WO2013028298A2 - Procédé de fracturation permettant d'améliorer la répartition d'un agent de soutènement afin de développer au maximum la connectivité entre la formation et le puits de forage - Google Patents

Procédé de fracturation permettant d'améliorer la répartition d'un agent de soutènement afin de développer au maximum la connectivité entre la formation et le puits de forage Download PDF

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Publication number
WO2013028298A2
WO2013028298A2 PCT/US2012/047787 US2012047787W WO2013028298A2 WO 2013028298 A2 WO2013028298 A2 WO 2013028298A2 US 2012047787 W US2012047787 W US 2012047787W WO 2013028298 A2 WO2013028298 A2 WO 2013028298A2
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WIPO (PCT)
Prior art keywords
treatment fluid
agent
placing
fracture network
subterranean formation
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PCT/US2012/047787
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English (en)
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WO2013028298A3 (fr
Inventor
David M. Adams
Stephen R. INGRAM
Nicholas Gardiner
Walt F. GLOVER
Mark Harris
Matt Oehler
Jonathan Smith
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Halliburton Energy Services, Inc.
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Application filed by Halliburton Energy Services, Inc. filed Critical Halliburton Energy Services, Inc.
Priority to CN201280041066.4A priority Critical patent/CN103748320A/zh
Priority to EP12743595.6A priority patent/EP2748431A2/fr
Priority to BR112014004099A priority patent/BR112014004099A2/pt
Priority to CA2843319A priority patent/CA2843319A1/fr
Priority to AU2012299397A priority patent/AU2012299397A1/en
Priority to MX2014002073A priority patent/MX2014002073A/es
Publication of WO2013028298A2 publication Critical patent/WO2013028298A2/fr
Publication of WO2013028298A3 publication Critical patent/WO2013028298A3/fr

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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
    • 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
    • E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping

Definitions

  • the present invention reiates generally to enhancing propping agent d istribution in order to maximize connectivity between a subterranean formation and a we! i bore so as to improve production from a subterranean formation.
  • Access to the subterranean formation can be achieved by first creating an access conduit from the wel!bore to the subterranean formation. Then, a fracturing fluid, called a pad, is introduced at pressures exceeding those required to maintain matrix flow in the formation permeability to create or enhance at least one fracture that propagates from at least one access conduit.
  • a fracturing fluid called a pad
  • a fluid comprising a propping agent to prop the fracture open after pressure is reduced
  • fractures can further branch into small fractures extending from a primary fracture giving depth and breadth to the fracture network created in the subterranean formation .
  • a "fracture network” refers to the access conduits, fractures, microfractures, and/or branches, man-made or otherwise, within a subterranean formation that are in fluid communication with the welibore.
  • the propping agents hold open the fracture network thereby maintaining the ability for fluid to flow through the fracture network to ultimately be produced at the surface.
  • Distribution of the propping agents is an important factor to maximizing production from the fracture network.
  • Propping agents like the fluid in which they are suspended, follow the path of least resistance, which in practice is typically into only a small percentage of fractures that have been created, and most definitely not into an appreciable number of branches that extend therefrom .
  • Heterogeneous distribution of propping agents within a fracture network often yields a production curve with shorter steady state production and steep production decline, shown in Figure la, i. e. , the formation produces hyd rocarbon for a shorter amount of time and production decline is very rapid. This is most often observed in shale and other very low permeability formations, Recovering a well after production decline typically involves refracturing, which can be cost!y and time consuming.
  • a packer or bridge plug may be used between sets of access conduits to divert a treatment fluid between the access conduits.
  • sand may be used as diverting agents to plug or bridge an access conduit.
  • balls commonly referred to as “perf bails,” may be used to seal off individual access conduits to divert fluid, and consequently propping agents, to other access conduits.
  • Such techniques may be only partially successful towards uniform distribution of propping agents, especially in dendritic and shattered fracture networks, because they only address the distribution issues at the weiibore, i.e., at the access conduit, not within the highly interconnected, multi- branched fracture network.
  • One of many problems in the use of some or all of the above described procedures may be that the means of diverting the treatment fluid requires an additional step of removing it from the weiibore to allow the maximum flow of produced hydrocarbon from the subterranean zone into the weiibore.
  • a bridge plug generally is removed or drilled out at the end of the operation to allow for production.
  • sand plugs or bridges are cleaned out. for production; sealing balls are often recovered for production, both of which incur additional time and expenses.
  • Particulate diverting agents may be difficult to remove completely from the subterranean formation, which may cause a residue to remain in the weiibore area following the fracturing operation, which may permanently reduce the permeability of the formation.
  • difficulty in removing conventional diverting agents from the formation may permanently reduce the permeability of the formation by between 5% to 40%, and may even cause a 100% permanent reduction in permeability in some instances.
  • the term "deviated weiibore” refers to a wellbore in which any portion of the well is in excess of about 55-degrees from a vertical inclination.
  • highly deviated wellbore refers to a wellbore that is oriented between 75-degrees and 90-degrees off-vertical (wherein 90-degrees off-vertical corresponds to a fully horizontal wellbore), That is, the term “highly deviated wellbore” may refer to a portion of a wellbore that is anywhere from fully horizontal (90-degrees off-vertical) to 75-degrees off -vertical.
  • the present invention relates generally to enhancing propping agent distribution in order to maximize connectivity between a subterranean formation and a wellbore so as to improve production from a subterranean formation.
  • the present invention provides a method that comprises; providing a wellbore penetrating a subterranean formation, wherein the subterranean formation is able to support a fracture network; providing at least one access conduit to the subterranean formation from the wellbore; placing a first treatment fluid into the subterranean formation through the at least one access conduit at a pressure sufficient to form at least a portion of a fracture network extending from the at least one access conduit; pumping a second treatment fluid comprising a propping agent into the fracture network such that the propping agent forms a proppan pack in at least a portion of the fracture network; placing a third treatment fluid comprising a secondary diverting agent into the wellbore such that the secondary diverting agent goes through the access conduit and into at least a portion of the fracture network so as to substantially inhibit fluid flow through at least a portion of the fracture network without substantiaiiy inhibiting fluid flow through the access conduit; and placing a fourth treatment fluid comprising a primary diver
  • the present invention provides a method tha comprises: providing a wellbore penetrating a subterranean formation, wherein the subterranean formation has a closure pressure greater than about 500 psi; providing at least one access conduit to the subterranean formation from the wellbore; placing a first treatment fluid into the subterranean formation through the at least one access conduit at a pressure sufficient to form at least a portion of a fracture network extending from the at least one access conduit; pumping a second treatment fluid comprising a propping agent into the fracture network such that the propping agent forms a proppant pack in at ieast a portion of the fracture network; placing a third treatment, fluid comprising a secondary diverting agent, into the wellbore such that, the secondary diverting agent goes through the access conduit and into at Ieast a portion of the fracture network so as to substantially inhibit fiuid flow through at Ieast a portion of the fracture network without substantially inhibiting fiuid flow through the access conduit
  • the present invention provides a method that comprises: providing a wellbore penetrating a subterranean formation, wherein the subterranean formation is able to support a fracture network and the wellbore has at.
  • Figures la-b illustrate the production curve of a subterranean formation based on distribution of propping agents.
  • Figure 2 illustrates the placement of elements within a dendritic fracture network
  • Figure 3 illustrates the placement of elements within a shattered fracture network.
  • Figure 4 illustrates a noniimiting example of a fracture network response to a method of the present invention.
  • Figure 5 illustrates a noniimiting example of wellbore pressure during a method of the present invention.
  • the present invention relates generally to enhancing propping agent distribution in order to maximize connectivity between a subterranean formation and a wellbore so as to improve production from a subterranean formation.
  • a fracture network may comprise access conduits, fractures, microfractures, and branches.
  • an "access conduit” refers to a passageway that provides fluid communication between the wellbore and the subterranean formation, which may include, but not be limited to, sliding sleeves, open holes in non-cased areas, hydrajetted holes, holes in the casing, perforations, and the like.
  • the methods of the present invention provide for treatment fluid and propping agent diversion in at least each of these fracture network components.
  • Uniform distribution of propping agents maximizes the connectivity between the formation and the welibore, thereby maximizing hydrocarbon production therefrom. Further, the diversion methods provided herein better dilate the branches that give depth and breadth to a fracture network. Without being bound by theory, it is believed that, dilated components of a fracture network more readily incorporate propping agents, which consequently yields more hydrocarbon in production operations. These methods may be particularly useful in deviated weiibores that are notorious for heterogeneous distribution of propping agents and heterogeneous fracture network dilation.
  • Uniform distribution of propping agents allows for the use of less overall propping agents, thereby reducing the cost of the operation.
  • uniform distribution of propping agents (Figure lb) may extend the lifetime of a well by increasing the length of the steady- state production and reducing the rate of production decline, as compared to heterogeneous propping agent distribution ( Figure la).
  • some embodiments may include some combination of the various diverting agents being degradabie, Degradabie diverting agents decrease, and may eliminate, the need for secondary operations to restore fluid conductivity within the fracture network when production operations begin, which consequently reduces the environmental impact of subterranean operations. This reduces the cost and time for fracturing operations.
  • any combination of propping agents, a primary diverting agent, a secondary diverting agent, and optionally a degradabie particle may be introduced via a treatment fluid into a welibore penetrating a subterranean formation.
  • the elements of a propping agent, a primary diverting agent, a secondary diverting agent, and optionally a degradabie particle may be introduced into a welibore via a single treatment fluid comprising ail of the elements, individual treatment fluids comprising a single element, a plurality of treatment fluids comprising some combination of at least two of the elements, and any combination thereof,
  • treatment refers to any subterranean operation that uses a fluid in conjunction with a desired function and/or for a desired purpose.
  • the term “treatment,” or “treating,” does not imply any particular action by the fluid.
  • a "diverting agent” refers to any material that can be used to substantially seal off a portion of a subterranean formation thereby substantially reducing , including blocking, fluid flow therethrough.
  • a "primary diverting agent” refers to a diverting agent that substantially inhibits fluid flow through an access conduit.
  • a “secondary diverting agent” refers to a diverting agent that substantially inhibits fluid flow through at least a portion of the fracture network.
  • Suitable diverting agents may comprise gels, particles, and/or fibers that are natural or synthetic; degradabie or nondegradabie; and mixtures thereof. Nonlimiting examples of suitable diverting agents are included below.
  • propping agents refers to any material or formulation that can be used to hold open at least a portion of a fracture network
  • a “proppant pack” is the collection of propping agents in a fracture network.
  • a “degradabie particle/' and derivatives thereof refers to any material that can be used in conjunction with a proppant pack that when substantially degraded leaves a void in the proppant pack.
  • the term “particulate” or “particle,” and derivatives thereof as used in this disclosure includes ail known shapes of materials, including substantially spherical materials, low to high aspect ratio materials, fibrous materials, polygonal materials (such as cubic materials), and mixtures thereof.
  • the terms “degradation” or “degradabie” refer to both the two relatively extreme cases of hydrolytic degradation that the degradabie material may undergo, e.g.
  • This degradation can be a result of, inter alia, a chemical or thermal reaction, or a reaction induced by radiation.
  • Nonlimiting examples of degradabie particles are included below.
  • At least one access conduit from the wellbore to the subterranean formation may be created .
  • at ieast one access conduit from the vvellbore to the subterranean formation may be provided .
