METHOD FOR TREATMENT OF UNDERGROUND FORMATION, SYSTEM FOR TREATMENT OF UNDERGROUND FORMATION, AND CU

专利摘要:
method for treating an underground formation, system for treating an underground formation, and curable composition for treating an underground formation. various embodiments described pertain to compositions including a curable resin and organophilically modified clay for underground oil well applications and methods utilizing the same. various embodiments provide a method for treating an underground formation including placing it in an underground formation with a curable composition that includes at least one of a curable organic resin and a thermostable polymer. the curable composition also includes an organophilically modified clay.
公开号:BR112017003050B1
申请号:R112017003050-0
申请日:2014-09-25
公开日:2022-01-18
发明作者:Herron J. Kennedy；Paul Joseph Jones；Lucas David Albrighton
申请人:Halliburton Energy Services, Inc；
IPC主号:

专利说明:

FUNDAMENTALS
[001] In the liquid state, the rheological profile of curable resin systems, such as epoxy resin systems, can be described as Newtonian and having little or no yield point. For exploration well cementing applications, it is often desirable to add solids to these systems to control density and effective placement of fluid in the exploration well, casing tube, or annular space. Current approaches to controlling density avoid the use of larger particles of thickening agent because these are more difficult to suspend and instead rely on the addition of thickening agents of micronized particles that are more easily suspended. As a result, options for thickening agents are limited. BRIEF DESCRIPTION OF THE FIGURES
[002] The figures, which are not necessarily drawn to scale in general, illustrate by way of example, but not by way of limitation, the various modalities discussed in this document.
[003] FIG. 1 illustrates a system or equipment for dispensing a composition in an underground formation, in accordance with the various embodiments.
[004] FIG. 2 illustrates a suspension of proppants in a curable composition that includes an organophilically modified clay, in accordance with various embodiments.
[005] FIG. 3 illustrates shear stress versus shear rate for various compositions in accordance with various embodiments.
[006] FIG. 4 illustrates the elastic limit versus percent volume of organically modified clay for various compositions according to various modalities. DETAILED DESCRIPTION OF THE INVENTION
[007] Reference will now be made in detail to certain embodiments of the disclosed subject, with examples which are illustrated in part in the accompanying figures. While the subject matter disclosed will be described in conjunction with the claims enumerated, it will be understood that the subject matter exemplified is not intended to limit the claims to the subject matter disclosed.
[008] Values expressed in a range format should be interpreted flexibly to include not only numerical values explicitly stated as the limits of the range, but also to include all individual numerical values or their sub-variations encompassed within this range, as if each numerical value and its sub-variations have been explicitly stated. For example, a range of "about 0.1% to about 5%" or "about 0.1% to about 5%" should be interpreted as including not just about 0.1% to about 5%, but also the individual values (e.g. 1%, 2%, 3% and 4%) and subranges (e.g. 0.1% to 0.5%, 1.1% to 2.2%, 3, 3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y” unless otherwise noted. Likewise, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z" unless otherwise noted.
[009] In this document, the terms “a” or “a/o” are used to include one or more than one, unless the context clearly indicates otherwise. The term “or” is used to refer to a non-exclusive “or” unless otherwise noted. The phrase "at least one of A and B" has the same meaning as "A, B or A and B". In addition, it should be understood that the phraseology or terminology employed in this document, and not defined otherwise, is for the purpose of description and not limitation. Any use of headings is intended to aid in the reading of the document and should not be construed as limiting; information relevant to a title may occur within or outside that particular section.
[0010] In the manufacturing methods described in this document, the steps can be performed in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly stated. Furthermore, specific actions may be performed simultaneously, unless the explicit language of the claim states that they are to be performed separately. For example, an action claimed to perform X and an action claimed to perform Y can be carried out simultaneously within a single operation and the resulting process will be part of the literal scope of the claimed process.
[0011] Selected substituents within the compounds described in this document are present recursively. In this context, "recursive substituent" means that a substituent may state another example of itself or of another substituent that itself reports the first substituent. Recursive substituents are an intended aspect of the disclosed subject matter. Due to the recursive nature of such substituents, theoretically, there could be a large number in any claim. A single person skilled in the art of organic chemistry understands that the total number of such substituents is reasonably limited by the desired properties of the intended compound. Such properties include, by way of example, but without limitation, physical properties such as molecular weight, solubility, and practical properties such as ease of synthesis. Recursive substituents can claim on themselves any suitable number of times, such as about 1 time, about 2 times, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, 100, 200, 300, 400, 500, 750, 1000, 1500, 2000, 3000, 4000, 5000, 10,000, 15,000, 20,000, 30,000, 50,000, 100,000, 200,000, 500,000, 750,000 or about 1,000,000 times or more.
