WO2012155045A2 - Récipients destructibles destinés au matériau de forage et à la fourniture de produits chimiques - Google Patents

Récipients destructibles destinés au matériau de forage et à la fourniture de produits chimiques Download PDF

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Publication number
WO2012155045A2
WO2012155045A2 PCT/US2012/037512 US2012037512W WO2012155045A2 WO 2012155045 A2 WO2012155045 A2 WO 2012155045A2 US 2012037512 W US2012037512 W US 2012037512W WO 2012155045 A2 WO2012155045 A2 WO 2012155045A2
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WO
WIPO (PCT)
Prior art keywords
containers
destructible
container
wellbore
special solid
Prior art date
Application number
PCT/US2012/037512
Other languages
English (en)
Other versions
WO2012155045A3 (fr
Inventor
Theodore LAFFERTY
John Daniels
Dmitry POTAPENKO
Bruno Lecerf
Marina Bulova
Original Assignee
Schlumberger Canada Limited
Services Petroliers Schlumberger
Schlumberger Holdings Limited
Schlumberger Technology B.V.
Prad Research And Development Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schlumberger Canada Limited, Services Petroliers Schlumberger, Schlumberger Holdings Limited, Schlumberger Technology B.V., Prad Research And Development Limited filed Critical Schlumberger Canada Limited
Priority to CN201280028793.7A priority Critical patent/CN103688018A/zh
Priority to RU2013154754/03A priority patent/RU2013154754A/ru
Priority to MX2013012912A priority patent/MX2013012912A/es
Priority to CA2835130A priority patent/CA2835130A1/fr
Priority to BR112013028953A priority patent/BR112013028953A2/pt
Publication of WO2012155045A2 publication Critical patent/WO2012155045A2/fr
Publication of WO2012155045A3 publication Critical patent/WO2012155045A3/fr

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
    • E21B27/00—Containers for collecting or depositing substances in boreholes or wells, e.g. bailers, baskets or buckets for collecting mud or sand; Drill bits with means for collecting substances, e.g. valve drill bits
    • E21B27/02—Dump bailers, i.e. containers for depositing substances, e.g. cement or acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/536—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning characterised by their form or by the form of their components, e.g. encapsulated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • 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
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures

Definitions

  • Drilling, cementing, stimulation, and various treatments, including workover operations, of oil and gas wells frequently require using various chemical additives. In some situations it is necessary to deliver such chemical additives downhole while minimizing their interactions with wellbore fluids or the wellbore itself.
  • An example of a need to deliver materials downhole without interaction with the injection fluid is the use of slugs of fiber-containing slurries for fracture isolation.
  • Treatments for example of horizontal oil and gas wells as well as multi-layered formations, frequently require using diverting techniques in order to enable treatment redirection between different zones. Diverting methods include, but are not limited to, using mechanical isolation devices such as packers and wellbore plugs, setting bridge plugs, pumping ball sealers, pumping slurried benzoic acid flakes and pumping removable and/or degradable particulates.
  • Fracture isolation with fibers is achieved by initial bridging of fibers inside the fracture, which results in plug formation by accumulation of the rest of the fiber material (and other solids if present) on the bridge formed.
  • Initiation of fiber bridging depends on the fiber concentration, so fracture isolation by this method is very sensitive to the degree of dilution of the fiber slurry with wellbore fluid during injection, which is difficult to control.
  • treatment diversion with particulates is typically based on bridging of particles of the diverting material behind the casing and forming a plug by accumulating the rest of the particles at the bridge formed.
  • Two typical problems related to treatment diversion with particulate materials are that 1) there may be reduced bridging ability of the diverting slurry during pumping resulting from dilution of the slurry by the wellbore fluid (because of interface mixing), and 2) when mixtures of particle sizes are used, there may be particle separation by size or other parameters during pumping which results in the formation of more permeable plugs and poorer treatment diversion.
  • Excessive volumes of diverting slurry typically must be pumped to minimize these effects, which increase costs and also result in a significant increase in the risk of wellbore plugging by the excess diverting material.
  • a method of delivery of a slurry that minimizes slurry dilution or alteration during injection would be valuable.
  • An example of the need to deliver chemicals downhole without their interaction with the wellbore is delivery of acid for zonal stimulation.
  • acid retarders which slow down the reaction of the acid with metal, are introduced into the pumping fluid.
  • Such retarders are not always effective and full casing protection is difficult to achieve.
  • a method of delivering acid to the bottom of a well without acid interaction with the wellbore would be desirable.
  • One embodiment is a method of treating a downhole region penetrated by a wellbore with a treatment agent.
  • the method includes delivering the treatment agent to the wellsite enclosed in one or more destructible containers, each having a shell, inserting the one or more destructible containers into the fluid being pumped down the well, and mechanically breaking the shell of the one or more destructible containers in the wellbore or in the formation to release the treatment agent.
  • the one or more destructible containers may be made of one or more materials. At least one of the materials making up the one or more destructible containers may be degradable. At least a portion of the treatment agent may also be degradable.
  • the breaking of the destructible container may be promoted by at least partial dissolution of the shell of the container in the wellbore fluid.
  • the treatment agent may be in the form of a slurry inside the one or more destructible containers.
  • the one or more destructible containers may include one or more fluid flow paths allowing entry of wellbore fluid into the container.
  • the one or more destructible containers may be mechanically destroyed by contact with one or more perforations.
  • a restriction may be placed in the wellbore to break the one or more destructible containers at a desired location; the restriction has an opening smaller than the smallest dimension of the one or more destructible containers.
  • more than one restriction may be placed in the wellbore, said restrictions successively smaller the farther away from the surface.
  • the container also may break when a fracture or wormhole in a formation becomes smaller than the container.
  • the one or more destructible containers may be made by shrink wrapping one or more films around the treatment agent.
  • the one or more destructible containers may have a hollow shell into which the treatment agent is placed.
  • the shell of the one or more destructible containers may be made of polyvinyl alcohol or gelatin.
  • a plurality of destructible containers may be used and the destructible containers may vary in one or more of size, composition, or contents.
  • Another embodiment is a method of treating a downhole region penetrated by a wellbore with a special solid diverting material.
  • the method includes delivering the special solid diverting material to the wellsite enclosed in one or more containers, each having a shell, inserting the one or more containers into fluid being pumped down the well, and allowing the one or more containers to release the special solid diverting material in the wellbore.
  • the one or more containers may be made of one or more materials. At least one of the materials making up the one or more containers is generally at least partially degradable. At least a portion of the special solid diverting material may be degradable. At least a portion of the special solid diverting material may include a blend of particles having at least three distinct sizes.
  • the special solid diverting material may include one or more of fibers, fiber flocks, fibrillated fibers, ribbons, flakes or platelets.
  • the special solid diverting material may be in the form of a slurry inside the container.
  • the one or more containers may include one or more fluid flow paths allowing entry of wellbore fluid into the container.
  • the release of the special solid diverting material may be by mechanical destruction of the container.
  • the release of the special solid diverting material may be promoted by a chemical that reacts with the container.
  • the release of the special solid diverting material may be promoted by dissolution of the container's shell in the wellbore fluid.
