterraneas.
AU2014271873A AU2014271873B2 (en) 2013-05-31 2014-05-20 Degradable balls for use in subterranean applications
CA2907934A CA2907934C (fr) 2013-05-31 2014-05-20 Billes degradables pour utilisation dans des applications souterraines
NO20151248A NO20151248A1 (en) 2013-05-31 2015-09-24 Degradable balls for use in subterranean applications

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/907,336 US9260935B2 (en) 2009-02-11 2013-05-31 Degradable balls for use in subterranean applications
US13/907,336 2013-05-31

Publications (1)

Publication Number Publication Date
WO2014193697A1 true WO2014193697A1 (fr) 2014-12-04

Family

ID=51989320

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/038739 Ceased WO2014193697A1 (fr) 2013-05-31 2014-05-20 Billes dégradables pour utilisation dans des applications souterraines

Country Status (6)

Country Link
AU (1) AU2014271873B2 (fr)
CA (1) CA2907934C (fr)
GB (1) GB2528798B (fr)
MX (1) MX2015014127A (fr)
NO (1) NO20151248A1 (fr)
WO (1) WO2014193697A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10414851B2 (en) 2013-06-28 2019-09-17 Kureha Corporation Rubber member for downhole tools, downhole tool, and method for recovering hydrocarbon resource
US10876374B2 (en) 2018-11-16 2020-12-29 Weatherford Technology Holdings, Llc Degradable plugs
CN114958321A (zh) * 2021-02-19 2022-08-30 中国石油天然气股份有限公司 一种压裂用暂堵球及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5253709A (en) * 1990-01-29 1993-10-19 Conoco Inc. Method and apparatus for sealing pipe perforations
US6380138B1 (en) * 1999-04-06 2002-04-30 Fairmount Minerals Ltd. Injection molded degradable casing perforation ball sealers fluid loss additive and method of use
US7503392B2 (en) * 2007-08-13 2009-03-17 Baker Hughes Incorporated Deformable ball seat
US7786051B2 (en) * 2006-12-07 2010-08-31 Schlumberger Technology Corporation Method of preventing or reducing fluid loss in subterranean formations
US20130062063A1 (en) * 2011-09-13 2013-03-14 Schlumberger Technology Corporation Completing a multi-stage well

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5253709A (en) * 1990-01-29 1993-10-19 Conoco Inc. Method and apparatus for sealing pipe perforations
US6380138B1 (en) * 1999-04-06 2002-04-30 Fairmount Minerals Ltd. Injection molded degradable casing perforation ball sealers fluid loss additive and method of use
US7786051B2 (en) * 2006-12-07 2010-08-31 Schlumberger Technology Corporation Method of preventing or reducing fluid loss in subterranean formations
US7503392B2 (en) * 2007-08-13 2009-03-17 Baker Hughes Incorporated Deformable ball seat
US20130062063A1 (en) * 2011-09-13 2013-03-14 Schlumberger Technology Corporation Completing a multi-stage well

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10414851B2 (en) 2013-06-28 2019-09-17 Kureha Corporation Rubber member for downhole tools, downhole tool, and method for recovering hydrocarbon resource
US10876374B2 (en) 2018-11-16 2020-12-29 Weatherford Technology Holdings, Llc Degradable plugs
CN114958321A (zh) * 2021-02-19 2022-08-30 中国石油天然气股份有限公司 一种压裂用暂堵球及其制备方法和应用

Also Published As

Publication number Publication date
CA2907934A1 (fr) 2014-12-04
GB2528798A (en) 2016-02-03
AU2014271873A1 (en) 2015-10-15
AU2014271873B2 (en) 2016-11-17
GB2528798B (en) 2017-04-05
CA2907934C (fr) 2016-11-08
GB201516827D0 (en) 2015-11-04
NO20151248A1 (en) 2015-09-24
MX2015014127A (es) 2016-04-20

Similar Documents

Publication Publication Date Title
US9926483B2 (en) Degradable balls for use in subterranean applications
US8936084B2 (en) Degradable perforation balls and associated methods of use in subterranean applications
US6949491B2 (en) Method and materials for hydraulic fracturing of wells
CA2909970C (fr) Bille de fracturation en mousse syntactique et ses procedes d'utilisation
US7581590B2 (en) Heterogeneous proppant placement in a fracture with removable channelant fill
US9670764B2 (en) Heterogeneous proppant placement in a fracture with removable channelant fill
CA2767427C (fr) Agents de derivation degradables et procedes correspondants
US20040261996A1 (en) Methods of diverting treating fluids in subterranean zones and degradable diverting materials
CA2907934C (fr) Billes degradables pour utilisation dans des applications souterraines
WO2014189766A2 (fr) Bille de fracturation en mousse syntactique et ses procédés d'utilisation
CN108368311B (zh) 组合物、井下工具用组合物、井下工具用分解性橡胶构件、井下工具、以及坑井挖掘方法
WO2013147796A1 (fr) Positionnement de pilier de soutènement dans une fracture contenant un fluide à haute teneur en matières solides
WO2016093690A1 (fr) Procédé de traitement de formation de méthane de couche de houille

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14804930

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2907934

Country of ref document: CA

Ref document number: 1516827

Country of ref document: GB

Kind code of ref document: A

Free format text: PCT FILING DATE = 20140520

WWE Wipo information: entry into national phase

Ref document number: 1516827.1

Country of ref document: GB

WWE Wipo information: entry into national phase

Ref document number: MX/A/2015/014127

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2014271873

Country of ref document: AU

Date of ref document: 20140520

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14804930

Country of ref document: EP

Kind code of ref document: A1