[0012] The term "about", as used in this document, may allow for a degree of variability in a value or range, for example, within 10%, 5% or 1% of a stated value or an established limit of an interval.
[0013] The term "substantially", as used herein, refers to a majority of or primarily as at least 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.
[0014] The term "organic group" as used herein refers to, but is not limited to, any carbon-containing functional group. For example, an oxygen-containing group, such as an alkoxyl group, aryloxyl group, aralkyloxy group, oxo(carbonyl) group, a carboxyl group, including a carboxylic acid, carboxylate, and a carboxylate ester; a sulfur-containing group, such as an alkyl and aryl sulfide group, and other heteroatom-containing groups. Non-limiting examples of organic groups include OR, OOR, OC(O)N(R)2, CN, CF3, OCF3, R, C(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O) R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, (CH2)0-2N(R)C(O)R, (CH2) 0-2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON( R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2 , C(O)N(OR)R or C(=NOR)R, where R can be hydrogen (in examples that include other carbon atoms) or a carbon-based moiety and where the carbon-based moiety can itself be replaced.
[0015] The term "substituted" as used herein refers to an organic group as defined herein in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. The term "functional group" or "substituent" as used herein refers to a group that can be or is substituted by a molecule or an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, Cl, Br and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides and enamines; and other heteroatoms in various other groups. Non-limiting examples of J substituents that may be attached to a carbon (or other) atom include F, Cl, Br, I, OR, OC(O)N(R)2, CN, NO, NO2, ONO2, azide, CF3, OCF3, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N( R)2, OC(O)N(R)2, C(S)N(R)2, (CH2)0-2N(R)C(O)R, (CH2)0-2N(R)N( R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R) SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O) N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(OR)R, C(=NH)N(R)2, C(O)N(OR )R or C(=NOR)R where R can be a hydrogen or carbon based moiety and where the carbon based moiety can itself also be substituted; for example wherein R may be hydrogen, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl or heteroarylalkyl, wherein any alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl or heteroarylalkyl or R may independently be mono or multi substituted with J; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen atoms may together with the oxygen atoms or atoms form a heterocyclyl which may be independently mono- or multi-substituted with J.
[0016] The term "alkyl" as used herein refers to straight and branched chain alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons, or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl and 2,2-dimethylpropyl groups. As used herein, the term "alkyl" encompasses n-alkyl, isoalkyl, and anteisoalkyl groups, as well as other branched-chain forms of alkyl. Representative substituted alkyl groups may be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy and halogen groups.
[0017] The term "alkenyl", as used herein, refers to cyclic and straight-chain or branched alkyl groups as defined herein, unless there is at least one double bond between two carbon atoms. Thus, alkenyl groups have 2 to 40 carbon atoms or 2 to about 20 carbon atoms, 2 to 12 carbon atoms, or, in some embodiments, 2 to 8 carbon atoms. Examples include, but are not limited to vinyl, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, -C(CH3) =CH(CH3), -C(CH2CH3 )=CH 2 , cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl and hexadienyl among others.
[0018] The term "alkynyl", as used herein, refers to straight and branched chain alkyl groups, unless there is at least one triple bond between two carbon atoms. Thus, alkynyl groups have 2 to 40 carbon atoms, 2 to about 20 carbon atoms, or 2 to 12 carbon atoms, or, in some embodiments, 2 to 8 carbon atoms. Examples include, but are not limited to -C=CH, -C=C(CH3), -C=C(CH2CH3), -CH2C=CH, -CH2C=C(CH3) and -C11.-C CiCII.- CII.) among others.
[0019] The term "acyl" as used herein refers to a group containing a carbonyl moiety, wherein the group is bonded through the carbonyl carbon atom. The carbonyl carbon atom is also bonded to another carbon atom which may be part of an alkyl, aryl, cycloalkyl aralkyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group or the like. In the special case where the carbonyl carbon atom is bonded to a hydrogen, the group is a "formyl" group, an acyl group as the term is defined herein. An acyl group can include from 0 to about 12-20 or 12-40 additional carbon atoms attached to the carbonyl group. An acyl group may include double or triple bonds within the meaning of this document. An acryloyl group is an example of an acyl group. An acyl group may also include heteroatoms within the meaning of this document. A nicotinoyl (pyridyl-3-carbonyl) group is an example of an acyl group within the meaning of this document. Other examples include acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl and acryloyl groups and the like. When the group containing the carbon atom that is bonded to the carbonyl carbon atom contains a halogen, the group is termed a "haloacyl" group. An example is a trifluoroacetyl group.