  • access conduits may be made by any means or techniq ue known in the art including, but not limited to, hyd rajetting ; laser inscribing ; perforating ; not casing at ieast. a portion of the vvellbore, and the like. Suitable examples of perforation toois and methods may include, but not be limited to, those disclosed in U .S. Patent Numbers 5,398.760; 5,701,957; 6,435,278; 7, 159,660; 7, 172,023 ; 7,225,869; 7,303,017; and 7,841,396, the entirety of which are incorporated herein by reference. Access conduits may be spaced randomly, spaced substantially equidistant from each other, clustered in groups (e.g. , an access conduit cluster), or any combination thereof along the length of the wellbore,
  • a treatment, fluid may be introduced into a vvellbore at. a pressure sufficient to form at Ieast one fracture extending from at Ieast one access conduit into a subterranean formation.
  • the pressure may be sufficient to form at Ieast one branch extending from at Ieast one fracture.
  • the pressure may be sufficient to form a fracture network,
  • the pressure may be sufficient to form at least a portion of a fracture network.
  • a fracture network may comprise access conduits, fractures, microfractures, branches, or any combination thereof including those which are natural and man - made.
  • a fracture network may be considered a dendritic fracture network, a shattered fracture network, or any combination thereof.
  • Figure 2 illustrates a noniimiting example of a dendritic fracture network extending from a vveiibore into a subterranean formation.
  • Figure 3 illustrates a noniimiting example of a shattered fracture network extending from a wellbore into a subterranean formation . These noniimiting examples illustrate two types of fracture networks extending from a horizontal well .
  • any single or combination of elements including propping agents, a primary diverting agent, a secondary diverting agent, and a degradabie particle may be piaced via a treatment fluid into a we!ibore penetrating a subterranean formation. It should be noted that, placing may include pumping, introducing, adding, injecting, inserting, and the like,
  • Some embodiments of the present, invention may include the following steps:
  • a method of treating a subterranean formation may comprise either step c or step d listed above.
  • a primary diverting agent may substantially inhibit fluid flow through an access conduit and/or divert fiuid flow to another access conduit.
  • a secondary diverting agent may substantially inhibit fluid flow within the fracture network, e.g. , through a fracture and/or a branch so as to divert fluid flow to branches extending from the fracture.
  • a degradabie particle may incorporate into a proppant pack such that when substantially degraded a void in the proppant pack is produced,
  • the steps provided above may be performed in order. In some embodiments, one or more steps may be performed more than once. In some embodiments, one or more steps may be performed simultaneously, in some embodiments, the steps provided above may be performed in any order, Nonlimiting examples of methods of the present invention may inciude the following :
  • the diversion methods of the present invention may provide for better dilation of the components of the fracture network, which enhances hydrocarbon prod uction .
  • Fig ure 4 illustrates the dilation (line thickening) of a fracture network as the steps of b/e - b/c - b/c - b/d - b/e - b/c are performed on an already fractured subterranean formation (propping agents not shown, only dilation progression) .
  • the amount of an element within a treatment fluid may vary during a step,
  • the introduction of propping agents in a treatment fluid may be at 30 pounds per gallon fppg" when the step begins then reduce to 10 ppg when the end of the step is complete.
  • changing the amount of an element in a treatment fluid may be an increase or decrease as a stepwise change, a gradient change, or any combination thereof, In some embodiments where multiple elements are introduced simultaneously, the amount, of one or more elements may change during the step.
  • the amount of element(s) may stay constant while the amount of other additive(s), including those described below, are changed . In some embodiments, both the amount of element(s) and additive(s) may change within a step.
  • the methods of the present invention optionally may comprise monitoring the flow of one or more treatment fluids in at least a portion of the subterranean formation during ail or part of a method of the present invention .
  • Monitoring may, for example, ensure a primary and/or secondary diverting material are being placed appropriately within the fracture network, determine the presence or absence of a primary and/or secondary diverting material in the fracture network, and/or determine whether a primary and/or secondary diverting material actually diverts fluids introduced into the subterranean formation. Monitoring may be accomplished by any technique or combination of techniques known in the art.
  • this may be accomplished by monitoring the fluid pressure at the surface of a wellbore penetrating the subterranean formation where fluids are introduced. For example, if the fluid pressure at the surface increases, this may indicate that the fluid is being diverted within the fracture network. Additionally, a pressure decrease or substantially steady-state pressure may indicate a portion of the fracture network is dilating. Pressure monitoring techniques may include various logging techniques and/or computerized fluid tracking techniques known in the art that are capable of monitoring fluid flow. Examples of commercially available services involving surface fluid pressure sensing that may be suitable for use in the methods of the present invention include those available under the tradename EZ-GAUGETM (surface pressure sensing tools, available from Halliburton Energy Services, Inc., Duncan, OK),
  • fluid pressure changes may not. always be observable at the wellbore surface during fluid diversion and/or fracture network dilation.
  • fluid diversion because of placement of a secondary diverting agent may occur without an observable by an increase in fluid pressure at the wellbore surface.
  • an element may be introduced into the wellbore after the wellbore pressure increases and begins to level off.
  • an element may be introduced into the wellbore during substantially steady-state wellbore pressure.
  • Figure 5 illustrates two possible operations using methods of the present invention. In Scenario 1, propping agents are introduced in a periodic fashion; while in Scenario 2, the propping agents are introduced continuously and increased step-wise over time. At steady-state wellbore pressure, secondary diverting agent is added in twice followed by introduction of the primary diverting agent. The primary diverting agent substantially blocks the flow of fluid through an access conduit causing wellbore pressure to increase. These steps are repeated with similar results.
  • monitoring the flow of one or more treatment fluids in at least, a portion of the subterranean formation may be accomplished, in part, by using a distributed temperature sensing (DTS) technique, These techniques may involve a series of steps.
  • a temperature sensing device e.g. , thermocouples, thermistors, or fiber optic cables
  • a fiber optic cable may be pre-instai!ed in a casing string before the casing string is placed in the wellbore.
  • an additional apparatus e.g. , coiled tubing
  • fluid e.g., fluid to place the fiber optic cable in the wellbore.
  • one may establish baseline temperature profile for all or part of the subterranean formation, and then monitor changes in temperature to determine the flow of fluids in various portions of the subterranean formation.
  • Various computer software packages may be used to process the temperature data and/or create visualizations based on that data.
  • Certain DTS techniques that may be suitable for use in the methods of the present invention may include commercially-available DTS services such as those known under the tradenames STIMWATCH ® (available from Halliburton Energy Services, Inc., Duncan, OK) or SENSATM (available from Schiumberger Technology Corporation, Sugar Land, TX).
  • DTS techniques that may be suitable for use in the methods of the present invention also may include those described in U.S. Patent Numbers 5,028, 146; 6,557,630; 6,751,556; 7,055,604; and 7,086,484, the entire disclosures of which are incorporated herein by reference.
  • the methods of the present invention may be used in any subterranean formation capable of being fractured. Formations where the present methods may be most advantageous include, but are not limited to, formations with at least a portion of the formation characterized by very low permeability; very low formation pore throat size; high closure pressures; high brittieness index; and any combination thereof.
  • a portion of a subterranean formation may have a permeabiiity ranging from a iower limit of about 0.1 nano Darcy (nD), 1 nD, 10 nD, 25 nD, 50 nD, 100 nD, or 500 nD to an upper iimit of about 10 mD, 1 mD, 500 microD, 100 microD, 10 microD, or 500 nD, and wherein the permeability may range from any Iower iimit to any upper iimit and encompass any subset, therebetween.
  • nD nano Darcy
  • At ieast a portion of a subterranean formation may have an average formation pore throat size ranging from a lower iimit of about 0.005 microns, 0.01 microns, 0,05 microns, 0.1 microns, 0.25 microns, or 0.5 microns to an upper Iimit of about 2,0 microns, 1.5 microns, 1.0 microns, or 0.5 microns, and wherein the average formation pore throat size may range from any iower iimit to any upper Iimit and encompass any subset, therebetween.
  • One method to determine the pore throat size of a subterranean formation inciudes the AAPG Buiietin, March 2009, v. 93, no, 3, pages 329-340, the entirety of which is incorporated herein by reference,
  • At ieast a portion of a subterranean formation may have a closure pressure greater than about 500 psi to an unlimited upper Iimit. While the ciosure pressure upper limit is believed to be unlimited, formations where the methods of the present invention may be appiicabie include formations with a closure pressure ranging from a iower iimit of about 500 psi, 1000 psi, 1500 psi, or 2500 psi to an upper Iimit of about.
  • closure pressure may range from any iower iimit to any upper Iimit and encompass any subset therebetween.
  • One method to determine the subterranean formation ciosure pressure inciudes the method presented in the Society for Petroleum Engineers paper number 60321, the entirety of which is incorporated herein by reference.
  • At ieast a portion of a subterranean formation may have a brittieness index ranging from a iower iimit of about 5, 10, 20, 30, 40, or 50 to an upper iimit of about 150, 125, 100, or 75, and wherein the brittieness index may range from any Iower Iimit to any upper iimit and encompass any subset therebetween.
  • Brittieness is a composite of Poisson's ratio and Young's modulus.
  • One method to determine the brittleness index of a subterranean formation includes the method presented in the Society for Petroleum Engineers paper number 132990, the entirety of which is incorporated herein by reference.
  • a!! or part of a we!ibore penetrating the subterranean formation may include casing pipes or strings placed in the wellbore (a "cased hole” or a “partially cased hole”), among other purposes, to facilitate production of fluids out of the formation and through the wellbore to the surface.
  • the wellbore may be an "open hole” that has no casing.
  • the methods disclosed herein may be used in conjunction with zipper fracture techniques.
  • Zipper fracture techniques use pressurized fracture networks in at least one wellbore to direct the fracture network of a second, nearby wellbore. Because the first fracture network is pressurized and exerting a stress on the subterranean formation, the second pressure network may extend through the path of least resistance, i.e. , the portions of the subterranean formation under less stress, Continuing to hold open portions of the fracture network with propping agent may continue to provide stress on the subterranean formation even with a reduced fluid pressure therein. Therefore, enhancing the uniform distribution of propping agents through a fracture network may enhance efficacy of a zipper fracture technique.
  • any of the diversion methods described herein may be implemented in at least one wellbore to enhance the fracture network of at least one nearby wellbore,
  • Suitable diverting agents for use in the present invention may be any known diverting agent including, but not limited to, any known lost circulation material, bridging agent, fluid loss control agent, diverting agent, plugging agent, or the like suitable for use in a subterranean formation.
  • Suitable diverting agents may comprise gels, particles, and/or fibers that are natural or synthetic; degradable or nondegradabie; and mixtures thereof.
  • Nonlimiting examples of commercially available diverting agents include diverting agents in the BIQVERT ® series (degradable diverting agents, available from Halliburton Energy Services, Inc.) including, but not.
  • BIOVERT ® NWB a biomodal, degradable diverting agent, available from Halliburton Energy Services, Inc.
  • BIOVERT ® CF a degradabie diverting agent, available from Halliburton Energy Services, Inc.
  • Primary diverting agents for use in the present invention may comprise particulates.
  • particulates of a primary diverting agent may have an average diameter ranging from a lower limit of about 0,5 microns, i micron, 10 microns, 100 microns, or 500 microns to an upper limit of about 10 mm, 5 mm, 1 mm, 500 microns, or 100 microns, and wherein the average diameter may range from any lower limit to any upper limit and encompass any subset therebetween.
  • particulates of a primary diverting agent may have a multi-modal diameter distribution including bimodai.
  • Secondary diverting agents for use in the present invention may comprise particulates.