  • the one or more containers may be made by shrink wrapping one or more films around the special solid diverting material.
  • the one or more containers may include a hollow shell into which the special solid diverting material is placed.
  • the shell of the one or more containers may be made of polyvinyl alcohol or gelatin.
  • a plurality of containers may be used and the containers may vary in one or more of size, composition, or contents.
  • Yet another embodiment is a system for delivery of a special solid diverting material to a downhole location without dilution or separation of special solid diverting material components; this system includes the special solid diverting material enclosed in one or more destructible containers.
  • the one or more destructible containers may be made of one or more materials. At least one of the materials making up the one or more containers may be degradable.
  • the one or more destructible containers may include one or more fluid flow paths.
  • the special solid diverting material may be in the form of a slurry inside the one or more destructible containers.
  • the one or more destructible containers may be mechanically destructible. At least a portion of the special solid diverting material may be degradable.
  • the one or more destructible containers may be made by shrink wrapping one or more films around the special solid diverting material.
  • the one or more destructible containers may include a hollow shell into which the special solid diverting material is placed.
  • the one or more destructible containers may be made of a shell made of polyvinyl alcohol or gelatin.
  • a plurality of destructible containers may be used and the destructible containers may vary in one or more of size, composition, or contents.
  • Figure 1 is a schematic of destruction of a destructible container at a perforation.
  • Figure 2 is a schematic of destruction of a destructible container at a restriction apparatus placed in a wellbore.
  • Figure 3 is a schematic of the destruction of a container having a dissolvable shell in a wellbore.
  • Figure 4 is a schematic of one device for introducing destructible containers into a high pressure flow line.
  • Figure 5 shows a schematic of the experimental apparatus for studying the release of particulate materials from destructible containers at perforations.
  • destructible containers for chemicals and materials and devised a method of using these destructible containers for downhole delivery of chemical and material treatment agents.
  • the method comprises introducing the destructible containers containing chemicals or materials into the pumping line or into the wellbore followed by bullheading the containers and their contents downhole.
  • the destructible containers minimize the risk of interaction of the chemicals or materials with wellbore fluid or with the wellbore itself until destruction of the containers, which may occur, for example:
  • the destructible container comprises a shell holding one or more treatment agents.
  • the shell separates the treatment agent or agents from the outside environment until the shell is destroyed, although if, desired a small amount of an outside fluid may be allowed to enter the shell before destruction of the shell.
  • the shell may also be defined as a chemical or physical barrier or bond, including some form of adhesion of particles and/or fibers due to interaction of a coating on the surface of the materials, holding chemicals and/or materials in a pre-defined volume until it is intended to expand the contents beyond the confines of the designed volume.
  • the shell may have various mechanical properties and may be, for example, rigid, flexible, elastic, hard, fragile, or not fragile.
  • Destruction of the containers may be brought about by mechanical destruction, chemical action, dissolution or thermal destruction.
  • the destruction is by a mechanical action, then it is preferred that the remains of the empty, or nearly empty, container be subsequently destroyed in the wellbore or in the near wellbore region by chemical action, dissolution or thermal destruction.
  • the treatment agent may be any chemical or particulate materials used in wellbores and formations, such as, but not limited to, fluid loss additives, pH changing agents, lost circulation materials, scale dissolvers, cross linking agents, oxidizers, sealing agents, diverting agents, viscosifying agents, fibers, fluid breakers and viscosity reducing additives, clean-up additives, surfactants, rigid gels, chemical plugs, salts, and chemicals that react exothermically.
  • the treatment agent in the shell may be only part of a final chemical or physical process in the well.
  • the treatment agent may be a crosslinker that reacts with polymer that was not in the destructible container to form a gel that performs some treatment in the well.
  • treatment agents inside the shell including diverting agents, may be coated, for example with a resin, a polymer, a salt, an organic compound, and/or an inorganic compound.
  • the destructible container consists of a destructible enclosure or shell filled with a diverting material, preferably a diverting material that is partially or completely degradable, soluble, reactible, meltable or otherwise destroyable other than mechanically.
  • the degradation may be caused or enhanced by a chemical inside the destructible container, for example in addition to the main treatment agent.
  • shell destruction optionally may be initiated by penetration of the wellbore fluid into the container (as examples, a water-soluble enzyme breaker placed inside a container having a gelatin shell; citric acid placed inside a container having an acid-soluble or acid-destructible shell such as one made of borate cross-linked guar or cellulose; or solids such as NaOH, Ca(OH) 2 , CaC0 3 or Mg(OH) 2 included in the contents of a polylactic acid shell).
  • a water-soluble enzyme breaker placed inside a container having a gelatin shell
  • citric acid placed inside a container having an acid-soluble or acid-destructible shell such as one made of borate cross-linked guar or cellulose
  • solids such as NaOH, Ca(OH) 2 , CaC0 3 or Mg(OH) 2 included in the contents of a polylactic acid shell.
  • a diverting material as being at least partially destroyable or degradable we mean that the diverting material, or at least one component of the diverting material is sufficiently destroyable or degradable that the ability of the plug or seal to block fluid flow is reduced so that it no longer blocks fluid flow; in some cases this may be as little as about 5 percent of the diverting material being destroyable or degradable.
  • the container whose shell protects the contents from dilution with wellbore fluids as well as from particle size and/or shape separation during pumping, is introduced into the wellbore and pumped downhole. The container is destroyed, for example mechanically, causing the release of the diverting material which plugs or seals a stimulated interval and provides treatment diversion to another region.
  • Several preferred mechanisms may be used for enclosure or shell destruction:
  • the container may be destroyed sufficiently by at least partial dissolution (for example more than 5% of the shell being dissolved) in the surrounding fluid (for example a polyvinyl alcohol shell), or by weakening of the shell by partial dissolution in the surrounding fluid followed by mechanical destruction (for example a gelatin shell).
  • the surrounding fluid for example a polyvinyl alcohol shell
  • destructible containers for fiber and/or particle delivery for fracture isolation allows maintenance of high fiber and/or particle concentrations at the downhole location by minimizing the risk of dilution of the fibers with wellbore fluid.
  • the fiber and/or particles in the destructible containers may be dried or slurried.
  • the liquid in which the solids are slurried may be, for example, an aqueous liquid or a linear or crosslinked aqueous polymer solution.
  • the solids may be slurried in situ in a wellbore fluid which penetrates the container.
  • the liquid phase of the slurry may also be non-aqueous, such as an alcohol (as examples glycerol, ethanol, methanol, and isopropanol, ethylene glycol); and/or liquid hydrocarbons such as diesel, hexane, or aromatic hydrocarbons such as benzene, toluene etc.
  • Delivery of acid in such containers with subsequent acid release of the acid downhole provides casing or wellbore wall protection during acid treatments.
  • Other treatment agents may be delivered advantageously, for example bases such as sodium hydroxide.
  • fibers and/or particulates are vacuum packed into small bundles (to maximize the concentration) and surrounded by a coating or put into an enclosure, for example shrink-wrapped or vacuum packed, that is engineered to have various degradation times or destruction degrees of difficulty.
  • an additive is used at various concentrations to interact with the coating or container at varying rates.