[0020] The term "cycloalkyl" as used herein refers to cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group may have from 3 to about 8-12 ring members, whereas in other embodiments, the number of ring carbon atoms ranges from 3 to 4, 5, 6, or 7. Additional cycloalkyl groups include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, canphenyl, isocanphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl and the like. Cycloalkyl groups also include rings that are substituted by straight chain or branched alkyl groups, as defined herein. Representative substituted cycloalkyl groups may be monosubstituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4-2,5- or 2,6-disubstituted cyclohexyl groups or mono-, di- or tri-substituted cycloheptyl or norbonyl which may be substituted by, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy and halogen groups. The term "cycloalkenyl", alone or in combination, denotes a cyclic alkenyl group.
[0021] The term "aryl", as used herein, refers to cyclic aromatic hydrocarbons which do not contain heteroatoms in the ring. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysynyl, biphenylenyl, anthracenyl and naphthyl groups. In some embodiments, aryl groups contain about 6 to about 14 carbons in the ring portions of the groups. Aryl groups may be unsubstituted or substituted, as defined herein. Representative substituted aryl groups may be monosubstituted or substituted more than once, such as, but not limited to, substituted 2-, 3-, 4-, 5- or 6-substituted phenyl groups or 2-8 substituted naphthyl groups, which may be substituted by carbon or non-carbon groups as listed herein.
[0022] The term "heterocyclyl" as used herein refers to aromatic and non-aromatic ring compounds containing 3 or more ring members of which one or more is a heteroatom, such as, but not limited to, N, O and S.
[0023] The term "amine" as used herein refers to primary, secondary and tertiary amines, having, for example, the formula N(group)3, in which each independent group may be H or non-H, such as alkyl, aryl and the like. Amines include, but are not limited to, R-NH 2 , for example, alkylamines, arylamines, alkylarylamines; R2NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like; and R3N wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines and the like. The term “amine” also includes ammonium ions, as used in this document.
[0024] The term "amino group", as used herein, refers to a substituent of the form -NH2, -NHR, -NR2, -NR3+, wherein each R is independently selected and the protonated forms of each, except for -NR3+, which cannot be protonated. Therefore, any compound substituted by an amino group can be viewed as an amine. An "amino group" within the meaning of this document can be a primary, secondary, tertiary or quaternary amino group. An "alkylamino" group includes a monoalkylamino, dialkylamino and trialkylamino group.
[0025] The terms "halo", "halogen" or "halide" group, as used herein, alone or as part of another substituent, mean, unless otherwise indicated, a fluorine, chlorine, bromine atom or iodine.
[0026] The term "haloalkyl" group, as used herein, includes monohalo alkyl groups, polyhalo alkyl groups in which all halo atoms may be the same or different, and perhalo alkyl groups in which all hydrogen atoms are replaced by halogen atoms, such as fluorine. Examples of haloalkyl include trifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo, 3,3-difluoropropyl, perfluorobutyl and the like.
[0027] The term "hydrocarbon" as used herein refers to a functional group or molecule that includes carbon and hydrogen atoms. The term can refer to a molecule or functional group that normally includes carbon and hydrogen atoms, but in which all hydrogen atoms are replaced by other functional groups.
[0028] As used herein, the term "hydrocarbyl" refers to a functional group derived from a straight-chain, branched or cyclic hydrocarbon and may be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl or any combination thereof.
[0029] The term "solvent" as used herein refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are silicones, organic compounds, water, alcohols, ionic liquids and supercritical fluids.
[0030] The term "room temperature", as used herein, refers to a temperature of about 15°C to 28°C.
[0031] The term “standard temperature and pressure” as used in this document refers to 20°C and 101 kPa.
[0032] As used herein, the term "polymer" refers to a molecule having at least one repeating unit, and may include copolymers.
[0033] The term "copolymer", as used herein, refers to a polymer that includes at least two different repeating units. A copolymer can include any suitable number of repeating units.
[0034] The term “downhole”, as used in this document, refers to below the earth's surface, as a location within or fluidly connected to an exploration well.
[0035] As used in this document, the term “drilling fluid” refers to fluids, slurries or slurries used in downhole drilling operations, such as during exploration well formation.
[0036] As used in this document, the term “stimulation fluid” refers to fluids or slurries used in the downhole during well stimulation activities that can increase the production of a well, including drilling activities. In some examples, a stimulation fluid may include a fracturing fluid or an acidifying fluid.