  • particulates of a secondary diverting agent may have an average diameter less than about 150 microns. Suitable average diameters for particulates of a secondary diverting agent may range from a lower limit of about 100 nm, 250 nm, 500 nm, 1 micron, 10 microns, or 50 microns to an upper limit of about 150 microns, 100 microns, 50 microns, or 10 microns, and wherein the average diameter may range from any lower limit to any upper limit and encompass any subset therebetween.
  • the secondary diverting agent may have an average diameter less than or equal to a proppant particulate of the propping agents.
  • the primary diverting agent may comprise particulates with a larger average diameter than particulates of a secondary diverting agent.
  • Suitable examples of materials for a diverting agent include, but are not limited to, sand, shale, ground marble, bauxite, ceramic materials, glass materials, metal pellets, high strength synthetic fibers, cellulose flakes, wood, resins, polymer materials (crossiinked or otherwise), poiytetrafluoroethylene materials, nut shell pieces, cured resinous particulates comprising nut shell pieces, seed shell pieces, cured resinous particulates comprising seed shell pieces, fruit pit pieces, cured resinous particulates comprising fruit pit pieces, composite particulates, and any combination thereof.
  • Suitable composite particulates may comprise a binder and a filler material wherein suitable filler materials include silica, alumina, fumed carbon, carbon black, graphite, mica, titanium dioxide, meta-si!icate, calcium silicate, kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres, solid glass, and any combination thereof.
  • a d iverting agent may be at least partially degradable.
  • suitable deg radable materials that may be used in the present invention include, but are not limited to, degradable polymers (crosslinked or otherwise), dehydrated compounds, and/or mixtures of the two.
  • deg radable solid particulates examples include U .S. Patent Numbers 7,036, 587 ; 6,896,058; 6,323,307; 5,216,050; 4,387,769 ; 3,912,692 ; and 2,703,316, the relevant disclosures of which are incorporated herein by reference.
  • the terms "polymer” or “polymers” as used herein do not imply any particular deg ree of polymerization ; for instance, oligomers are encompassed within this definition .
  • a polymer is considered to be “degradable” herein if it is capable of undergoing an irreversible degradation when used in subterranean applications, e.g. , in a welibore.
  • degradable means that the degradable material should degrade in situ (e.g. , within a welibore) but should not recrystallize or reconsoiidate in situ after degradation (e.g. , in a welibore) ,
  • Deg radable materials may include, but not. be limited to, dissolvable materials, materials that deform or melt upon heating such as thermoplastic materials, hydrolyticaliy deg radable materials, materials degradable by exposure to radiation, materials reactive to acidic fluids, or any combination thereof.
  • degradable materials may be degraded by temperature, presence of moisture, oxygen, microorganisms, enzymes, pH, free radicals, and the like.
  • degradation may be initiated in a subsequent treatment fluid introduced into the subterranean formation at some time when d iverting is no longer necessary.
  • degradation may be initiated by a delayed-release acid, such as an acid-releasing degradable material or an encapsulated acid, and this may be included in the treatment fluid comprising the degradable material so as to reduce the pH of the treatment fluid at a desired time, for example, after introduction of the treatment fluid into the subterranean formation .
  • a delayed-release acid such as an acid-releasing degradable material or an encapsulated acid
  • a boric acid derivative may not be included as a degradable material in the well d rill-in and servicing fluids of the present invention where such fluids use guar as the viscosifier, because boric acid and guar are generally incompatible.
  • guar as the viscosifier
  • the degradabiiity of a degradabie polymer often depends,, at least in part, on its backbone structure. For instance, the presence of hydroiyzable and/or oxidizable linkages in the backbone often yields a material that will degrade as described herein.
  • the rates at which such polymers degrade are dependent on the type of repetitive unit, composition, sequence, length, molecular geometry, molecular weight, morphology (e.g., crystaliinity, size of spherulites, and orientation), hydrophilicity, hydrophobicity, surface area, and additives.
  • the environment to which the polymer is subjected may affect how it degrades, e.g., temperature, presence of moisture, oxygen, microorganisms, enzymes, pH, and the like.
  • Suitable examples of degradabie polymers for a solid particulate of the present invention include, but are not limited to, polysaccharides such as cellulose; chitin; chitosan; and proteins.
  • Suitable examples of degradabie polymers that may be used in accordance with the present invention include, but are not limited to, those described in the publication of Advances in Polymer Science, Vol. 157 entitled "Degradabie Aliphatic Polyesters," edited by A, C. Albertsson, pages 1-138. Specific examples include homopolymers, random, block, graft, and star- and hyper- branched aliphatic polyesters.
  • Such suitable polymers may be prepared by polycondensation reactions, ring-opening polymerizations, free radical polymerizations, anionic polymerizations, carbocationic polymerizations, coordinative ring-opening polymerizations, as well as by any other suitable process.
  • degradabie polymers examples include, but are not limited to, aliphatic polyesters; poly(lactides); poiy(glycolides); poly(s-caproiactones); poly(hydroxy ester ethers); poly(hydroxybutyrates); poly(anhydrides); polycarbonates; poiy(orthoesters); poiy(amino acids); poiy(ethyiene oxides); poly(phosphazenes); poiy(ether esters), polyester amides, polyamides, and copolymers or biends of any of these degradabie polymers, and derivatives of these degradabie polymers.
  • copolymer as used herein is not limited to the combination of two polymers, but includes any combination of polymers, e.g. , terpo!ymers and the like.
  • derivative is defined herein to include any compound that is made from one of the listed compounds, for example, by replacing one atom in the base compound with another atom or group of atoms.
  • aliphatic polyesters such as poly(laclic acid), poiy(anhydrides), poly(orthoesters), and po!y(!acfcide)-co ⁇ poiy(g!yco!ide) copolymers are preferred, Po!y(iactic acid) is especially preferred, Poly(orthoesters) also may be preferred.
  • Other degradabie polymers that are subject to hydro!ytic degradation also may be suitable. One's choice may depend on the particular application and the conditions involved . Other guidelines to consider include the degradation products that result, the time required for the requisite degree of degradation, and the desired result of the degradation (e.g. , voids).
  • Aliphatic polyesters degrade chemically, inter alia, by hydroiytic cleavage.
  • Hydrolysis can be catalyzed by either acids or bases.
  • carboxyiic end groups may be formed during chain scission, which may enhance the rate of further hydrolysis. This mechanism is known in the art as "autocata!ysis,” and is thought to make polyester matrices more bulk-eroding,
  • Suitable aliphatic polyesters have the general formula of repeating units shown below:
  • n is an integer between 75 and 10,000 and R is selected from the group consisting of hydrogen, alkyl, ary!, a!kylary!, acetyl, heteroatoms, and mixtures thereof.
  • the aliphatic polyester may be poiy(lactide).
  • Poly(lactide) is synthesized either from lactic acid by a condensation reaction or, more commonly, by ring-opening polymerization of cyclic iactide monomer.
  • poiy(lactic acid ) refers to writ of formula I without any limitation as to how the polymer was made (e.g., from iactides, lactic acid, or oligomers), and without reference to the degree of polymerization or level of plasticization.
  • the lactide monomer exists generally in three different forms: two stereoisomers (L- and D-!actide) and racemic D f L-!actide (meso- iactide).
  • the oligomers of lactic acid and the oligomers of lactide are defined by the formula :
  • m is an integer in the range of from greater than or equai to about 2 to less than or equal to about 75.
  • m may be an integer in the range of from greater than or equal to about 2 to less than or equal to about 10. These limits may correspond to number average molecular weights below about 5,400 and below about 720, respectively.
  • the chiraiity of the lactide units provides a means to adjust, inter alia, degradation rates, as well as physical and mechanical properties.
  • Poly(L-iactide) for instance, is a semicrystalline polymer with a relatively slow hydrolysis rate.
  • Poly(D,L-lactide) may be a more amorphous polymer with a resultant faster hydrolysis rate. This may be suitable for other applications in which a more rapid degradation may be appropriate.
  • the stereoisomers of lactic acid may be used individually, or may be combined in accordance with the present invention, Additionally, they may be copolymerized with, for example, glycolide or other monomers like ⁇ -caproiactone, l,5-dioxepan-2-one, trimethy!ene carbonate, or other suitable monomers to obtain polymers with different properties or degradation times.
  • the lactic acid stereoisomers can be modified by blending high and low molecular weight poiyiactide or by blending poiyiactide with other polyesters, in embodiments wherein poiyiactide is used as the degradabie material, certain preferred embodiments employ a mixture of the D and L stereoisomers, designed so as to provide a desired degradation time and/or rate, Examples of suitable sources of degradable material are commercially available 625QD 5 M (poly(!actic acid), available from Cargiil Dow) and 5639A 1 M (poly(Sactic acid), available from Cargil! Dow).
  • Aliphatic polyesters useful in the present invention may be prepared by substantially any of the conventionally known manufacturing methods such as those described in U.S. Patent Numbers 2,703,316; 3,912,692; 4,387,769; 5,216,050; and 6,323,307, the relevant disclosures of which are incorporated herein by reference.
  • Po!yanhydrides are another type of degradable polymer that may be suitable for use in the present invention. Poiyanhydride hydrolysis proceeds, inter alia, via free carboxyiic acid chain-ends to yield carboxylic acids as final degradation products. Their erosion time can be varied over a broad range of changes in the polymer backbone.
  • suitable polyanhydrides include poly(adipic anhydride), poiy(suberic anhydride), poiy(sebacic anhydride), and poiy(dodecanedioic anhydride). Other suitable examples include, but. are not limited to, poly(maieic anhydride) and po!y(benzoic anhydride).
  • degradable polymers may depend on several factors including, but not limited to, the composition of the repeat units, flexibility of the chain, presence of polar groups, molecular mass, degree of branching, crystal Unity, and orientation.
  • short chain branches may reduce the degree of crystaliinity of polymers while long chain branches may lower the melt viscosity and may impart, inter alia, extensions! viscosity with tension -stiffening behavior.
  • the properties of the material utilized further may be tailored by blending, and copo!ymerizing it with another polymer, or by a change in the macrorno!ecu!ar architecture (e.g. , hyper-branched polymers, star-shaped, or dendrimers, and the like).
  • any such suitable degradable polymers ⁇ e.g., hydrophobicity, hydrophiiicity, rate of degradation, and the like) can be tailored by introducing select functional groups along the polymer chains.
  • poly(phenyllactide) will degrade at about one-fifth of the rate of racemic poly(lactide) at a pH of 7,4 at 55 °C.
  • One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine the appropriate functional groups to introduce to the polymer chains to achieve the desired physical properties of the degradable polymers.
  • Suitable dehydrated compounds for use as solid particulates in the present invention may degrade over time as they are rehydrated .
  • particulate solid anhydrous borate matersai that degrades over time may be suitable for use in the present invention.
  • 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.
  • the degradabie matersai may have any shape, including, but not limited to, particles having the physical shape of platelets, shavings, flakes, ribbons, rods, strips, spheroids, toroids, pellets, tablets, or any other physical shape.
  • the degradabie matersai used may comprise a mixture of fibers and spherical particles.
  • degradabie material In choosing the appropriate degradabie material, one should consider the degradation products that will result, and choose a degradabie matersai that will not yield degradation products that would adversely affect other operations or components utilized in that particular application.
  • the choice of degradabie material also may depend, at least in part, on the conditions of the well (e.g., ellbore temperature). For instance, iactides have been found to be suitable for lower temperature wells, including those within the range of 60 °F to 150 °F, and poiylactides have been found to be suitable for wellbore temperatures above this range.
  • the degradation of the degradabie material could result in a final degradation product having the potential to affect the pH of the self-degrading cement compositions utilized in the methods of the present invention.