  • a shell or coating may optionally quickly be degraded or destroyed after introduction of fiber (or other shape) and/or particle packs into the treating fluid so that fiber (or other shape) and/or particle dispersion occurs in the mixing and/or pumping equipment or while traveling downhole. This method may still deliver higher concentrations of special solid diverting materials to a location downhole.
  • containers for fibers or other shapes simplifies fiber (or other shapes) delivery.
  • These containers may be introduced through a blender in large amounts and simple equipment may be used. Premature destruction of some of the containers in the treating equipment is not critical as long as the majority (for example at least about 60 %) of the containers survive to enter the wellbore. Note that if a container is made of multiple layers, it is not considered destroyed until all of the layers have been destroyed to the point that the contents can be released. The ultimate fiber concentration that can reliably be obtained downhole is much higher than if fibers are fed directly into the fluid.
  • the inventors are not aware of any method of downhole delivery of any chemical agents or solid materials that are placed in destructible containers that are pre-formed empty and then filled, or are placed around the agents or materials, and then broken in surface equipment or in the wellbore by special apparatus previously placed in the wellbore or by perforations to release the contents into a formation or fracture, such as but not limited to, bags or hollow balls (that may optionally be rigid and may optionally dissolve, degrade, etc. after release of the contents).
  • bags or hollow balls that may optionally be rigid and may optionally dissolve, degrade, etc. after release of the contents.
  • 7,049,272 discloses a method of treating a well with solids, liquids or apparatuses by 1) encasing said solids, liquids or apparatuses in a pre-formed water soluble shell such as a PVA cylinder, 2) conveying said encased solids, liquids or apparatuses to a predetermined location in the well, and 3) allowing the water-soluble shell to dissolve in the aqueous phase in the wellbore.
  • the shell is "resistant to diffusion in either direction" and “able to resist substantial physical and mechanical forces without breaking"; illustrative examples include placing encased soap at the bottom of the well for assisting in gas-lift, and placing corrosion inhibitors.
  • U. S. Pat. No. 6,794,340 discloses a method of removing drill cuttings from wellbores and drilling fluids by crosslinking drilling fluid with a crosslinker and a crosslinker activator that is encapsulated and released by destruction of the capsule as it passes through the drill bit or that is released by dissolution or melting of the encapsulation material. All encapsulated material and any remaining encapsulation material are returned to the surface.
  • 4,614,599 discloses a lost circulation treatment comprising encapsulating lime in a reaction-preventive protective casing (such as a film of wax) in a circulating drilling fluid to prevent the lime from reacting with clays in the borehole until it is desired to breach the casing; if lost circulation occurs, circulation is slowed or stopped so that the temperature rises and the time of the fluid in the lost circulation pathway lengthens and the coating dissolves or melts and the lime reacts with clays in the drilling fluid and/or the formation to plug the lost circulation pathway.
  • a reaction-preventive protective casing such as a film of wax
  • Capsules may also degrade in the wellbore or formation, or dissolve, or melt, or be ruptured by entrance of a fluid by osmosis.
  • diversion methods include but are not limited to diversion with 1) viscous fluids or fluids that become viscous, such as the so-called self-diverting fluids, 2) foams and emulsions, 3) ball sealers, including degradable and soluble ball sealers, 4) mechanical tools and well completion tools, 5) limited entry perforation diverting techniques, and 6) stress assisted diversion.
  • the destructible containers are made of a material that is at least partially degradable, soluble, reactible, meltable or otherwise destroyable other than mechanically, or are made of more than one component, at least one of which is destroyable other than mechanically, so that after destruction at least part of the container will disappear.
  • a container as at least partially destroyable or degradable we mean that at least 5 %, preferably at least 50 %, of the container is destroyable or degradable.
  • existing or modified delivery equipment may be used, depending on the mechanism of the destruction of the containers and the purpose of their use.
  • the location at which the destruction occurs may be determined by selection, adaptation, or special design of surface and/or downhole equipment.
  • Some embodiments include delivering diverting materials downhole in destructible containers.
  • the principle advantages include 1) delivering the material to a desired location downhole in concentrated form while eliminating or reducing the problems of dilution or size or density separation of the materials before they arrive at the desired downhole location, and 2) convenient delivery to the well site and convenient injection into the injection fluid without the problems associated with transporting and metering materials that may be difficult to handle, such as fibers and mixtures of different sizes of, or different shapes of, materials.
  • Embodiments may be described here in terms of solid diverting materials in fracturing, but the destructible container can carry any inert or active solids, fluids, or combinations of solids and fluids to any desired downhole location for any purpose.
  • the container is generally either a pre-formed container such as a hollow sphere, for example of polylactic acid (PLA), or a bag that is filled after it is made or a similar structure that is fashioned around the contained material; either way, it is sealed after it is filled.
  • the container may be referred to as a shell, envelope, etc.
  • the container is then introduced into the fluid being injected downhole, is carried to the desired location, and then is deliberately broken there to release the contents.
  • special solid diverting material by destructible “container” we do not mean a coating of another material that is put on by spray coating or polymerization and the like as is often meant in the literature when a material is described as "encapsulated”.
  • special solid diverting material we mean, for example, fibers; other shapes such as flakes, platelets, ribbons, rods, precipitated material from chemical reactions, grains, pellets; mixtures of different sizes of approximately spherical materials; and mixtures of fibers or flakes or other shapes and one or more sizes of approximately spherical materials (for example having aspect ratios of less than about 5, preferably less than about 3).
  • Non-limiting examples of approximately spherical materials include plastic beads, sand, ceramic beads, glass, wax beads, proppant, silica flour, alumina, and calcium carbonate. All such special solid diverting materials are designed to plug openings of a certain size, such as a wellbore, a vug, a fluid loss pathway, a hydraulic fracture, wormhole etc. Special solid diverting materials may be enclosed in any way and be within the scope of embodiments. Preferably the special solid diverting material is degradable and/or removable under downhole conditions. Chemicals or materials other than special solid diverting materials enclosed in mechanically destructible containers are within the scope of embodiments.
  • Figures 1, 2, and 3 show several methods of deliberately breaking destructible containers downhole.
  • release of diverting material is caused by destruction of downhole containers at perforations.
  • the wellbore is shown as horizontal but may be in any orientation.
  • the container flows along the wellbore (A) and is pressed against the opening of the first perforation it encounters, by the fluid pressure, and the container breaks (B), which is believed to be due to differential pressure across the perforation.
  • the perforations have dimensions smaller than the smallest dimension of the container.
  • the destruction is caused by a special restriction, having a cross section smaller than that of the destructible container that has been placed in the wellbore; the restriction typically is placed upstream of the perforations and has a diameter smaller than the smallest dimension of the container. After the container is broken the contents enter downstream perforations.
  • a variation of this system is the use of varying sizes of destructible containers and several progressively smaller restrictions along the perforated zone. Smaller containers pass through the first, larger, restrictions and do not break until they reach a restriction smaller than the container. This ensures that all the perforations receive treatment material; this scheme can also be used to deliver different materials to different regions of the perforated zone. Not shown is that in these cases the perforations may optionally be larger than at least some of the containers, or alternatively some of the containers may be broken by perforations.