[0037] As used in this document, the term “cleaning fluid” refers to fluids or slurries used in the downhole during downhole cleaning activities, such as any treatment to remove material obstructing the flow of desired material from the underground formation. . In one example, a cleaning fluid may be an acidification treatment to remove material formed by one or more perforation treatments. In another example, a cleaning fluid can be used to remove a filter cake.
[0038] As used in this document, the term “fracturing fluid” refers to fluids or slurries used in the downhole during fracturing operations.
[0039] As used in this document, the term “spotting fluid” refers to fluids or slurries used at the downhole during localized injection operations and can be any fluid designed for localized treatment of a downhole region. of well. In one example, a spot injection fluid may include a loss-of-circulation material for treating a specific section of the exploration well, such as to seal fractures in the exploration well and prevent deposition. In another example, a spot injection fluid may include a water control material. In some examples, a spot injection fluid can be designed to release a stuck piece of drilling or extraction equipment, can reduce torque and drag with drilling lubricants, prevent differential sticking, promote well stability, and can help to control the weight of the mud.
[0040] As used herein, the term "completion fluid" refers to fluids or slurries used in the downhole during the completion phase of a well, including cementing compositions.
[0041] As used in this document, the term “remedial treatment fluid” refers to fluids or slurries used downhole for corrective treatment of a well. Corrective treatments may include treatments designed to maintain or increase a well's production rate, such as stimulation or cleaning treatments.
[0042] As used in this document, the term “abandonment fluid” refers to fluids or slurries used in the downhole during or before the abandonment phase of a well.
[0043] As used in this document, the term “acidification fluid” refers to fluids or slurries used in the downhole during acidification treatments. In one example, an acidifying fluid is used in a cleaning operation to remove material that is obstructing the flow of the desired material, such as material formed during a drilling operation. In some instances, an acidifying fluid may be used to remove damage.
[0044] As used in this document, the term “cementing fluid” refers to fluids or slurries used during well cementing operations. For example, a cementing fluid may include an aqueous mixture, including at least one of cement and cement kiln powder. In another example, a cementing fluid may include a curable resin material such as a polymer that is in an at least partially uncured state.
[0045] As used in this document, the term “water control material” refers to a solid or liquid material that interacts with downhole aqueous material so that the hydrophobic material can more easily travel to the surface. and so that the hydrophilic material (including water) can be less easily displaced to the surface. A water control material can be used to treat a well to cause the proportion of produced water to decrease and to cause the proportion of produced hydrocarbons to increase, such as by selectively linking materials between water-producing underground formations and the well. exploration, while still allowing formations producing hydrocarbons to maintain their production.
[0046] As used in this document, the term “plug fluid” refers to fluids or pastes that can be placed in the annular region of a well between the pipeline and the outer casing above a plug. In several examples, the plug fluid can provide hydrostatic pressure to reduce differential pressure across the sealing element, lower differential pressure over the exploration well and casing to prevent collapse, and protect metals and elastomers from corrosion.
[0047] As used herein, the term “fluid” refers to liquids and gels, unless otherwise noted.
[0048] As used in this document, the term "subterranean material" or "underground formation" refers to any material beneath the earth's surface, including under the surface of the ocean floor. For example, an underground formation or material may be from any section of an exploration well and any section of a formation or region of oil production or groundwater in fluid contact with the exploration well. The placement of a material in an underground formation may include contacting the material with any section of an exploration well or with any underground region in fluid contact with it. Underground materials can include any materials placed inside the exploration well, such as cement, drill shafts, liners, tubes, casing tubes or screens. Placing a material in an underground formation may include contact with such underground materials. In some examples, an underground formation or material can be any region below ground that can produce liquid or gaseous materials from petroleum, water, or any section below ground in fluid contact with the ground. For example, an underground formation or material may be at least one area desired to be fractured, a fracture or area around a fracture and a fluid path or an area around a fluid path, where a fracture or a fluid path may optionally be fluidly connected to an underground water or oil producing region, either directly or through one or more fractures or flow paths.
[0049] As used herein, “treatment of an underground formation” may include any activity directed at extracting water or petroleum materials from an underground water or oil producing formation or region, for example, including drilling, stimulation, hydraulic fracturing, cleaning, acidification, completion, cementing, remedial treatment, abandonment and the like.