  • the degradation of the poiy(iactic add) to produce lactic acid may alter the pH of the self-degrading cement composition.
  • a buffer compound may be included within the self-degrading cement compositions utilized in the methods of the present invention in an amount sufficient, to neutralize the final degradation product. Examples of suitable buffer compounds include, but are not limited to, calcium carbonate, magnesium oxide, ammonium acetate, and the like.
  • a buffer compound to include in the self-degrading cement composition for a particular application.
  • An example of a suitable buffer compound comprises commercially available BA ⁇ 20 1 M (ammonium acetate, available from Halliburton Energy Services,, Inc.) .
  • a diverting agent may be a gel.
  • the gel may be a crosslinked gel.
  • gel diverting agents may include, but not be limited to, fluids with high concentration of gels such as xanthan.
  • crosslinked gels examples include, but are not Iimited to, high concentration gels such as DELTA FRAC i i ' fluids (high viscosity borate gel, available from Halliburton Energy Services, Inc.), K-MAX i l>1 fluids (crosslinkable hydroxyethyi cellulose, available from Halliburton Energy Services, Inc.), and K-MAX-PLUS 1 M fluids (crosslinkable hydroxyethyi cellulose, available from Halliburton Energy Services, Inc.), Gels may also be used by mixing the crosslinked gels with delayed chemical breakers, encapsulated chemical breakers, which will later reduce the viscosity, or with a material such as PLA (poly-lactic acid) beads, which although being a solid material, with time decomposes into acid, which will liquefy the K- AXTM fluids or other crosslinked gels.
  • high concentration gels such as DELTA FRAC i i ' fluids (high viscosity borate gel,
  • the gel diverting agents suitable for use in the present invention may comprise any substance (e.g. , a polymeric material) capable of increasing the viscosity of the treatment fluid
  • the gelling agent may comprise one or more polymers that have at least two molecules that, are capable of forming a crosslink in a crosslinking reaction in the presence of a crosslinking agent, and/or polymers that have at least two molecules that are so crosslinked (/,e, , a crosslinked gelling agent).
  • the gel diverting agents may be naturally-occurring gel diverting agents, synthetic gel diverting agents, or a combination thereof.
  • the gel diverting agents also may be cationic, anionic, amphoteric, or a combination thereof.
  • Suitable gel diverting agents include, but are not limited to, polysaccharides, biopolymers, and/or derivatives thereof that contain one or more of these monosaccharide units: galactose, mannose, glucoside, glucose, xylose, arabinose, fructose, glucuronic acid, or pyranosyi sulfate.
  • suitable polysaccharides include, but are not limited to, guar gums (e.g. , hydroxyethyi guar, hydroxypropyl guar, carboxymethyi guar, carboxymethyihyd roxyethyl guar, and carboxymethyihydroxypropy!
  • the gelling agents comprise an organic carboxylated polymer, such as CMHPG.
  • Suitable synthetic polymers for use as gel diverting agents include, but are not limited to, 2,2'-azobis(2,4-dimethyl vaieronitriie), 2,2'- azobis(2,4-d imethyi-4-methoxy vaieronitriie), polymers and copolymers of acrylamide ethyitrimethyi ammonium chloride, acry!amide, acryiamido-and methacry!amido-aikyl triaikyl ammonium salts, acryiamidomethy!propane sulfonic acid, acryiamidopropyi trimethyl ammonium chloride, acrylic acid, dimethyiaminoethyi methacrylamide, dimethylaminoethyl methacrylate, dimethylaminopropyi methacrylamide,, d imetbylaminopropylmethacryla ide, dimethyldiai
  • ammonium betaine ⁇ , ⁇ - dimethylacr iamide, N -met.hylacrylamide, nonylphenoxypoly(ethyieneoxy)ethyi methacrylate, partially bydrolyzed polyacryiamide, poly 2-amino-2-methyi propane sulfonic acid, polyvinyl alcohol, sodium 2-acry!amido-2-methy!propane sulfonate, quaternized dimethylaminoethyiacrylate, quaternized d imethyiaminoethylmethacryiate, and derivatives and combinations thereof.
  • the gelling agent comprises an acrylamide/2-(methacryloyioxy)ethyltrimethylammonium methyl sulfate copolymer.
  • the gelling agent may comprise an acryiamide/2-(methacryloyioxy)ethyitrimethylammonium chloride copolymer.
  • the gelling agent may comprise a derivatized cellulose that comprises cellulose g rafted with an ally! or a vinyl monomer, such as those disclosed in U.S. Patent Numbers 4,982,793 ; 5,067, 565; and 5, 122,549, the entire disclosures of which are incorporated herein by reference.
  • polymers and copolymers that comprise one or more functional groups ⁇ e.g., hydroxy!, cis-hydroxyi, carboxy!ic acids, derivatives of carboxylic acids, sulfate, sulfonate, phosphate, phosphonate, amino, or amide groups) may be used as gel diverting agents.
  • the treatment fluid comprising the gel diverting agents and/or a subsequent treatment fluid may comprise one or more crossisnking agents.
  • the crosslinking agents may comprise a borate ion, a metal ion, or similar component that is capable of cross!inking at least two molecules of the gelling agent.
  • suitable crossisnking agents include, but are not limited to, borate ions, magnesium ions, zirconium IV ions, titanium IV ions, aluminum ions, antimony ions, chromium ions, iron ions, copper ions, magnesium ions, and zinc ions.
  • ions may be provided by providing any compound that is capable of producing one or more of these ions.
  • examples of such compounds include, but are not limited to, ferric chloride, boric acid, disodium octaborate tetra hydrate, sodium diborate, pentaborates, ulexite, coiemanite, magnesium oxide, zirconium lactate, zirconium triethanoi amine, zirconium lactate triethanolamsne, zirconium carbonate, zirconium acetyiacetonate, zirconium malate, zirconium citrate, zirconium diisopropylamine lactate, zirconium glycoiate, zirconium triethanoi amine glycoiate, zirconium lactate glycoiate, titanium lactate, titanium malate, titanium citrate, titanium ammonium lactate, titanium triethanolamine, and titanium acetyiacetonate, aluminum lactate, aluminum citrate, antimony compounds,, chromium
  • the crosslinking agent may be formulated to remain inactive until it is "activated" by, among other things, certain conditions in the fluid (e.g., pH, temperature, etc.) and/or interaction with some other substance.
  • the activation of the crossisnking agent may be delayed by encapsulation with a coating ⁇ e.g., a porous coating through which the crossisnking agent may diffuse slowly, or a degradabie coating that degrades downhoie) that delays the release of the crosslinking agent until a desired time or place.
  • crosslinking agent may be governed by several considerations that should be recognized by one skilled in the art, including, but not limited to, the following : the type of gelling agent included, the molecular weig ht of the gel d iverting agents, the conditions in the subterranean formation being treated, the safety handling req rindments, the pH of the treatment fluid, temperature, and/or the desired delay for the cross!inking agent to crosslink the gel diverting agents,
  • Stimuli-degradabie and can be found in U .S. Patent Number 7,306,040, the relevant disclosure of which is incorporated herein by reference.
  • Stimuli that may lead to the deg radation of stimuli-degradable gei diverting agents include any change in the cond ition or properties of the gei includ ing, but not limited to, a change in pH (e.g. , caused by the buffering action of the rock or the decomposition of materials that release chemicals such as acids) or a change in the temperature (e.g. , caused by the contact of the fluid with the rock formation) .
  • degradable crosshnkers may be used to crosslink gelling agents comprising "ethylenically unsaturated monomers.
  • Suitable gelling agents for stimuli -degradable gel diverting agents include, but are not limited to, ionizable monomers (such as 1- ⁇ , ⁇ -diethy!aminoethy!methacry!ate) ; d iai!yidimethy!ammonium chloride; 2- acryiamido-2-methyl propane sulfonate; acrylic acid ; allylic monomers (such as di-aliyl phthalate; di-aliyl maleate; allyl diglycol carbonate; and the like) ; vinyl formate; vinyl acetate; vinyl propionate; vinyl butyrate; crotonsc acid ; itaconic acid acrylamide; methacrylamide; methacryionitriie; acrolein ; methyl
  • the deg radable crosslinker for use in stimuli-degradable gel diverting agents may contain a degradable group(s) including, but not limited to, esters, phosphate esters, amides, acetals, ketals, orthoesters, carbonates, anhydrides, siiyi ethers, alkene oxides, ethers, imines, ether esters, ester amides, ester urethanes, carbonate urethanes, amino acids, any derivative thereof, or any combination thereof,
  • the choice of the degradable group may be determined by pH and temperature, the details of which are available in known literature sources.
  • the unsaturated terminal groups may include substituted or unsubs ituted ethylenicaliy unsaturated groups, vinyl groups, allyl groups, acryl groups, or acryioyi groups, which are capable of undergoing polymerization with the above-mentioned gelling agents to form crosslinked gel diverting agents.
  • Suitable degradable crossiinkers for stimuli-degradab!e gel diverting agents include, but are not limited to, unsaturated esters such as diacrylates, dimetbacry!ates, and dibutyl acrylates; acry!amides; ethers such as divinyi ethers; and combinations thereof.
  • a stimuli- degradabie crosslinking agent comprises one or more degradable crosslink and two vinyl groups.
  • these crosslinking agents are sensitive to changes in pH, such as ortho ester-based embodiments, acetai-based embodiments,, ketal-based embodiments, and silicon-based embodiments.
  • the ortho ester-based embodiments should be stable at pHs of above 10, and should degrade at a pH below about 9;
  • the acetai-based embodiments should be stable at pHs above about 8 and should degrade at pH below about 6;
  • the ketal-based embodiments should be stable at pHs of about 7 and should degrade at a pH below 7;
  • the silicon- based embodiments should be stable at pHs above about 7 and should degrade faster in acidic media,
  • the relative stability of these groups should decrease in the following order: amides> ketals>orthoester.
  • the more stable crosslinking groups contain amides or ethers and would be preferred over other choices including esters, acetals,
  • the gel diverting agents may be present in the treatment fluids useful in the methods of the present invention in an amount sufficient to provide the desired viscosity.
  • the gel diverting agents may be present in an amount in the range of from a lower limit of about 0.1%, 0.15%, 0.25%, 0.5%, 1%, 5%, or 10% by weight of the treatment fluid to an upper limit of about 40%, 30%, 25%, or 10% by weight of the treatment fluid, and wherein the amount may range from any lower limit to any upper limit and encompass any subset therebetween.
  • suitable crosslinking agents may be present, in the treatment fluids useful in the methods of the present invention in an amount sufficient to provide the desired degree of crossiinking between molecules of the gel diverting agents.
  • the crossiinking agent may be present in the first treatment fluids and/or second treatment fluids of the present invention in an amount in the range of from about 0.005% to about 1% by weight of the treatment fluid
  • the crossiinking agent may be present in the treatment fluids of the present invention in an amount, in the range of from about 0.05% to about 1% by weight of the first treatment fluid and/or the second treatment fluid .
  • crossiinking agent to include in a treatment fluid of the present invention based on, among other things, the temperature conditions of a particular application, the type of gel diverting agents used, the molecular weight of the gel d iverting agents, the desired degree of viscosification, and/or the pH of the treatment fluid .
  • any derivative, any mixture, and any combination of the d iverting agents described herein may be used as primary diverting agents or secondary d iverting agents.
  • a primary diverting agent or a secondary diverting agent may be a hybrid of two or more diverting agents described herein .
  • treatment fluids comprising gel diverting agents may include internal gel breakers such as enzyme, oxidizing, acid buffer, or delayed gel breakers.