  • destruction of the container may be caused by shear downhole in the wellbore (for example at a change in direction or a narrowing of the wellbore), or by passing near or collision with other apparatus downhole such as a perforating gun.
  • Deliberate mechanical destruction may be aided by partial chemical destruction or dissolution or thermal weakening of the shell or by a combination of such processes.
  • Destructible containers may also be sized to break at a certain point inside a fracture or wormhole.
  • Destructible containers may be tested, preferably in the laboratory, to ensure that they break where desired. For example, if the destructible containers are to be broken by a downhole restriction or by perforations, they may be tested to ensure that they are not broken by high differential pressures encountered first or by striking surface line or wellbore walls (for example at bends). If necessary, the strength of the shell may be increased or holes or a leaf valve or leaf burst valve may be used to relieve differential pressure. Dissolvable container may be tested by measuring the time required for sufficient destruction of the shell by dissolution at conditions emulating the conditions during pumping (shear rate, temperature, pressure, etc.). The shell is considered to have been destroyed at the point at which, although the shell may not have been completely dissolved, the mechanical integrity has been reduced significantly enough that the contents can be released.
  • the mechanically destructible downhole container may be of any shape, but is preferably spherical or has an aspect ratio of less than about 3.
  • An approximately spherical shape is advantageous because: (1) if the container is not approximately spherical and one dimension is significantly longer than the others, then the container may become trapped in surface lines or connections if it is not correctly oriented when it enters a connection or pipe; (2) surface handling of spheres is easier than surface handling of non-spherical shapes and the orientation when feeding the container into the well is not an issue; and (3) for spheres, the same equipment, calculations, and considerations established for ball sealers may be used.
  • the volume of the destructible downhole containers varies from about 0.5 cm 3 (which corresponds to a sphere having a diameter of about 1 cm), to about 24 L (which corresponds to a cylinder having a diameter of about 17.5 cm and a length of about 100 cm).
  • the preferred volume of the destructible downhole containers ranges from about 8 cm 3 to about 2.8 L (which corresponds to spheres having diameters from about 2.5 cm to about 17.5 cm).
  • the most preferred volume of the destructible downhole containers is in the range of from about 20 cm 3 to about 1 L (which corresponds to spheres having diameters from about 5 cm to about 12.5 cm).
  • the preferred volume of the containers is in the range of about 0.5 cm 3 and about 2 cm 3 , which allows pumping such containers through typical surface equipment.
  • the outer enclosure or shell (or bag or envelope, etc.) of the destructible container which may be rigid or flexible, is made of a material which is mechanically destructible at downhole conditions. Examples of such materials include plastics, glass, ceramics, gelatin etc.
  • the shell of the container in some embodiments may also be chemically degradable, dissolvable or meltable. Normally, degradation takes place after the shell is broken.
  • the shell may be degradable in, or soluble in, the wellbore or formation fluids. This minimizes the risk of formation damage by the shell material and assists in wellbore and formation clean-up.
  • degradable materials which may be used for making the shell of the destructible downhole container are polyesters (including PLA, PGA, esters of lactic acid, glycolic acid, other hydroxyacids, and copolymers thereof; polyamides and copolymers thereof; polyethers and copolymers thereof); polyurethanes, etc.
  • Nonlimiting examples of degradable materials include certain polymer materials that are capable of generating acids upon degradation. These polymer materials may herein be referred to as "polymeric acid precursors"; they can be used as destructible shell materials or as degradable diverting materials, depending on their properties. These materials are typically solids at room temperature.
  • the polymeric acid precursor materials include the polymers and oligomers that hydrolyze or degrade in certain chemical environments under known and controllable conditions of temperature, time and pH to release organic acid molecules that may be referred to as "monomeric organic acids.”
  • the expression “monomeric organic acid” or “monomeric acid” may also include dimeric acid or acid with a small number of linked monomer units that function similarly to monomer acids composed of only one monomer unit, in that they are fully in solution at room temperature.
  • Polymer materials may include those polyesters obtained by polymerization of hydroxycarboxylic acids, such as the aliphatic polyesters of lactic acid, referred to as polylactic acid; of glycolic acid, referred to as poly glycolic acid; of 3-hydroxbutyric acid, referred to as polyhydroxybutyrate; of 2-hydroxyvaleric acid, referred to as polyhydroxyvalerate; of epsilon caprolactone, referred to as polyepsilon caprolactone or polycaprolactone; the polyesters obtained by esterification of hydroxyl aminoacids such as serine, threonine and tyrosine; and the copolymers obtained by mixtures of the monomers listed above.
  • a general structure for the above-described homopolyesters is:
  • Rl, R2, R3, and R4 are either H, linear alkyl, such as CH 3 , CH 2 CH 3 (CH 2 ) n CH 3 , branched alkyl, aryl, alkylaryl, a functional alkyl group (bearing carboxylic acid groups, amino groups, hydroxyl groups, thiol groups, or others) or a functional aryl group (bearing carboxylic acid groups, amino groups, hydroxyl groups, thiol groups, or others); x is an integer between 1 and 11 ;
  • y is an integer between 0 and 10;
  • z is an integer between 2 and 50,000.
  • polyesters such as those described here may hydrolyze and degrade to yield hydroxycarboxylic acids and compounds such as those acids referred to in the foregoing as "monomeric acids.”
  • a suitable degradable polymeric acid precursor is the polymer of lactic acid, sometimes called polylactic acid, "PLA," polylactate or polylactide.
  • Lactic acid is a chiral molecule and has two optical isomers. These are D-lactic acid and L-lactic acid.
  • the poly(L-lactic acid) and poly(D-lactic acid) forms are generally crystalline in nature.
  • Polymerization of a mixture of the L- and D-lactic acids to poly(DL-lactic acid) results in a polymer that is more amorphous in nature.
  • the polymers described herein are essentially linear.
  • the degree of polymerization of the linear polylactic acid can vary from as few units as necessary to make them solids under downhole conditions to several thousand units (e.g. 2000-5000). Cyclic structures may also be used.
  • the degree of polymerization of these cyclic structures may be smaller than that of the linear polymers.
  • These cyclic structures may include cyclic dimmers if they are solids under storage and well
  • polymer of glycolic acid also known as polyglycolic acid (“PGA”), or polyglycolide.
  • PGA polyglycolic acid
  • Other materials suitable as polymeric acid precursors are all those polymers of glycolic acid with itself or with other hydroxy-acid-containing moieties, for example as described in U.S. Patent Nos. 4,848,467; 4,957, 165; and 4,986,355.
  • the polylactic acid and polyglycolic acid may each be used as homopolymers, which may contain less than about 0.1% by weight of other comonomers.
  • homopolymer(s) is meant to include polymers of D-lactic acid, L-lactic acid and/or mixtures or copolymers of pure D-lactic acid and pure L-lactic acid. Additionally, random copolymers of lactic acid and glycolic acid and block copolymers of polylactic acid and polyglycolic acid may be used. Combinations of the described homopolymers and/or the above-described copolymers may also be used.
  • polyesters of hydroxycarboxylic acids that may be used as polymeric acid precursors are the polymers of hydroxyvaleric acid (polyhydroxyvalerate), hydroxybutyric acid (polyhydroxybutyrate) and their copolymers with other hydroxycarboxylic acids.