[0050] As used in this document, a downhole "flow path" may include any appropriate underground flow path through which two underground locations are in fluid connection. The flow path may be sufficient for oil or water to flow from an underground location to the exploration well or vice versa. A flow path may include at least one of a hydraulic fracture and a fluidic connection through a screen, through wire mesh, through proppants, including through resin-bound proppants or proppant deposited in a fracture, and through sand. . The flow path may include a natural underground passage through which fluids can flow. In some embodiments, a flow path may be a source of water and may include water. In some embodiments, a flow path may be a source of oil and may include oil. In some embodiments, a flow path may be sufficient to bypass an exploration well, fracture or flow path connected thereto to at least one of water, downhole fluid or produced hydrocarbon.
[0051] As used herein, a "carrier fluid" refers to any fluid suitable for suspending, dissolving, mixing or emulsifying with one or more materials to form a composition. For example, the carrier fluid can be at least one of crude oil, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethylformamide, diethylene glycol methyl ether, ethylene glycol butyl ether , diethylene glycol butyl ether, butylglycidyl ether, propylene carbonate, D-limonene, a C2C40 C1-C10 alkyl ester fatty acid (e.g. a fatty acid methyl ester), tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxyethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethyl sulfoxide, dimethylformamide, a petroleum fraction distillation product (e.g., diesel, kerosene, naphthas and the like), mineral oil, a hydrocarbon oil, a hydrocarbon, including a carbon-carbon aromatic bond (e.g., benzene, toluene), a hydrocarbon, including an alpha-olefin, xylenes, an ionic liquid, methyl ethyl keton a, an oxalic ester, maleic or succinic acid, methanol, ethanol, propanol (iso- or normal), butyl alcohol (iso-, tert-, or normal), an aliphatic hydrocarbon (e.g. cyclohexanone, hexane), water, saline solution, produced water, backflow water, brackish water and sea water. The fluid can form from about 0.001% by weight to about 99.999% by weight of a composition or mixture containing the same, or about 0.001% by weight or less, from 0.01% by weight, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99 or about 99.999% by weight or more.
[0052] In various embodiments, the present invention provides a method for treating an underground formation. The method includes placing a curable composition in an underground formation. The curable composition includes at least one of a curable organic resin and a thermostable polymer. The curable composition also includes an organophilically modified clay.
[0053] In various embodiments, the present invention provides a method for treating an underground formation. The method includes placing a curable composition in an underground formation that includes a curable epoxy resin and an organophilically modified montmorillonite clay.
[0054] In various embodiments, the present invention provides a system that includes a curable composition. The curable composition includes at least one of a curable organic resin and a thermostable polymer. The curable composition also includes an organophilically modified clay. The system also includes an underground formation that includes the curable composition therein.
[0055] In various embodiments, the present invention provides a curable composition for treating an underground formation. The curable composition includes a curable epoxy resin and an organophilically modified montmorillonite clay.
[0056] In various embodiments, the present invention provides a method of preparing a curable composition for treating an underground formation. The method includes forming a curable composition. The curable composition includes at least one of a curable organic resin and a thermostable polymer. The curable composition also includes an organophilically modified clay.
[0057] Various embodiments of the present invention provide certain advantages over other curable compositions and methods for using the same in underground formations. For example, suspending particles in curable compositions can be difficult due to the lack of a yield point or due to a low yield point. As a result, small particles are generally used, which are easier to suspend than larger particles. In contrast, various embodiments of the present invention feature a curable rheologically modified composition from an organophilically modified clay component that provides a higher yield strength over curable compositions (which generally do not have a yield strength), allowing suspension of larger particles. In various embodiments, the ability of the curable composition to suspend larger particles can provide improved options for the types of materials that can be suspended in curable resin compositions, such as thickening agents, proppants, or other materials.