  • the gel breakers may cause the gel diverting agents of the present invention to revert to thin fluids that can be produced back to the surface, for example, after they have diverted fluid within a fracture network.
  • the gel breaker may be formulated to remain inactive until i is "activated" by, among other things, certain conditions in the fluid (e.g. , pH, temperature, etc. ) and/or interaction with some other substance.
  • the gel breaker may be delayed by encapsulation with a coating (e.g.
  • the gel breaker may be a degradabie material (e.g. , poiyiactic acid or poiygylcoiic acid) that releases an acid or alcohol in the present of an aqueous liquid .
  • the gel breaker used may be present in a treatmen fluid in an amount in the range of from about 0.0001 % to about 200% by weig ht of the gelling agent.
  • a gel breaker to include in certain treatment fluids of the present invention based on, among other factors, the desired amount of delay time before the gel breaks, the type of gel diverting agents used, the temperature conditions of a particular application, the desired rate and degree of viscosity reduction, and/or the pH of the treatment fluid.
  • Degradable particulates for use in the present invention may have an average diameter about, the diameter of the propping agents including, but not limited to, about 2 mesh to about 400 mesh on the U.S. Sieve Series. However, in certain circumstances, other mean particulate sizes may be desired and will be entirely suitable for practice of the present invention.
  • Degradable particles may comprise any materials suitable for use in a subterranean formation provided at least a portion of the degradable particulate is degradable. Suitable compositions include those disclosed herein for use in diverting agents including any derivative, any mixture, and any combination thereof, A noniimiting example of a commercially available degradable particulate includes degradable particulates in the BIOVOID ® series (degradable particles, available from Halliburton Energy Services, inc.). Degradable particles may be seif-degradable, stimuli-degradable, or any combination thereof.
  • a treatment fluid may be introduced into the wellbore with an additive designed to initiate, accelerate, slow, or delay degradation of the degradable particles. In some embodiments, such an additive may be introduced simultaneously with the degradable particulates,
  • propping agents for use in the present invention may comprise a plurality of proppant particulates.
  • Proppant particulates suitable for use in the present invention may comprise any material suitable for use in subterranean operations. Suitable materials for these proppant particulates include, but are not limited to, sand, bauxite, ceramic materials, glass materials, polymer materials, polytetrafluoroethyiene materials, nut shell pieces, cured resinous particulates comprising nut shell pieces, seed shell pieces, cured resinous particulates comprising seed shell pieces, fruit pit pieces, cured resinous particulates comprising fruit pit pieces, wood, composite particulates, and combinations thereof.
  • Suitable composite particulates may comprise a binder and a filler material wherein suitable filler materials include silica, alumina, fumed carbon, carbon black, graphite, mica, titanium dioxide, meta-silicate, calcium silicate, kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres, solid glass, and combinations thereof.
  • suitable filler materials include silica, alumina, fumed carbon, carbon black, graphite, mica, titanium dioxide, meta-silicate, calcium silicate, kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres, solid glass, and combinations thereof.
  • the mean particulate size generally may range from about 2 mesh to about 400 mesh on the U.S. Sieve Series; however, in certain circumstances, other mean particulate sizes may be desired and will be entirely suitable for practice of the present, invention.
  • preferred mean particulates size distribution ranges are one or more of 6/12, 8/16, 12/20, 16/30, 20/40, 30/50, 40/60, 40/70, or 50/70 mesh.
  • a proppant particle may be any known shape of material, including substantially spherical materials, fibrous materials, polygonal materials (such as cubic materials), and combinations thereof.
  • fibrous materials that may or may not be used to bear the pressure of a closed fracture, may be included in certain embodiments of the present invention.
  • the proppant particulates may be present in a treatment fluid for use in the present invention in an amount in the range of from about 0, 1 pounds per gallon ("ppg") to about 30 ppg by volume of the treatment, fluid,
  • a primary diverting agent, a secondary diverting agent, a degradabie particulate, a proppant particulate, or any combination thereof may be coated with a consolidating agent.
  • a consolidating agent As used herein, the term "coating,” and the like, does not imply any particular degree of coating on the particulate.
  • a primary diverting agent, a secondary diverting agent, a degradabie particulate, a proppant particulate, or any combination thereof may be coated with a consolidating agent prior to introduction into a we!!bore, after introduction into a wellbore, simultaneous to introduction into a weiibore, or any combination thereof.
  • a coating, including degree of coating may be used to control the rate of degradation of a primary diverting agent, a secondary diverting agent, a degradabie particulate, a proppant particulate, or any combination thereof.
  • Consolidating agents suitable for use in the methods of the present invention generally comprise any compound that is capable of minimizing particulate migration.
  • ISioniimiting examples of consolidating agents include SANDWEDGE ® (an adhesive substance, available from Halliburton Energy Services, Inc.) and EXPEDITE ® (a two-component resin system, available from Halliburton Energy Services, Inc.).
  • the consolidating agent may comprise a consolidating agent selected from the group consisting of: non-aqueous tackifying agents; aqueous tackifying agents; resins; siiyi-modified poiyamide compounds; crosslinkabie aqueous polymer compositions; and consolidating agent emulsions.
  • the type and amount of consolidating agent included in a particular method of the present invention may depend upon, among other factors, the composition and/or temperature of the subterranean formation, the chemical composition of formation fluids, the flow rate of fluids present in the formation, the effective porosity and/or permeability of the subterranean formation, pore throat size and distribution, and the like.
  • the concentration of the consolidating agent can be varied, inter alia, to either enhance bridging to provide for a more rapid coating of the consolidating agent or to minimize bridging to allow deeper penetration into the subterranean formation. It is within the ability of one skilled in the art, with the benefit, of this disclosure, to determine the type and amount of consolidating agent to include in the methods of the present invention to achieve the desired results,
  • the consolidating agent may comprise a consolidating agent emulsion that comprises an aqueous fluid, an emulsifying agent, and a consolidating agent.
  • the consolidating agent in suitable emulsions may be either a non-aqueous tackifying agent or a resin.
  • These consolidating agent emulsions have an aqueous external phase and organic-based internal phase.
  • emulsion and any derivatives thereof as used herein refers to a combination of two or more immiscible phases and includes, but is not limited to, dispersions and suspensions,
  • Suitable consolidating agent emulsions comprise an aqueous external phase comprising an aqueous fluid.
  • Suitable aqueous fluids that may be used in the consolidating agent emulsions of the present invention include freshwater, salt water, brine, seawater, or any other aqueous fluid that, preferably, does not adversely react with the other components used in accordance with this invention or with the subterranean formation.
  • a more suitable aqueous fluid may be one that is substantially free of salts.
  • the aqueous fluid may be present in the consolidating agent emulsions in an amount in the range of about 20% to 99.9% by weight of the consolidating agent emulsion composition. In some embodiments, the aqueous fluid may be present in the consolidating agent, emulsions in an amount in the range of about. 60% to 99.9% by weight of the consolidating agent, emulsion composition. In some embodiments, the aqueous fluid may be present in the consolidating agent emulsions in an amount in the range of about 95% to 99.9% by weight of the consolidating agent emulsion composition.
  • the consolidating agent in the emulsion may be either a nonaqueous tackifying agent or a resin.
  • the consolidating agents may be present in a consolidating agent emulsion in an amount in the range of about 0.1% to about 80% by weight of the consolidating agent emulsion composition. In some embodiments, the consolidating agent may be present in a consolidating agent emulsion in an amount in the range of about 0, 1% to about. 40% by weight of the composition. In some embodiments, the consolidating agent may be present in a consolidating agent emulsion in an amount in the range of about 0.1% to about 5% by weight of the composition.
  • the consolidating agent emulsions comprise an emulsifying agent.
  • suitable emulsifying agents may include surfactants, proteins, hydrolyzed proteins, lipids, glycoiipids, and nanosized particulates, including, but not limited to, fumed silica. Combinations of these may be suitable as well,
  • the consolidating agent may comprise a non-aqueous tackifying agent
  • a particularly preferred group of non-aqueous tackifying agents comprises polyamides that are liquids or in solution at the temperature of the subterranean formation such that they are, by themselves, non-hardening when introduced into the subterranean formation.
  • a particularly preferred product is a condensation reaction product comprised of a commercially available polyacid and a polyamine. Such commercial products include compounds such as combinations of dibasic acids containing some trimer and higher oligomers and also small amounts of monomer acids that are reacted with polyamines.
  • Other polyacids include trimer acids, synthetic acids produced from fatty acids, maleic anhydride, acrylic acid, and the like. Combinations of these may be suitable as well,
  • Additional compounds which may be used as non-aqueous tackifying agents include liquids and solutions of, for example, polyesters, polycarbonates, silyl-modified poiyamide compounds, polycarbamates, urethanes, natural resins such as shellac, and the like. Combinations of these may be suitable as well,
  • Non-aqueous tackifying agents suitable for use in the present invention may either be used such that they form a non-hardening coating on a surface or they may be combined with a multifunctional material capable of reacting with the non-aqueous tackifying agent to form a hardened coating.
  • a "hardened coating” as used herein means that the reaction of the tackifying compound with the multifunctional material should result in a substantially non- flowabie reaction product that exhibits a higher compressive strength in a consolidated agglomerate than the tackifying compound alone with the particulates, in this instance, the non-aqueous tackifying agent may function similarly to a hardenabie resin.
  • Multifunctional materials suitable for use in the present invention include, but. are not limited to, aldehydes; dialdehydes such as glutaraidehyde; hemiaceta!s or aldehyde releasing compounds; diacid halides; dihalides such as dichlorides and dibromides; polyacid anhydrides; epoxides; furfuraidehyde; aldehyde condensates; and silyl-modified poiyamide compounds; and the like; and combinations thereof.
  • Suitable silyl-modified poiyamide compounds that may be used in the present invention are those that are substantially self- hardening compositions capable of at least partially adhering to a surface or to a particulate in the unhardened state, and that are further capable of self- hardening themselves to a substantially non-tacky state to which individual particulates such as formation fines will not adhere to, for example, in formation or proppant pack pore throats.
  • Such silyl-modified polyamides may be based, for example, on the reaction product of a silating compound with a poiyamide or a combination of polyamides.
  • the poiyamide or combination of polyamides may be one or more poiyamide intermediate compounds obtained, for example, from the reaction of a polyacid (e.g., diacid or higher) with a polyamine (e.g., diamine or higher) to form a poiyamide polymer with the elimination of water.
  • a polyacid e.g., diacid or higher
  • a polyamine e.g., diamine or higher
  • the multifunctional material may be mixed with the tackifying compound in an amount, of about 0,01% to about 50% by weight, of the tackifying compound to effect, formation of the reaction product. In other embodiments, the multifunctional material is present in an amount of about 0,5% to about 1% by weight of the tackifying compound. Suitable multifunctional materials are described in U.S. Patent Number 5,839,510, the entire disclosure of which is herein incorporated by reference.
  • Aqueous tackifying agents suitable for use in the present invention are usually not generally significantly tacky when placed onto a particulate, but are capable of being "activated” (e.g., destabilized, coalesced and/or reacted) to transform the compound into a sticky, tackifying compound at a desirable time. Such activation may occur before, during, or after the aqueous tackifier agent is placed in the subterranean formation.
  • a pretreatment may be first contacted with the surface of a particulate to prepare if to be coated with an aqueous tackifier agent.
  • Suitable aqueous tackifying agents are generally charged polymers that comprise compounds that, when in an aqueous solvent or solution, will form a non-hardening coating (by itself or with an activator) and, when placed on a particulate, will increase the continuous critical resuspension velocity of the particulate when contacted by a stream of water.