  • Polyesters resulting from the ring opening polymerization of lactones such as epsilon caprolactone (polyepsiloncaprolactone) or copolymers of hydroxyacids and lactones may also be used as polymeric acid precursors.
  • Polyesters obtained by esterification of other hydroxyl-containing acid- containing monomers such as hydroxyaminoacids may be used as polymeric acid precursors.
  • Naturally occurring aminoacids are L-aminoacids.
  • the three most common aminoacids that contain hydroxyl groups are L-serine, L-threonine, and L- tyrosine. These aminoacids may be polymerized to yield polyesters at the appropriate temperature and using appropriate catalysts by reaction of their alcohol and their carboxylic acid groups.
  • D-aminoacids are less common in nature, but their polymers and copolymers may also be used as polymeric acid precursors (destructible shell or degradable diverting materials, depending upon properties).
  • Polymeric acid precursors destructible shell or degradable diverting materials, depending upon properties.
  • NatureWorks, LLC, Minnetonka, MN, USA produces solid cyclic lactic acid dimer called "lactide” and from it produces lactic acid polymers, or polylactates, with varying molecular weights and degrees of crystallinity, under the generic trade name NATUREWORKSTM PLA.
  • the PLA's currently available from NatureWorks, LLC have number average molecular weights (M n ) of up to about 100,000 and weight averaged molecular weights (M w ) of up to about 200,000, although any polylactide (made by any process by any manufacturer) may be used. Those available from NatureWorks, LLC typically have crystalline melt temperatures of from about 120 to about 170 °C, but others are obtainable. Poly(d,l-lactide) of various molecular weights is also commercially available from Bio-Invigor, Beijing and Taiwan. Bio-Invigor also supplies polyglycolic acid (also known as polyglycolide) and various copolymers of lactic acid and glycolic acid, often called “polygalactin” or poly(lactide-co-glycolide).
  • M n number average molecular weights
  • M w weight averaged molecular weights
  • Poly(d,l-lactide) of various molecular weights is also commercially available from Bio-Invigor
  • the extent of the crystallinity can be controlled by the manufacturing method for homopolymers and by the manufacturing method and the ratio and distribution of lactide and glycolide for the copolymers. Additionally, the chirality of the lactic acid used also affects the crystallinity of the polymer.
  • Polyglycolide can be made in a porous form. Some of the polymers dissolve very slowly in water before they hydrolyze.
  • Amorphous polymers may be useful in certain applications.
  • An example of a commercially available amorphous polymer is that available as NATUREWORKS 4060D PLA, available from NatureWorks, LLC, which is a poly(DL-lactic acid) and contains approximately 12% by weight of D-lactic acid and has a number average molecular weight (M n ) of approximately 98,000 g/mol and a weight average molecular weight (M w ) of approximately 186,000 g/mol.
  • polyesters obtained by polymerization of polycarboxylic acid derivatives such as dicarboxylic acid derivatives with polyhydroxy-contaning compounds, in particular dihydroxy containing compounds.
  • Polycarboxylic acid derivatives that may be used are those of dicarboxylic acids such as oxalic acid, propanedioic acid, malonic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, pentanedioic acid, adipic acid, phthalic acid, isophthalic acid, terphthalic acid, aspartic acid, or glutamic acid; polycarboxylic acid derivatives are those such as of citric acid, poly and oligo acrylic acid and methacrylic acid copolymers; other materials that may be used if they are solids, or may be used as starting materials for polymerization if they are liquids, are dicarboxylic acid anhydrides, such as, maleic anhydride, succinic anhydride, pentan
  • Useful polyhydroxy containing compounds for making useful degradable polymers are those dihydroxy compounds such as ethylene glycol, propylene glycol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, hydroquinone, resorcinol, bisphenols such as bisphenol acetone (bisphenol A) or bisphenol formaldehyde (bisphenol F); and polyols such as glycerol.
  • dihydroxy compounds such as ethylene glycol, propylene glycol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, hydroquinone, resorcinol, bisphenols such as bisphenol acetone (bisphenol A) or bisphenol formaldehyde (bisphenol F); and polyols such as glycerol.
  • bisphenols such as bisphenol acetone (bisphenol A) or bisphenol formaldehyde (bisphenol F)
  • Rl and R2 are linear alkyl, branched alkyl, aryl, and alkylaryl groups; and z is an integer between 2 and 50,000.
  • polyesters derived from phthalic acid derivatives such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like.
  • polyesters such as those described herein can "hydrolyze” and “degrade” to yield polycarboxylic acids and polyhydroxy compounds, regardless of the original polyester synthesized from any of the polycarboxylic acid derivatives listed above.
  • the polycarboxylic acid compounds yielded by the polymer degradation process are also considered monomeric acids.
  • polymer materials that may be used are those obtained by the polymerization of sulfonic acid derivatives with polyhydroxy compounds, such as polysulphones or phosphoric acid derivatives with polyhydroxy compounds, such as polyphosphates.
  • Such solid polymeric acid precursor material may be capable of undergoing an irreversible breakdown into fundamental acid products downhole.
  • irreversible will be understood to mean that the solid polymeric acid precursor material, once broken downhole, does not reconstitute downhole, e.g., the material breaks down in situ but does not reconstitute in situ.
  • break down refers to both of the two extreme cases of hydrolytic degradation that the solid polymeric acid precursor material may undergo, e.g., bulk erosion and surface erosion, and any stage of degradation in between these two. This degradation can be a result of, inter alia, a chemical reaction. The rate at which the chemical reaction takes place may depend on, inter alia, the chemicals added, temperature and time.
  • the breakdown of solid polymeric acid precursor materials may or may not depend, at least in part, on their structure. For instance, the presence of hydrolyzable and/or oxidizable linkages in the backbone often yields a material that will break down as described herein.
  • the rates at which such polymers break down are dependent on factors such as, but not limited to, the type of repetitive unit, composition, sequence, length, molecular geometry, molecular weight, morphology (e.g., crystallinity, size of spherulites, and orientation), hydrophilicity, hydrophobicity, surface area, and additives.
  • the manner in which the polymer breaks down also may be affected by the environment to which the polymer is exposed, e.g., temperature, presence of moisture, oxygen, microorganisms, enzymes, pH, and the like.
  • solid polymeric acid precursor materials that may be used include, but are not limited to, those described in the publication in Advances in Polymer Science, Vol. 157, entitled “Degradable Aliphatic Polyesters,” edited by A. C. Albertsson, pages 1-138.
  • polyesters that may be used include homopolymers, and random, block, graft, and star- and hyper-branched aliphatic polyesters.
  • polyamides and polyimides are suitable solid polymeric materials that may be used as destructible containers and/or degradable diversion materials.
  • Such polymers may comprise hydrolyzable groups in the polymer backbone that may hydrolyze under the conditions that exist downhole.
  • suitable polyamides include proteins, polyaminoacids, nylon, and poly(capro lactam).
  • Another class of polymers that may be suitable for use is those polymers that may contain hydrolyzable groups, not in the polymer backbone, but as pendant groups. Hydrolysis of the pendant groups may generate a water-soluble polymer and other byproducts.