[0058] In various embodiments, the curable composition can be easily densified by adding additives with minimal risk of sedimentation during or after placement of the curable composition in an underground formation, providing an effective curable composition for well control or providing better displacement of fluid for insulation purposes. In various embodiments, the yield point of the curable composition may allow the curable composition to better maintain the rheological hierarchy during pumping operations, e.g. where the displacement fluid (e.g. the curable composition) maintains a yield point or higher plastic viscosity relative to the fluid being displaced. In various embodiments, the yield point of the curable composition can provide better fluid displacement and can provide superior insulation or chemical or hydraulic sealing at the downhole. In various embodiments, the yield point of the curable composition can assist in eliminating the dynamic or static fluid inversion that occurs due to gravity differences in fluid density within the exploration well. In various embodiments, the yield point of the curable composition can assist in making the curable composition static in the desired location, for example, until specific chemical reactions are completed to achieve a desired result. In various embodiments, the yield point of the curable composition can prevent solids from settling within the curable composition during mixing, pumping, and after placement when the system is in a static condition. Method for treating an underground formation
[0059] In various embodiments, the present invention provides a method for treating an underground formation. The method may include placing a curable composition in an underground formation. Placing the curable composition in the underground formation may include contacting the curable composition and any appropriate part of the underground formation, or contacting the curable composition and an underground material, such as any suitable underground material. The underground formation can be any suitable underground formation. The curable composition can include a curable resin including at least one of a curable organic resin and a thermostable polymer. The curable composition may include some components that are not curable, provided that the curable composition includes at least some components that are curable. The curable composition may also include an organophilically modified clay. The organophilically modified clay and the curable resin can be mixed significantly and uniformly in the curable composition so that the clay is approximately evenly distributed throughout the curable resin. Organophilically modified clay can impart an initial shear stress or yield point (LE) to the curable composition to improve suspension of solids and prevent or decrease sedimentation of solid particles during underground operations such as a well cementing process. exploration, an exploration well repair operation, a consolidation procedure, a corrective treatment procedure, an abandonment procedure, or a fracturing procedure.
[0060] In some examples, placement of the curable composition in the underground formation includes contacting the curable composition with or placing the curable composition in at least one of a fracture, at least a part of an area around a fracture, a path flow, an area around a flow path, and a desired area to fracture. The placement of the curable composition in the underground formation may be any suitable placement and may include any suitable contact between the underground formation and the curable composition. Placing the curable composition in the underground formation may include at least partial deposition of the curable composition in a fracture, flow path or area around it. In some embodiments, the method includes obtaining or providing the curable composition, including the curable resin and the organophilically modified clay. The procurement or delivery of the curable composition may take place at any suitable time and at any suitable location. Obtaining or delivering the curable composition can take place above the surface. Obtaining or supplying the curable composition can take place in the underground formation (eg downhole).
[0061] In various embodiments, the method includes cementing or repairing an exploration well in the underground formation. For example, the curable composition can be placed in an annular space between a casing tube and the exploration well or between two casing tubes, and can then be cured. In some embodiments, the curable composition may include a cement or may be placed adjacent to a cement composition. In some examples, the method may include placing the curable composition in a damaged region of an exploration well and then curing the curable composition. The curable composition can be used for any suitable type of cement, such as primary cement (e.g. initial cement in the well, usually between casing tube and annular space outside the casing) or as a secondary cement (e.g. corrective cementation , such as due to loss of zonal insulation or loss of casing pipe integrity).
[0062] In various embodiments, the method includes using the curable composition to perform a well abandonment procedure. The composition may be used in any suitable form during abandonment. For example, the curable composition can be used to fill or seal the well, such as to fill or seal a casing tube.
[0063] In various embodiments, the method includes consolidation of particles at the bottom of the well. For example, the method may include placing the curable composition in a region of the underground formation that includes fine particles, gravel or other particles, allowing the curable composition to cure such that the particles are significantly fixed in place. In various embodiments, the method may include administering lost circulation, such as by placing the curable composition in an underground region that is experiencing fluid loss, and curing the composition.
[0064] The method may include hydraulic fracturing, such as a hydraulic fracturing method to generate a fracture or flow path. The placement of the curable composition in the underground formation or the contact of the underground formation and hydraulic fracturing can occur at any time with respect to each other; for example, hydraulic fracturing can occur at least before, during and after contact or placement. In some embodiments, contact or placement occurs during hydraulic fracturing, such as during any suitable phase of hydraulic fracturing, e.g. during at least one of a pre-pad step (e.g. during water injection without proppant, and, additionally and optionally with medium to low strength acid), a pad step (e.g. when injecting fluid only without any proppant, with some viscosity, such as when starting to enter an area and starting fracturing to produce sufficient penetration and width to allow entry of later stages loaded with proppants) or a paste step of fracturing (eg viscous fluid with proppant). The method may include performing a stimulation treatment, at least one of before, during and after placing the curable composition in the subsurface formation at the fracture, flow path or area around it. The stimulation treatment can be, for example, at least one of drilling, acidification, injection of cleaning fluids, thruster stimulation and hydraulic fracturing. In some embodiments, the stimulation treatment at least partially generates a fracture or flow path, where the curable composition is placed or contacted or the curable composition is placed or contacted with an area around the fracture or flow path. generated.