  • the aqueous tackifier agent may enhance the g ain -to -grain contact between the individual particulates within the formation (be they diverting agents, proppant particulates, formation fines, or other particulates), helping bring about the consolidation of the particulates into a cohesive, flexible, and permeable mass.
  • Suitable aqueous tackifying agents include any polymer that can bind, coagulate, or flocculate a particulate. Also, polymers that function as pressure-sensitive adhesives may be suitable. Examples of aqueous tackifying agents suitable for use in the present invention include, but are not limited to: acrylic acid polymers; acrylic acid ester polymers; acrylic acid derivative polymers; acrylic acid homopoiymers; acrylic acid ester homopoiymers (such as poly(methyi acrylate), poly(butyl acrylate), and poly(2-ethylhexyl acrylate)) ; acrylic acid ester co-po!ymers; methacrySic acid derivative polymers; methacryiic acid homopo!ymers; methacryiic acid ester homopo!ymers (such as po!y(methy!
  • tackifying agents are described in U.S. Patent Number 5,249,627, the entire disclosure of which is incorporated herein by reference, which discloses aqueous tackifying agents that, comprise at least one member selected from the group consisting of benzyl coco di-(hydroxyethyl) quaternary amine, p-T-amyl- pbenol condensed with formaldehyde,, and a copolymer comprising from about 80% to about 100% Cl-30 alkylmethacryiate monomers and from about 0% to about 20% hydrophilic monomers.
  • the aqueous tackifying agent may comprise a copolymer that comprises from about 90% to about 99.5% 2-ethylhexylacryiate and from about 0.5% to about 10% acrylic acid.
  • Suitable hydrophiilic monomers may be any monomer that will provide polar oxygen-containing or nitrogen-containing groups.
  • Suitable hydrophiilic monomers include diaikyl amino aikyl (meth)acryiates and their quaternary addition and acid salts, acryiarnide, N-- (diaikyl amino aikyl) acryiarnide, methacryiamides and their quaternary addition and acid salts, hydroxy aikyl (meth)acryiates, unsaturated carboxylic acids such as methacryiic acid or acrylic acid, hydroxyethyl acrylate, acryiarnide, and the like. Combinations of these may be suitable as well.
  • These copolymers can be made by any suitable emulsion polymerization technique. Methods of producing these copolymers are disclosed, for example, in U.S. Patent Number 4,670,501, the entire disclosure of which is incorporated herein by reference.
  • the consolidating agent may comprise a resin.
  • resin refers to any of numerous physically similar polymerized synthetics or chemically modified natural resins including thermoplastic materials and thermosetting materials. Resins that may be suitable for use in the present invention may include substantially aii resins known and used in the art,
  • One type of resin suitable for use in the methods of the present invention is a two-component epoxy-based resin comprising a liquid hardenable resin component and a liquid hardening agent component.
  • the liq uid hardenable resin component comprises a hardenable resin and an optional solvent.
  • the solvent may be added to the resin to reduce its viscosity for ease of handling, mixing and transferring . It is within the ability of one skilled in the art, with the benefit of this d isclosure, to determine if and how much solvent may be needed to achieve a viscosity suitable to the subterranean conditions. Factors that may affect this decision inciude geographic location of the well, the surrounding weather cond itions, and the desired long-term stability of the consolidating agent.
  • the second component is the liquid hardening agent component, which comprises a hardening agent, an optional siiane coupling agent, a surfactant, an optional hydrolyzable ester for, among other things, breaking gelled fracturing fluid films on particulates, and an optional liquid carrier fluid for, among other things, reducing the viscosity of the hardening agent component.
  • hardenable resins that can be used in the liquid hardenable resin component include, but are not limited to, organic resins such as bisphenol A digiycidyl ether resins, butoxymethyi butyl glycidyl ether resins, bisphenol A-epichiorohyd rin resins, bisphenol F resins, poiyepoxide resins, novoiak resins, polyester resins, phenol-aldehyde resins, urea-aldehyde resins, furan resins, urethane resins, glycidyl ether resins, other epoxide resins, and combinations thereof.
  • organic resins such as bisphenol A digiycidyl ether resins, butoxymethyi butyl glycidyl ether resins, bisphenol A-epichiorohyd rin resins, bisphenol F resins, poiyepoxide resins, novoiak resins, polyester resins,
  • the hardenable resin may comprise a urethane resin
  • suitable urethane resins may comprise a polyisocyanate component and a polyhydroxy component
  • suitable hardenable resins, including urethane resins that may be suitable for use in the methods of the present invention inciude those described in U .S. Patent N umbers 4,585, 064; 6,582,819; 6, 677,426; and 7, 153, 575, the entire disclosures of which are herein incorporated by reference.
  • the hardenable resin may be included in the liquid hardenable resin component in an amount in the range of about 5% to about 100% by weight of the liq uid hardenable resin component, It is within the ability of one skilled in the art, with the benefit of this disclosure, to determine how much of the liquid hardenable resin component may be needed to achieve the desired results. Factors that may affect this decision include which type of liquid hardenable resin component, and liquid hardening agent component are used.
  • Any solvent that, is compatible with the hardenable resin and achieves the desired viscosity effect may be suitable for use in the liquid hardenable resin component.
  • Suitable solvents may include butyl lactate, dipropylene glycol methyl ether, dipropyiene glycol dimethyl ether, dimethyl formamide, diethyieneglycol methyl ether, ethyieneglycol butyl ether, diethyieneglycol butyl ether, propylene carbonate, methanol, butyl alcohol, d'iimonene, fatty acid methyl esters, and butylglycidyl ether, and combinations thereof.
  • aqueous dissolvable solvents such as methanol, isopropanol, butanoi, and glycol ether solvents, and combinations thereof.
  • Suitable glycol ether solvents include, but are not limited to, diethyiene glycol methyl ether, dipropylene glycol methyl ether, 2-hutoxy ethanol, ethers of a C2 to C6 dihydric alkanol containing at ieast. one CI to C6 alkyl group, mono ethers of dihydric aikanols, methoxypropanoi, butoxyetbanol, and hexoxyethanol, and isomers thereof. Selection of an appropriate solvent is dependent on the resin composition chosen and is within the ability of one skilled in the art, with the benefit of this disclosure.
  • a solvent in the liquid hardenable resin component is optional but may be desirable to reduce the viscosity of the hardenable resin component, for ease of handling, mixing, and transferring. However, as previously stated, it may be desirable in some embodiments to not. use such a solvent for environmental or safety reasons. It is within the ability of one skilled in the art, with the benefit of this disclosure, to determine if and how much solvent is needed to achieve a suitable viscosity. In some embodiments, the amount of the solvent used in the liquid hardenable resin component may be in the range of about 0.1% to about 30% by weight of the liquid hardenable resin component.
  • the liquid hardenable resin component may be heated to reduce its viscosity, in place of, or in addition to, using a solvent.
  • amines and cycio-aliphatic amines such as piperidine, triethylamine, tris(dimethyiaminomethyi) phenol, and dimethylaminomethyi)phenoi may be preferred.
  • 4,4'-diaminodipheny! sulfone may be a suitable hardening agent.
  • Hardening agents that comprise piperazine or a derivative of piperazine have been shown capable of curing various hardenable resins from temperatures as low as about 50 °F to as high as about 350 °F,
  • the hardening agent used may be included in the liquid hardening agent component in an amount sufficient to at least partially harden the resin composition, in some embodiments of the present invention, the hardening agent used is included in the liquid hardening agent component in the range of about 0.1% to about 95% by weight of the liquid hardening agent component. In other embodiments, the hardening agent used may be included in the liquid hardening agent component in an amount of about 15% to about. 85% by weight of the liquid hardening agent component. In other embodiments, the hardening agent used may be included in the liquid hardening agent component in an amount of about 15% to about 55% by weight of the liquid hardening agent component.
  • the consolidating agent may comprise a liquid hardenable resin component emulsified in a liquid hardening agent component, wherein the liquid hardenable resin component is the internal phase of the emulsion and the liquid hardening agent component is the external phase of the emulsion.
  • the liquid hardenable resin component may be emulsified in water and the liquid hardening agent component may be present in the water.
  • the liquid hardenable resin component may be emulsified in water and the liquid hardening agent component may be provided separately.
  • both the liq uid hardenable resin component and the liq uid hardening agent component may both be emulsified in water,
  • the optional silane coupling agent may be used, among other things, to act as a mediator to help bond the resin to particulates.
  • suitable siiane coupiing agents include, but are not limited to, N-2--(aminoetbyl) - 3-aminopropyltrimethoxysiiane, and 3-g!ycidoxypropyltrirnetboxysi!ane, and combinations thereof.
  • the silane coupling agent may be included in the resin component or the liq uid hardening agent component (according to the chemistry of the particular group as determined by one skilled in the art with the benefit of this d isclosure) .
  • the siiane coupling agent used is included in the liquid hardening agent component in the range of about 0.1 % to about 3% by weight of the liquid hardening agent component,
  • any surfactant compatible with the hardening agent and capable of facilitating the coating of the resin onto particulates in the subterranean formation may be used in the liquid hardening agent component.
  • Such surfactants include, but are not limited to, an alkyi phosphonate surfactant (e.g. , a C12-C22 alkyl phosphonate surfactant), an ethoxylated nonyl phenol phosphate ester, one or more cationic surfactants, and one or more nonionic surfactants, Combinations of one or more cationic and nonionic surfactants also may be suitable. Examples of such surfactant combinations are described in U .S.
  • the surfactant or surfactants that may be used are included in the liquid hardening agent component in an amount in the range of about 1% to about 10% by weight of the liquid hardening agent component.
  • hydrolyzable esters that may be used in the liquid hardening agent component include, but are not limited to, a combination of dimethyigiutarate, dimethy!adipate, and d imethylsuccinate; dimethyithioiate; methyl salicylate; d imethyl salicylate; and dimethylsuccinate; and combinations thereof,
  • a hydrolyzable ester is included in the liquid hardening agent component in an amount in the range of about 0, 1% to about 3% by weig ht, of the liquid hardening agent component.
  • a hyd rolyzable ester is included in the liq uid hardening agent component in an amount in the range of about 1% to about 2.5% by weight of the liquid hardening agent component.
  • a diluent or liquid carrier fluid in the liquid hardening agent component is optional and may be used to reduce the viscosity of the liquid hardening agent component, for ease of handling, mixing, and transferring. As previously stated, it may be desirable in some embodiments to not use such a solvent for environmental or safety reasons.
  • Any suitable carrier fluid that, is compatible with the liquid hardening agent component and achieves the desired viscosity effects is suitable for use in the present invention.
  • Some suitable liquid carrier fluids are those having high flash points ⁇ e.g., about 125 °F.
  • solvents include, but are not limited to, butyl lactate, dipropy!ene glycol methyl ether, dipropyiene glycol dimethyl ether, dimethyl formamide, diethylenegiycoi methyl ether, ethyieneglycol butyl ether, diethylenegiycoi butyl ether, propylene carbonate, methanol, butyl alcohol, d'iimonene, and fatty acid methyl esters, and combinations thereof.
  • suitable liquid carrier fluids include aqueous dissolvable solvents such as, for example, methanol, isopropanol, butano!, glycol ether solvents, and combinations thereof
  • Suitable glycol ether liquid carrier fluids include, but are not limited to, diethylene glycol methyl ether, dipropyiene glycol methyl ether, 2-butoxy ethanol, ethers of a C2 to C6 dihydric alkanol having at least one Ci to C6 alkyl group, mono ethers of dihydric alkanols, methoxypropanoi, butoxyethano!, and hexoxyethanol, and isomers thereof, Combinations of these may be suitable as well. Selection of an appropriate liquid carrier fluid is dependent, on, inter alia, the resin composition chosen.