  • a nonlimiting example of such a polymer is polyvinylacetate, which upon hydrolysis forms water-soluble polyvinylalcohol and acetate salts.
  • Other suitable materials include polysaccharides, chitins, chitosans, orthoesters, polyanhydrides, polycarbonates, poly(orthoesters), poly(ethylene oxdides), and polyphosphazenes
  • the shell may be made of a material that will disintegrate into smaller pieces at downhole conditions over a time which is much longer (for example at least 100 times longer, preferably at least 5 times longer, most preferably at least 3 times longer) than the time it takes to pump the container to the release location. It should be noted that some materials that disintegrate also degrade by other mechanisms and vice versa. Materials that eventually disintegrate include plastics such as polylactic acid (PLA), polyamides and composite materials comprising degradable plastic and non-degradable fine solids. It should be mentioned that some degradable materials pass through a disintegration stage during the degradation process. An example is PLA, which turns into a fragile material before complete degradation.
  • PLA polylactic acid
  • the shell of the destructible downhole container may also be deformable and engineered to minimize the risk of premature destruction during pumping through the surface equipment and the wellbore if desired.
  • the shell of the destructible downhole container may be engineered to be broken during pumping through the surface equipment and the wellbore if desired.
  • the shell may also have perforations or holes in its surface to allow fluid, for example wellbore fluid, penetration inside the destructible container.
  • the holes may be in the form of check valves or one-way valves such as leaf valves or leaf burst valves.
  • Such perforations may (a) equalize the hydraulic pressure outside and inside the container and thus minimize the risk of premature destructing of the container by hydraulic pressure, and/or (b) enable greater mobility of the material inside the container, which will assist in better release of the material, such as special solid diverting material, from the container after its destruction.
  • Many solid diverting materials are suitable for delivery by destructible containers for the purpose of creating a fluid-diverting plug. Suitable solid diverting agents include, but are not limited to, rock salt, wax beads, oil-soluble resins, benzoic acid flakes, degradable polymer particles and fibers, cellophane flakes, various precipitates, nuts, and shells.
  • Diversion may be used to enable treatment redirection in matrix stimulation operations below fracture pressure as well as in single or multistage hydraulic fracturing.
  • matrix stimulation the effect may be achieved by reducing the permeability of the formation because of solids penetration.
  • the mechanism for solid-assisted diversion during fracturing operations is more complicated and is based on bridging of the fibers and/or particulates in the fracture with subsequent accumulation of additional solid material on the bridge, creating a plug.
  • the advantage of diversion with solids over other treatment redirection methods is in lower cost and simplicity.
  • Diverting materials inside destructible downhole containers may be in many forms, such as particulates, approximately spherical particles, particles having aspect ratios less than about 5 and preferably less than about 3; fibers, flakes, viscous or viscosifiable fluids, and mixtures thereof.
  • Such diverting materials may be degradable, removable, soluble in wellbore or formation fluids, or meltable.
  • some components of such mixtures may be stable at downhole conditions and some may be degradable, removable, soluble in wellbore or formation fluids, or meltable. Diverting materials may also disintegrate into smaller pieces under downhole conditions after creating seals.
  • one example of special solid diverting materials, destructible downhole containers are filled with blends of particles designed for sealing narrow voids such as perforations, fractures, wormholes, etc.
  • the diverting agent is a blend including a first amount of particulates having a first average particle size between about 2 mm and 2 cm and a second amount of particulates having a second average size between about two and ten times smaller than the first average particle size or a second amount of flakes having a second average size up to ten times smaller than the first average particle size.
  • the blend includes a first amount of particulates having a first average particle size between about 50 to 100 % of the perforation diameter and a second amount of particulates having a second average size between about 1.6 and 20 times smaller than the first average particle size, or a second amount of flakes having a second average size up to ten times smaller than the first average particle size.
  • a blend having an amount of particles having a first average particle size between about 200 and about 2000 microns, an amount of particles having a second average particle size between about three and about ten times smaller than the first average particle size, and an amount of particles having a third average particle size smaller than the second average particle size.
  • U. S. Patent No. 7,784,541 a blend having an amount of particles having a first average particle size between about 200 and about 2000 microns, an amount of particles having a second average particle size between about three and about ten times smaller than the first average particle size, and an amount of particles having a third average particle size smaller than the second average particle size.
  • S. Patent No. 7,004,255 a blend of coarse particles having diameters from about 0.20 mm to about 2.35 mm, and a quantity of smaller particles selected from medium particles, fine particles, and mixtures thereof; preferably the coarse particles have diameters from about 0.20 mm to about 0.43 mm, the medium particles have diameters from about 0.10 mm to about 0.20 mm, and the fine particles have diameters less than about 0.10 mm.
  • the coarse particles have diameters from about 0.20 mm to about 0.43 mm
  • the medium particles have diameters from about 0.10 mm to about 0.20 mm
  • the fine particles have diameters less than about 0.10 mm.
  • the diverting material includes a mixture of coarse particles, for example having an average particle size of from 300 to 1200 ⁇ , medium particles, for example having an average particle size of from 20 to 150 ⁇ and optionally fine particles, for example having an average particle size of from 5 to 15 ⁇ , and a blend of long fibers, for example having an average length of from 8 to 15 mm and short fibers, for example having an average length of from 1 to 8 mm; the long fibers are rigid and the short fibers are flexible; the long fibers form a tridimensional mat or net, for example in a lost-circulation pathway, that traps the mixture of particles and short flexible fibers to form a plug.
  • a mixture of coarse particles for example having an average particle size of from 300 to 1200 ⁇
  • medium particles for example having an average particle size of from 20 to 150 ⁇ and optionally fine particles, for example having an average particle size of from 5 to 15 ⁇
  • a blend of long fibers for example having an average length of from 8 to 15 mm and short fibers, for example having
  • 2010/0298175 a blend of coarse, medium and optional fine particles, and a blend of two different rigid fibers that includes fibers of different lengths or different diameters or different compositions, in which at least a portion of the medium particles or coarse particles or both swells in the presence of oil. Additional blends that may be used as special solid diverting materials are known or may be developed. It is particularly important that such blends of special solid diverting materials be delivered to the diverting site with as little dilution or size or shape separation as possible; this is achieved by the destructible containers.
  • the diverting material may optionally be placed inside the container in slurried form.
  • the liquid phase acts as a lubricant, as well as a suspension agent, and helps the particles to be released rather than forming agglomerates that don't break apart.
  • diverting material is loaded into a destructible container in a dry form and then becomes slurred in wellbore fluid which penetrates the container after exposure of the container to the wellbore fluid.
  • the thickness of the container shell may range from about 0.01 mm to about 5 mm, preferably from about 0.05 mm to about 2 mm, and most preferably from about 0.1 mm to about 1 mm.
  • the container may be made with several layers, for example up to about 10 layers, that may be the same or different. Multiple layers increases the mechanical stability of the container and/or allows control of the dissolution time of the shell.