[0065] The curable composition may have any suitable yield point. As used herein, yield strength refers to the amount of shear stress required to cause a curable composition to undergo plastic deformation or yield, wherein yielding occurs when the applied shear stress exceeds the yield strength. For example, the curable composition may have a yield point that is from about 1 lbf/100 ft 2 to about 10,000 lbf/100 ft 2 , about 15 lbf/100 ft 2 to about 100 lbf/100 ft 2 , about 1 lbf/100 ft2 or less or about 2 lbf/100 ft2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55 , 60, 65, 70, 75, 80, 85, 90, 95, 100, 150, 200, 250, 500, 750, 1,000, 1,500, 2,000, 2,500, 5,000, 7,500 or about 10,000 lbf/100 ft2 or more .
[0066] The curable composition may have any suitable shear stress at a specific shear rate. For example, at about 10°C to about 40°C and normal pressure, at about 0.5 s -1 to about 50 s -1 , the composition can have a shear stress of about 10 lbf/ 100 ft2 to about 300 lbf/100 ft2, about 40 lbf/100 ft2 to about 220 lbf/100 ft2 or about 10 lbf/100 ft2 or less or about 15 lbf/100 ft2, 20, 25, 30 , 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230 , 240, 250, 260, 270, 280, 290 or about 300 lbf/100 ft2 or more. For example, at about 10°C to about 40°C and standard pressure at about 50 s -1 to about 200 s -1 , the composition can have a shear stress of about 100 lbf/100 ft2 at about 1000 lbf/100 ft2, about 200 lbf/100 ft2 to about 500 lbf/100 ft2 or about 100 lbf/100 ft2 or less or about 110 lbf/100 ft2, 120, 130, 140, 150, 160 , 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 350, 400, 450, 500, 600, 700, 800, 900 or about 1,000 lbf/ 100 ft2 or more. For example, at about 50°C to about 100°C and standard pressure at about 0.5 to about 50 s-1, the curable composition may have a shear stress of about 10 lbf/100 ft2 at about 100 lbf/100 ft2, about 15 lbf/100 ft2 to about 220 lbf/100 ft2, about 10 lbf/100 ft2 or less or about 15 lbf/100 ft2, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or about 100 lbf/100 ft 2 . For example, at about 50°C to about 100°C and standard pressure at about 50 s-1 to about 200 s-1, the curable composition may have a shear stress of about 30 lbf/100 ft2 at about 150 lbf/100 ft2, about 50 lbf/100 ft2 at about 200 lbf/100 ft2, about 30 lbf/100 ft2 or less, or about 35 lbf/100 ft2, 40, 45, 50, 55 , 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145 or about 150 lbf/100 ft 2 . The method may include using any suitable shear rate, such as from about 0 s -1 to about 5000 s -1 or about 10 s -1 to about 1500 s -1 .
[0067] The curable composition may have any suitable density. The curable composition can have a density of about 50 kg/m3 to about 5000 kg/m3 about 200 kg/m3 to about 3000 kg/m3 or about 50 kg/m3 or less or about 100 kg/m3 I , 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3250, 3500 , 3750, 4000, 4250, 4500, 4750 or about 5000 kg/m 3 or more.
[0068] The curable composition or a mixture including the same may include a thickening agent. The thickening agent may be any suitable thickening agent. For example, the thickening agent may be at least one of calcium carbonate, aluminum oxide, awaruite, barium carbonate, barium oxide, baryte sulfate, baryte, calcium carbonate, calcium oxide, cenospheres, chromite, chromium, copper, copper oxide, dolomite, galena, hausmanite, hematite, hollow glass microspheres, ilmenite, iron oxide, siderite, magnetite, magnesium oxide, manganese carbonate, manganese dioxide, manganese(IV) oxide , manganese oxide, manganese tetroxide, manganese(II) oxide, manganese(III) oxide, molybdenum(IV) oxide, molybdenum oxide, molybdenum trioxide, Portland cement, pumice, pyrite, spharelite, siderite , silica, silver, tenorite, titania, titanium (II) oxide, titanium (III) oxide, titanium (IV) dioxide, zirconium oxide, zirconium silicate, zinc oxide, kiln cement powder, non-perlite expanded and expanded, attapulgite, bentonite, zeolite, elastomers, sand, micronized polymers, ce ras, polymer fibers, inorganic fibers and any combination thereof. The thickening agent can have any suitable density, such as about 50 kg/m 3 or less or about 100 kg/m 3 , 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700 I , 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3250, 3500, 3750, 4000, 4250, 4500, 4750 or about 5000 kg/m3 or more. The thickening agent can be any suitable particle size (e.g., the largest particle size), such as about 1 nm to about 10 mm, about 100 nm to about 5 mm, about 300 nm to about 5 mm. 600 nm or about 1 nm or less, about 5 nm, 10, 20, 25, 50, 75, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900 nm, 1 mm , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or about 10 mm or more. The weighting agent can form any suitable proportion of the curable composition or mixture containing the same, such as from about 0.001% by weight to about 80% by weight, from about 0.01% by weight to about 50% by weight. weight, about 1% by weight to about 40% by weight or about 0.001% by weight or less, or about 0.01% by weight, 0.1, 0.5, 1, 1.5, 2 , 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or about 80% by weight or more. curable resin