  • furan-based resins include, but are not limited to, furfury! alcohol resins, furfural resins, combinations of furfury! alcohol resins and aldehydes, and a combination of furan resins and phenolic resins. Of these, furfury! alcohol resins may be preferred.
  • a furan-based resin may be combined with a solvent to control viscosity if desired.
  • Suitable solvents for use in the furan-based consolidation fluids of the present invention include, but are not limited to, 2-butoxy ethanol, butyl lactate, butyl acetate, tetrahydrofurfuryi metnacrylate, tetrahydrofurfuryi acrylate, esters of oxalic, maleic and succinic acids, and furfury! acetate. Of these, 2-butoxy ethanol is preferred.
  • the furan-based resins suitable for use in the present invention may be capable of enduring temperatures well in excess of 350 °F without degrading . In some embodiments, the furan-based resins suitable for use in the present invention are capable of enduring temperatures up to about 700 °F without degrading.
  • the furan -based resins suitable for use in the present invention may further comprise a curing agent to facilitate or accelerate curing of the furan-based resin at lower temperatures.
  • a curing agent may be particularly useful in embodiments where the furan-based resin may be placed within subterranean formations having temperatures below about 350 °F.
  • suitable curing agents include, but are not limited to, organic or inorganic acids, such as, inter alia, maieic acid, fumaric acid, sodium bisuifate, hydroch!oric acid, hydrofluoric acid, acetic acid, formic acid, phosphoric acid, sulfonic acid, alkyi benzene sulfonic acids such as toluene sulfonic acid and dodecyi benzene sulfonic acid ("DDBSA”), and combinations thereof.
  • the furan-based resin may cure autocatalytica!!y,
  • Still other resins suitable for use in the methods of the present invention are phenolic-based resins.
  • Suitable phenolic-based resins include, but are not limited to, terpo!ymers of phenol, phenolic formaldehyde resins, and a combination of phenolic and furan resins. In some embodiments, a combination of phenolic and furan resins may be preferred.
  • a phenolic-based resin may be combined with a solvent to control viscosity if desired.
  • Suitable solvents for use in the present invention include, but. are not limited to, butyl acetate, butyl lactate, furfuryi acetate, and 2-butoxy ethanol. Of these, 2-butoxy ethanol may be preferred in some embodiments,
  • Yet another resin-type material suitable for use in the methods of the present invention is a phenol/phenol formaldehyde/furfuryl alcohol resin comprising of about 5% to about 30% phenol, of about 40% to about 70% phenol formaldehyde, of about 10% to about 40% furfuryi alcohol, of about 0.1% to about 3% of a siiane coupling agent, and of about 1% to about 15% of a surfactant.
  • suitable siiane coupling agents include, but are not limited to, N-2- (aminoethyi)-3-aminopropyltrimethoxysilane, and 3-giycidoxypropyitrimethoxysilane.
  • Suitable surfactants include, but are not limited to, an ethoxyiated nonyl phenol phosphate ester, combinations of one or more cationic surfactants, and one or more nonionic surfactants and an alky! phosphonate surfactant.
  • resins suitable for use in the consolidating agent emulsion compositions of the present invention may optionally comprise filler particles.
  • Suitable filler particles may include any particle that does not adversely react with the other components used in accordance with this invention or with the subterranean formation.
  • suitable filler particles include silica, g lass, clay, alumina, fumed silica, carbon black, graphite, mica, meta-silicate, calcium silicate, calcine, kaoline, talc, zirconia, titanium dioxide, fly ash, and boron, and combinations thereof.
  • the filler particles may range in size of about 0.01 ⁇ to about 100 pm.
  • the filler particles may be included in the resin composition in an amount of about 0. 1 % to about 70% by weight of the resin composition. In other embodiments, the filler particles may be included in the resin composition in an amount of about 0.5% to about 40% by weight of the resin composition. In some embodiments, the filler particles may be included in the resin composition in an amount of about 1% to about 10% by weig ht of the resin composition .
  • Silyl- mod ified polyamide compounds may be described as substantially self-hardening compositions that are capable of at least partially adhering to particulates in the unhardened state, and that are further capable of self-hardening themselves to a substantially non-tacky state to which individ ual particulates such as formation fines will not adhere to, for example, in formation or proppant pack pore throats,
  • Such silyl-modified poiyamides may be based, for example, on the reaction product of a silating compound with a polyamide or a combination of poiyamides.
  • the polyamide or combination of poiyamides may be one or more polyamide intermediate compounds obtained, for example, from the reaction of a poiyacid (e.g.
  • the consolidating agent comprises cross!inkabie aqueous polymer compositions.
  • suitable crosslinkable aqueous polymer compositions comprise an aqueous solvent, a crosslinkable polymer, and a cross!inking agent.
  • Such compositions are similar to those used to form gelled treatment fluids, such as fracturing fluids, but according to the methods of the present invention, they are not exposed to breakers or de- linkers, and so they retain their viscous nature over time.
  • the aqueous solvent may be any aqueous solvent in which the crosslinkable composition and the cross!inking agent may be dissolved, mixed, suspended, or dispersed therein to facilitate gel formation.
  • the aqueous solvent used may be freshwater, salt water, brine, seawater, or any other aqueous liquid that does not adversely react with the other components used in accordance with this invention or with the subterranean formation,
  • crosslinkable polymers that can be used in the crosslinkable aqueous polymer compositions include, but are not limited to, carboxylate-containing polymers and acryiamide-containing polymers.
  • carboxylate-containing polymers and acryiamide-containing polymers.
  • the most suitable polymers are thought to be those that would absorb or adhere to the rock surfaces so that the rock matrix may be strengthened without occupying a lot of the pore space and/or reducing permeability.
  • suitable acryiamide-containing polymers include polyacry!amide, partially hydrolyzed po!yacry!amide, copolymers of acryiamide and acrylate, and carboxylate- containing terpoiymers and tetrapo!ymers of acrylate. Combinations of these may be suitable as well.
  • suitable crosslinkable polymers include hydratable polymers comprising polysaccharides and derivatives thereof, and that contain one or more of the monosaccharide units, galactose, mannose, glucoside, glucose, xylose, arabinose, fructose, glucuronic acid, or pyranosyi sulfate.
  • Suitable natural hydratable polymers include, but are not limited to, guar gum, locust bean gum, tara, konjak, tamarind, starch, cellulose, karaya, xanthan, tragacanth, and carrageenan, and derivatives of ail of the above. Combinations of these may be suitable as well.
  • Suitable hydratable synthetic polymers and copolymers that may be used in the crosslinkable aqueous polymer compositions include, but are not limited to, po!ycarboxyiates such as polyacryiates and polymethacry!ates; polyacry!amides; methy!vinyl ether polymers; polyvinyl alcohols; and polyvinylpyrrolidone, Combinations of these may be suitable as well.
  • the crossiinkabie polymer used should be included in the crossiinkabie aqueous polymer composition in an amount, sufficient to form the desired gelled substance in the subterranean formation.
  • the crossiinkabie polymer may be included in the crossiinkabie aqueous poiymer composition in an amount in the range of from about 1% to about 30% by weight of the aqueous solvent. In another embodiment of the present invention, the crossiinkabie polymer may be included in the crossiinkabie aqueous poiymer composition in an amount in the range of from about 1% to about 20% by weight of the aqueous solvent.
  • the crossiinkabie aqueous polymer compositions of the present invention further comprise a crosslinking agent for crosslinking the crossiinkabie polymers to form the desired gelled substance.
  • the crosslinking agent is a molecule or complex containing a reactive transition metal cation
  • a most, preferred crosslinking agent comprises trivending chromium cations compiexed or bonded to anions, atomic oxygen, or water.
  • suitable crosslinking agents include, but are not limited to, compounds or complexes containing chromic acetate and/or chromic chloride.
  • Other suitable transition metal cations include chromium VI within a redox system, aluminum ⁇ , iron II, iron III, and zirconium IV.
  • the crosslinking agent should be present in the crossiinkabie aqueous polymer compositions of the present invention in an amount sufficient to provide, among other things, the desired degree of crosslinking.
  • the crosslinking agent may be present in the crossiinkabie aqueous polymer compositions of the present invention in an amount in the range of from about 0.01% to about 5% by weight of the crossiinkabie aqueous poiymer composition.
  • the exact type and amount of crosslinking agent or agents used depends upon the specific crossiinkabie polymer to be crossiinked, formation temperature conditions, and other factors known to those individuals skilled in the art.
  • the crossiinkabie aqueous polymer compositions may further comprise a crosslinking delaying agent, such as a polysaccharide crosslinking delaying agent, derived from guar, guar derivatives, or cellulose derivatives,
  • a crosslinking delaying agent such as a polysaccharide crosslinking delaying agent, derived from guar, guar derivatives, or cellulose derivatives
  • the crosslinking delaying agent may be included in the cross!inkabie aqueous polymer compositions, among other things, to delay crosslinking of the crosslinkabie aqueous polymer compositions until desired.
  • a crosslinking delaying agent such as a polysaccharide crosslinking delaying agent, derived from guar, guar derivatives, or cellulose derivatives
  • the crosslinking delaying agent may be included in the cross!inkabie aqueous polymer compositions, among other things, to delay crosslinking of the crosslinkabie aqueous polymer compositions
  • the consolidating agents useful in the methods of the present invention comprise polymerizable organic monomer compositions.
  • suitable po!ymerizable organic monomer compositions comprise an aqueous-base fluid, a water-soluble polymerizable organic monomer, an oxygen scavenger, and a primary initiator.
  • the aqueous-based fluid component of the polymerizable organic monomer composition generally may be freshwater, salt water, brine, seawater, or any other aqueous liquid that does not adversely react with the other components used in accordance with this invention or with the subterranean formation,
  • the water-soluble polymerizable organic monomer should be seif-crosslinking .
  • Suitable monomers which are thought to be self crosslinking include, but are not limited to, hydroxyethylacryiate, hydroxymetbyiacry!ate, hydroxyethylmethacry!ate, -hydroxy methylacry!amide, N-hydroxymethyi- methacrylamide, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene gylcol acrylate, and polypropylene glycol methacrylate, and combinations thereof.
  • hydroxyethylacryiate may be preferred in some instances.
  • An example of a particularly suitable monomer is hydroxyethylceliulose-vinyl phosphoric acid .
  • the water-soluble polymerizable organic monomer (or monomers where a combination thereof is used) should be included in the polymerizable organic monomer composition in an amount sufficient to form the desired geiled substance after piacement of the poiymerizabie organic monomer composition into the subterranean formation,
  • the water-solubie poiymerizabie organic monomer may be included in the poiymerizabie organic monomer composition in an amount in the range of from about. 1% to about 30% by weight of the aqueous-base fluid.
  • the water-soiub!e poiymerizabie organic monomer may be included in the poiymerizabie organic monomer composition in an amount in the range of from about 1% to about 20% by weight of the aqueous-base fluid.
  • an oxygen scavenger such as stannous chloride
  • stannous chloride may be included in the poiymerizabie monomer composition.
  • the stannous chloride may be predissolved in a hydrochloric acid solution,
  • the stannous chloride may be dissolved in a 0.1% by weight aqueous hydrochloric acid solution in an amount of about 10% by weight of the resulting soiution.