  • the material for example special solid diverting material, is placed into heat shrinkable plastic film (for example a polyvinyl alcohol film or fabric, embossed polyvinyl alcohol film, polyethylene film, other polyolefin films, PVC film, oriented films having at least one or two oriented layers, multilayer oriented films, shrinkable polyester films such as those made of polylactic acid, polyglycolic acids or other polyesters or copolymers thereof, polysaccharide films such as starch films or cellulose films, etc.), sealed in, heated to cause shrinkage to form a container, and if desired for greater strength the first container is placed into a second heat shrinkable film, sealed in, and heated to cause shrinkage to form a stronger container. Additional films may also be used.
  • heat shrinkable plastic film for example a polyvinyl alcohol film or fabric, embossed polyvinyl alcohol film, polyethylene film, other polyolefin films, PVC film, oriented films having at least one or two oriented layers, multilayer oriented films, shrinkable polyester films such
  • the films may be the same or different. Such film or films may optionally be selected to degrade at a desired rate.
  • the material for example special solid diverting material, is placed into a hollow plastic ball that is initially in at least two components that are then sealed together. In one specific example these components are two half spheres.
  • the components may be made of a gelatin, for example from a mixture including water, a water-soluble polymer gelatin material that may include, for example, agar or processed seaweed, non toxic white glue, and the like, plasticizers, and a preserving additive such as benzoic acid, that is formed and dried.
  • the tensile strength of the container shell is preferably in the range of from about 1 MPa to about 1000 MPa, more preferably from about 5 MPa to about 300 MPa, and most preferably from about 10 MPa to about 100 MPa.
  • the Young's Modulus for the container shells is preferably in the range of from about 0.01 GPa to about 200 GPa, more preferably from about 0.1 GPa to about 100 GPa, and most preferably from about 0.1 GPa to about 10 GPa.
  • the preferred time for this to occur is from about 1 second to about 1 hour, more preferably from about 10 seconds to about 30 minutes, and most preferably from about 1 minute to about 15 minutes, at a preferred temperature range of from about 1 °C to about 100 °C, more preferably from about 10 °C to about 50 °C, and most preferably from about 10 °C to about 30 °C.
  • destructible containers with their contents having a density similar to that of the injected fluid, although higher density destructible containers may be used at high pumping rates.
  • the preferred density is from about 0.5 to about 5 times the fluid density, more preferably from about 1 to about 2.5 times the fluid density.
  • the preferred density is from about 0.5 kg/L to about 5 kg/L, more preferably from about 1 kg/L to about 2.5 kg/L.
  • WO 1992/022355 discloses making a water-soluble golf ball "comprising a core, said core, formed of a first water soluble material, and an external skin formed from two skin halves or semi-spheres, said skin formed of a second water soluble material, when the two skin halves or semi-spheres and core are adhered together with a water soluble non toxic adhesive.
  • the skin is made for example from paper pulp or from material selected from gelatin, agar, processed seaweed, and non toxic glue.
  • Containers comprising various filling materials can be made by placing such materials into hollow objects or chambers, preferably of spherical shape. Methods of making hollow plastic spheres are disclosed in Japanese Patents 56021836, 57066920, and 61239936; and Japanese Patent Application 2005349678 also discloses a plastic ball containing a closed cell foam.
  • U. S. Patent No. 7,395,646 discloses an article packaging device and a method for packing individual articles in a tubular thermoplastic sheet.
  • U. S. Patent No. 7,306,093 describes a method and apparatus of packing materials, including fiber- comprising bulk materials, into a sealed package shaped like a bale.
  • U. S. Patent No. 7,739,857 also discloses a method and apparatus for vacuum packing of fiber and other materials into one or more bales and packages. All these methods and devices may be adapted for use in some embodiments.
  • Containers with various fillers can also be prepared for use by surrounding portions of the fillers with a polymer or thermoplastic material.
  • shrinkable films or stretch films can be used.
  • Shrinkable films and methods of making such films are disclosed in U. S. Patent Nos. 7,846,517 (polylactic acids), 6,340,532 (polyesters), 7,638,203 (polyesters), 7,744,806 (polyamides), and 6,340,532 (polyethylenes).
  • a method of shrink-wrapping a material into a shrinkable plastic film with sample holes is disclosed in U. S. Patent No. 7, 172,065
  • U. S. Patent No. 6,898,921 A process of preparing water-soluble containers is disclosed in U. S. Patent No. 6,898,921.
  • the process comprises a) thermoforming a first poly(vinyl alcohol) film having a water content of less than 5% to produce a pocket; b) filling the pocket with a composition; c) placing a second film on the top of the pocket; and d) sealing the first film and the second film together.
  • the process may be adapted for use in some embodiments.
  • Destructible containers are intended to be introduced into a wellbore and pumped down to a target zone.
  • a standard or modified flow injector for example those used for ball sealers may be placed in the high pressure line.
  • Such devices are typically used for injection of large destructible containers (greater than about 10 mm in diameter) and the injector is commonly installed after the pumping units so the destructible containers are not subjected to forces that would break them in the surface equipment.
  • a schematic is shown in Figure 4. Destructible containers are loaded into the accumulator, which is isolated from the main pumping line by two remotely operated valves.
  • the same technique can be used to increase the concentration of destructible containers in the accumulator as is used to increase the concentration of particles in a fluid: use a mixture of a first size of destructible containers, and a second size of from about 7 to about 10 times smaller than the first, optionally a third size of from about 7 to about 10 times smaller than the second, and optionally additional sizes.
  • This mixture of sizes can also be used for selective destruction (for example of selected amounts) at specific locations (for example by different-sized restrictions) and for selective delivery of different materials (in different sized destructible containers) at different locations.)
  • the accumulator is closed, valves are opened and the containers are flushed from the accumulator by pumping fluid.
  • a simple flow-through injection apparatus may also be used. When it is desired that the containers be destroyed at the surface, flow-through blenders or blenders equipped with dry additive systems can be used.
  • destructible downhole containers may be used for setting temporary seals (plugs) formed by the contents of the containers.
  • plugs temporary seals
  • degradable materials are polyesters, including esters of lactic acid, glycolic acid, other hydroxy acids and copolymers thereof; polyamides and copolymers thereof; polyethers and copolymers thereof; polyurethanes, etc. Other examples of degradable materials were described above.
  • Some examples of materials that may be removed by reacting with other agents are carbonates including calcium and magnesium carbonates and mixtures thereof (reactive to acids and chelating agents); acid soluble cement (reactive to acids); polyesters including PGA, PLA, esters of lactic acid, glycolic acid, other hydroxy acids, and copolymers thereof (can be hydrolyzed with acids and bases); active metals such as magnesium, aluminum, zinc and their alloys (reactive to water, acids and bases), etc.
  • Dissolution of at least one component of the sealing composition is also achieved through physical dissolution of at least one of the components of the diverting blend in the surrounding fluid. Solubility of the component(s) may depend significantly on the temperature. In this case, post- treatment temperature recovery in the sealed zone can trigger the removal of the seal.
  • Materials that dissolve in water include water-soluble polymers, water-soluble elastomers, carbonic acids, rock salt, amines, and inorganic salts.
  • Materials that dissolve in oil include oil-soluble polymers, oil-soluble resins, oil-soluble elastomers, polyethylenes, carbonic acids, amines, and waxes.
  • Disintegration of at least one component of the sealing composition is also achieved through disintegration of the seal into smaller pieces that are flushed away.