  • the resulting stannous chloride-hydrochloric acid solution may be included in the poiymerizabie organic monomer composition in an amount in the range of from about 0.1% to about 10% by weight of the poiymerizabie organic monomer composition, Generally, the stannous chloride may be included in the poiymerizabie organic monomer composition of the present invention in an amount, in the range of from about 0,005% to about. 0.1% by weight of the poiymerizabie organic monomer composition,
  • a primary initiator may be used, among other things, to initiate polymerization of the water-soluble poiymerizabie organic monomer(s). Any compound or compounds that form free radicals in aqueous solution may be used as the primary initiator, The free radicals act, among other things, to initiate polymerization of the water-soluble poiymerizabie organic monomer present in the poiymerizabie organic monomer composition.
  • Compounds suitable for use as the primary initiator include, but are not limited to, alkali metal persuifat.es; peroxides; oxidation-reduction systems employing reducing agents, such as sulfites in combination with oxidizers; and azo polymerization initiators.
  • Suitable azo polymerization initiators include 2,2'-azohis(2-imidazole- 2-hydroxyethy!) propane, 2 f 2'-azobis(2-aminopropane) f 4,4'-azobis(4- cyanova!eric acid), and 2,2'-azobis(2-methyl-N-(2-hydroxyethy! propionamide.
  • the primary initiator should be present in the poiymerizabie organic monomer composition in an amount, sufficient to initiate polymerization of the water-soiub!e poiymerizabie organic monomer(s).
  • the primary initiator may be present in the poiymerizabie organic monomer composition in an amount in the range of from about 0.1% to about 5% by weight of the water-soluble poiymerizabie organic monomer(s).
  • the poiymerizabie organic monomer compositions further may comprise a secondary initiator.
  • a secondary initiator may be used, for example, where the immature aqueous gel is placed into a subterranean formation that is relatively cool as compared to the surface mixing, such as when placed below the mud line in offshore operations.
  • the secondary initiator may be any suitable water-soluble compound or compounds that may react with the primary initiator to provide free radicals at a lower temperature.
  • An example of a suitable secondary initiator is triethanolamine.
  • the secondary initiator is present in the poiymerizabie organic monomer composition in an amount in the range of from about 0.1% to about 5% by weight of the water-soluble poiymerizabie organic monomer(s),
  • the poiymerizabie organic monomer compositions of the present invention may further comprise a crosslinking agent for crosslinking the poiymerizabie organic monomer compositions in the desired gelled substance
  • the crosslinking agent is a molecule or complex containing a reactive transition metal cation.
  • a suitable crosslinking agent comprises trivalent chromium cations complexed or bonded to anions, atomic oxygen, or water, Examples of suitable crosslinking agents include, but are not limited to, compounds or complexes containing chromic acetate and/or chromic chloride.
  • transition metal cations include chromium VI within a redox system, aluminum HI, iron II, iron ⁇ , and zirconium IV,
  • the crosslinking agent may be present in poiymerizabie organic monomer compositions in an amount in the range of from 0.01% to about 5% by weight of the polymerizab!e organic monomer composition ,
  • a treatment fluid may comprise a base fluid selected from an oil-based fluid, an aqueous-based fluid, a water-in-oii emulsion, or an oil-in-water emulsion .
  • the base fluid may vary for the different steps described above. In such embodiments, one skilled in the art should understand that a pill may optionally need to be inserted between steps to properly change base fluids.
  • Suitable oil-based fluids may include an alkane, an olefin, an aromatic organic compound, a cyclic alkane, a paraffin, a diesel fluid, a mineral oil, a desulfurized hydrogenated kerosene, and any combination thereof.
  • suitable invert emulsions include those disclosed in U .S. Patent Number 5,905,061 5,977,031 ; and 6,828,279, each of which are incorporated herein by reference.
  • Aqueous base fluids suitable for use in the treatment fluids of the present invention may comprise fresh water, saltwater (e.g. , water containing one or more salts d issolved therein), brine (e.g. saturated salt water), seawater, or combinations thereof.
  • the water may be from any source, provided that it does not contain components that might adversely affect the stability and/or performance of the first treatment fluids or second treatment fluids of the present invention .
  • the density of the aqueous base fluid can be adjusted , among other purposes, to provide additional particulate transport and suspension in the treatment fluids used in the methods of the present invention .
  • the pH of the aq ueous base fluid may be adjusted (e.g. , by a buffer or other pH adjusting agent), among other purposes, to activate a crosslinking agent, and/or to reduce the viscosity of the first treatment fluid (e.g.
  • the pH may be adjusted to a specific level, which may depend on, among other factors, the types of gelling agents, acids, and other additives included in the treatment fluid .
  • the types of gelling agents, acids, and other additives included in the treatment fluid may depend on, among other factors, the types of gelling agents, acids, and other additives included in the treatment fluid .
  • a treatment fluid for use in the present invention may further comprise an additive including, but. not limited to, a salt; a weighting agent; an inert solid ; a fluid loss control agent; an emulsifier; a dispersion aid ; a corrosion inhibitor; an emulsion thinner; an emulsion thickener; a viscosifying agent; a high-pressure, high-temperature emuisifier-fi!tration control agent; a surfactant; a particulate; a lost circulation material; a foaming agent; a gas; a pH control additive; a breaker; a biocide; a crosslinker; a stabilizer; a chelating agent; a scale inhibitor; a mutual solvent; an oxidizer; a reducer; a friction reducer; a clay stabilizing agent; and any combination thereof.
  • an additive including, but. not limited to, a salt; a weighting agent; an inert solid ; a fluid loss control agent; an
  • the present invention provides for of treating a subterranean formation able to support a fracture network having at least one access conduit to the subterranean formation from a wellbore, Treating the subterranean formation may include the steps, not necessarily in this order or performed independently, placing a first treatment fluid into the subterranean formation through the at least one access conduit at a pressure sufficient to form at least a portion of a fracture network extending from the at least one access conduit; pumping a second treatment fluid comprising a propping agent into the fracture network such that, the propping agent forms a proppant pack in at least, a portion of the fracture network; placing a third treatment fluid comprising a secondary diverting agent into the wellbore such that the secondary diverting agent goes through the access conduit and into at least a portion of the fracture network so as to substantially inhibit fluid flow through at least a portion of the fracture network without substantially inhibiting fluid flow through the access conduit; and placing a fourth treatment fluid comprising a primary diverting agent into the
  • the present invention provides for of treating a subterranean formation having a closure pressure greater than about 500 psi and having at least one access conduit to the subterranean formation from a wellbore
  • Treating the subterranean formation may include the steps, not necessarily in this order or performed independently, placing a first treatment fluid into the subterranean formation through the at least one access conduit at a pressure sufficient to form at least a portion of a fracture network extending from the at least one access conduit; pumping a second treatment fluid comprising a propping agent into the fracture network such that the propping agent forms a proppant pack in at.
  • a third treatment fluid comprising a secondary diverting agent into the wellbore such that the secondary diverting agent goes through the access conduit and into at least a portion of the fracture network so as to substantially inhibit fluid flow through at least a portion of the fracture network without substantially inhibiting fluid flow through the access conduit; and placing a fourth treatment fluid comprising a primary diverting agent into the wellbore such that, the primary diverting agent substantially inhibits fluid flow through the access conduit,
  • the present invention provides for of treating a subterranean formation able to support a fracture network having at least one access conduit to the subterranean formation from a wellbore, Treating the subterranean formation may include the steps, not necessarily in this order or performed independently, placing a first treatment fluid into the subterranean formation at a pressure sufficient to form at least a portion of a fracture network extending from at least one access conduit; pumping a second treatment fluid comprising a propping agent into the fracture network such that the propping agent forms a proppant pack in at. least a portion of the fracture network, wherein the propping agent comprises proppant particulates at.
  • a third treatment fluid comprising a secondary diverting agent into the wellbore such that the secondary diverting agent goes through the access conduit and into at least a portion of the fracture network so as to substantially inhibit fluid flow through at least a portion of the fracture network without substantially inhibiting fluid flow through the access conduit, wherein the secondary diverting agent is at least partially degradable; placing a fourth treatment, fluid comprising a primary diverting agent into the wellbore such that the primary diverting agent substantially inhibits fluid flow through the access conduit, wherein the primary diverting agent is at least partially degradable; and repeating at least one step selected from the group consisting of pumping the second treatment fluid, placing the third treatment fluid, placing the fourth treatment fluid, placing the fifth treatment fluid, and any combination thereof,
  • 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 disciosed 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 disciosed. In particular, every range of values (of the form, “from about, a to about, b,” or, equivendingiy, “from approximately a to b,” or, equivalently, “from approximately a-b”) disciosed herein is to be understood to set forth every number and range encompassed within the broader range of values.

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Abstract

Un procédé de traitement d'une formation souterraine peut comprendre le placement d'un premier fluide de traitement dans une formation souterraine par le biais d'une conduite d'accès raccordant la formation souterraine à un puits de forage à une pression suffisante pour former au moins une partie d'un réseau de fracture ; le pompage d'un deuxième fluide de traitement comprenant un agent de soutènement dans le réseau de fracture de sorte que l'agent de soutènement forme un bloc de soutènement dans au moins une partie du réseau de fracture ; le placement d'un troisième fluide de traitement comprenant un agent de déviation secondaire dans le réseau de fracture de manière à empêcher sensiblement le fluide de s'écouler à travers au moins une partie du réseau de fracture sans empêcher sensiblement le fluide de s'écouler à travers la conduite d'accès ; et le placement d'un quatrième fluide de traitement comprenant un agent de déviation primaire dans le puits de forage de sorte que l'agent de déviation primaire empêche sensiblement le fluide de s'écouler à travers la conduite d'accès.
PCT/US2012/047787 2011-08-23 2012-07-23 Procédé de fracturation permettant d'améliorer la répartition d'un agent de soutènement afin de développer au maximum la connectivité entre la formation et le puits de forage WO2013028298A2 (fr)

Priority Applications (6)

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CN201280041066.4A CN103748320A (zh) 2011-08-23 2012-07-23 增强支撑剂分布以使地层和井筒之间的连通性最大化的压裂方法
EP12743595.6A EP2748431A2 (fr) 2011-08-23 2012-07-23 Procédé de fracturation permettant d'améliorer la répartition d'un agent de soutènement afin de développer au maximum la connectivité entre la formation et le puits de forage
BR112014004099A BR112014004099A2 (pt) 2011-08-23 2012-07-23 método
CA2843319A CA2843319A1 (fr) 2011-08-23 2012-07-23 Procede de fracturation permettant d'ameliorer la repartition d'un agent de soutenement afin de developper au maximum la connectivite entre la formation et le puits de forage
AU2012299397A AU2012299397A1 (en) 2011-08-23 2012-07-23 Fracturing process to enhance propping agent distribution to maximize connectivity between the formation and the wellbore
MX2014002073A MX2014002073A (es) 2011-08-23 2012-07-23 Proceso de fracturacion para mejorar la distribucion de materiales de apoyo para aumentar al maximo la conectividad entre la formacion y el sondeo.

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US13/215,848 US20130048282A1 (en) 2011-08-23 2011-08-23 Fracturing Process to Enhance Propping Agent Distribution to Maximize Connectivity Between the Formation and the Wellbore
US13/215,848 2011-08-23

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BR112014004099A2 (pt) 2017-03-14
WO2013028298A3 (fr) 2013-11-28
US20130048282A1 (en) 2013-02-28
CA2843319A1 (fr) 2013-02-28
AR087622A1 (es) 2014-04-09
CN103748320A (zh) 2014-04-23
MX2014002073A (es) 2014-05-28
EP2748431A2 (fr) 2014-07-02

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