  • Materials that can disintegrate include plastics such as PLA, polyamides and composite materials comprising degradable plastics and non- degradable fine solids. It should be noted that some degradable materials pass through a disintegration stage during the degradation process; an example is PLA, which turns into fragile materials before complete degradation.
  • the discussion above emphasizes delivery of materials in containers that are deliberately mechanically destroyed in the wellbore
  • the contents of the container comprise special solid diverting materials designed to divert fluid flow, such as fibers, fiber flocks, and other shapes designed to form plugs such as flakes, ribbons, platelets, rods, solid precipitates, grains, and pellets; mixtures of different sizes of approximately spherical materials; and mixtures of fibers and/or or other shapes such as flakes and one or more sizes of approximately spherical materials
  • the container may also be destroyed by self-degradation, chemical degradation, osmotic rupturing, dissolution, melting and other mechanisms known for release of conventionally encapsulated materials delivered to a downhole location; optionally the container may be partially degraded by one of these mechanisms and then the release of the contents completed by a mechanical method.
  • a container for special solid diverting materials may optionally be a coating that is engineered to degrade at a specific rate to release the enclosed material at a predetermined time, or pressure, or depth.
  • the container may optionally degrade before it reaches the zone to be treated, in which case it releases a concentrated aggregation of the container contents.
  • destructible containers are used for wellsite delivery of materials that may be difficult to handle, such as fibers, fiber flocks, fibrillated fibers, ribbons, platelets, flakes, etc. that may be difficult to transport to a well site and then to meter into a fluid.
  • fibers, fiber flocks, fibrillated fibers, ribbons, platelets, flakes, etc. may be tightly packed and enclosed in a destructible coating so that the size of the containers is, for example, in the range of about 1 to about 10 mm.
  • Various mechanisms of coating destruction may be used, such as dissolution in water, mechanical destruction, reaction with chemicals, or combination thereof.
  • the coating is a film made of water, a soluble polymer such as polyvinyl alcohol, starch or a gelatin.
  • the gelatin may be made, for example, from a mixture including water, a water-soluble polymer gelatin material that may include, for example, agar or processed seaweed, non toxic white glue, and the like, plasticizers, and a preserving additive such as benzoic acid which quickly dissolves in water after introduction of the containers into a pumping fluid.
  • Such containers comprising packed fibers, fiber flocks, fibrillated fibers, ribbons, platelets, flakes, etc., can be introduced into the treating fluid on-the-fly using the surface equipment traditionally used for wellsite delivery of proppants and other particulate materials.
  • Such equipment includes, but is not limited to, flow-through blenders, dry-additive systems, ball injectors etc. Upon introduction of such containers into the treating fluid, the shell is destroyed, releasing the material, which is dispersed in the treating fluid.
  • This approach has several advantages over the traditionally used methods of delivery as it enables better metering and eliminates the risk of plugging surface equipment with fibers, fiber flocks, fibrillated fibers, ribbons, flakes, etc.
  • Example 1 Some embodiments may be understood further from the following example.
  • Example 1
  • the slurry used for filling the container in experiment 2 was designed according to the recommendations for designing high solids content fluids given in U. S. Patent Application Publication No. 2009/0025934. Such a slurry is characterized by its high loading of solid material and good fluidity properties.
  • FIG. 5 shows a schematic of the experimental apparatus used for studying the release of particulate materials from destructible containers.
  • the apparatus consisted of a 50 mm transparent pipe, equipped with an injector for containers, and having one 8.4 mm perforation hole.
  • the destructible container had an approximately spherical shape with a volume of 60 ml.
  • the pipe was connected to a water pump having a maximum pumping capacity of 36 L/min. Before the experiment a destructible container was placed in the apparatus through the injector and the removable plug on the injector was replaced. Then the pump was started and the container was displaced to the perforation by water at the maximum pumping rate.
  • Example 1 shows that this approach significantly increased the reliability of delivery and release of the diverting material from a destructible container.

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  • Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)

Abstract

La présente invention a trait à un procédé permettant de traiter une région de forage pénétrée par un puits avec un agent de traitement, lequel procédé inclut les étapes consistant à fournir l'agent de traitement à l'emplacement du forage enfermé dans un ou plusieurs récipients destructibles, à insérer le ou les récipients destructibles dans le fluide qui est pompé en dehors du puits et à rompre mécaniquement le ou les récipients destructibles dans le puits ou dans la formation de manière à libérer l'agent de traitement. La présente invention a également trait à un procédé permettant de traiter une région de forage pénétrée par un puits avec un matériau de répartition solide spécial, qui inclut des formes spéciales telles que des fibres ou des flocons et/ou des mélanges de particules spécialement dimensionnées, lequel procédé inclut les étapes consistant à fournir le matériau de répartition solide spécial à l'emplacement du forage enfermé dans un ou plusieurs récipients, à insérer le ou les récipients dans le fluide qui est pompé en dehors du puits et à permettre au(x) récipient(s) de libérer le matériau de répartition solide spécial dans le puits.
PCT/US2012/037512 2011-05-11 2012-05-11 Récipients destructibles destinés au matériau de forage et à la fourniture de produits chimiques WO2012155045A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201280028793.7A CN103688018A (zh) 2011-05-11 2012-05-11 用于井底材料以及化学品输送的可破坏容器
RU2013154754/03A RU2013154754A (ru) 2011-05-11 2012-05-11 Разрушаемые контейнеры для доставки в скважину материалов и химических веществ
MX2013012912A MX2013012912A (es) 2011-05-11 2012-05-11 Contenedores destructibles para el suministro de material y químicos en el fondo del pozo.
CA2835130A CA2835130A1 (fr) 2011-05-11 2012-05-11 Recipients destructibles destines au materiau de forage et a la fourniture de produits chimiques
BR112013028953A BR112013028953A2 (pt) 2011-05-11 2012-05-11 método de tratar uma região de fundo de poço penetrada por um furo de poço com um agente de tratamento, método de tratar uma região de fundo de poço penetrada por um furo de poço com um material de desvio sólido especial, e sistema para fornecimento de um material de desvio sólido especial para um local de fundo de poço sem diluição ou separação de componentes de material de desvio sólido especial.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/105,586 2011-05-11
US13/105,586 US20120285695A1 (en) 2011-05-11 2011-05-11 Destructible containers for downhole material and chemical delivery

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WO2012155045A2 true WO2012155045A2 (fr) 2012-11-15
WO2012155045A3 WO2012155045A3 (fr) 2013-01-10

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US (1) US20120285695A1 (fr)
CN (1) CN103688018A (fr)
BR (1) BR112013028953A2 (fr)
CA (1) CA2835130A1 (fr)
MX (1) MX2013012912A (fr)
RU (1) RU2013154754A (fr)
WO (1) WO2012155045A2 (fr)

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BR112013028953A2 (pt) 2017-03-01
US20120285695A1 (en) 2012-11-15
CN103688018A (zh) 2014-03-26
CA2835130A1 (fr) 2012-11-15
WO2012155045A3 (fr) 2013-01-10
MX2013012912A (es) 2015-03-06
RU2013154754A (ru) 2015-06-20

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