[0069] The curable composition includes a curable resin. The curable resin may include at least one of a curable organic resin and a thermostable polymer. As used herein, "curing" refers to undergoing a physical or chemical reaction that results in hardening or an increase in viscosity. The curing can be at least one of a polymerization reaction and a crosslinking reaction. The curable composition may be a hydrophobic curable composition. The curable resin or curable composition may include various components, such as curing agent components (eg, amines or anhydrides), polymerizable components (eg, curable organic resins, such as epoxides) or initiator components. The one or more polymerizable components can form any suitable proportion of the curable composition or curable resin, such as about 1% by weight to about 99% by weight, about 5% by weight to about 95% by weight, about 40% by weight to about 90% by weight, about 1% by weight or less or about 2, 3, 4, 5, 6, 8, 10, 12, 14, 15, 20, 25, 30, 35 , 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 92, 94, 96, 97, 98 or about 99% by weight or more. The one or more curing agent or initiator components of the curable composition or curable resin can form any suitable proportion of the curable composition, such as about 1% by weight to about 99% by weight, about 5% by weight to about 95% by weight, about 40% by weight to about 90% by weight, about 1% by weight or less, or about 2, 3, 4, 5, 6, 8, 10, 12, 14 , 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 92, 94, 96, 97, 98 or about 99 wt. most.
[0070] In various embodiments, the method includes curing the curable composition to provide a cured product of the curable composition. Curing of the curable composition can occur at least partially above the surface such that partial curing occurs prior to placing the curable composition in the underground formation. Curing of the curable composition can occur at least partially in the underground formation such that all or part of the curing occurs when the curable composition is at the bottom of the well, such as when the curable composition is in a desired location at the bottom of the well. Curing can take place at any suitable time, at any suitable temperature, and at an appropriate pressure, such as for 10 minutes, 20, 30, 40, 50 minutes, 1 hour, 1.5, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22 hours, 1 day, 1.5, 2, 3, 4, 5, 6 days, 1 week, 1.5, 2, 3 weeks or about a month or more, such as at about 0°C to about 500°C or about 20°C to about 400°C or about 0°C or less, or about 10°C, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 350, 400, 450 or about 500° C or more.
[0071] Any suitable proportion of the curable composition or curable resin may be the curable organic resin, the thermoset polymer or a combination thereof, provided that the curable composition can be cured, such as about 1% by weight to about 99.99 % by weight, about 30% by weight to about 98% by weight, about 50% by weight to about 95% by weight, or about 1% by weight or less, or about 2% by weight, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 76, 78, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9 or about 99.99% by weight or more.
[0072] The curable organic resin or thermoset polymer may include at least one of a shellac, a polyamide, a silyl-modified polyamide, a polyester, a polycarbonate, a polycarbamate, a urethane, a natural resin, a epoxy-based resin (e.g., epoxy-amine or epoxy-anhydride), a furan-based resin, a phenolic-based resin, a urea-aldehyde resin, and a phenol-phenol formaldehyde furfuryl alcohol resin. In some embodiments, the curable organic resin or thermosetting polymer can be at least one of bisphenol A diglycidyl ether resin, butoxymethyl butyl glycidyl ether resin, bisphenol A epichlorohydrin resin, bisphenol F resin, and bisphenol S resin. In some embodiments, the curable organic resin or thermosetting polymer may be at least one of an acrylic acid polymer, an acrylic acid ester polymer, an acrylic acid homopolymer, an acrylic acid ester homopolymer, poly(methyl acrylate), poly(methyl acrylate) butyl), poly(2-ethylhexyl acrylate), an acrylic acid ester copolymer, a methacrylic acid derivative polymer, a methacrylic acid homopolymer, a methacrylic acid ester homopolymer, poly(methyl methacrylate), poly(methacrylate) butyl), poly(2-ethylhexyl methacrylate), an acrylamidomethylpropane sulfonate polymer or copolymer or a derivative thereof, and an acrylic acid/acrylamide sulfonate copolymer methylpropane. In some embodiments, the curable organic resin or thermostable polymer can include at least one of a trimer acid, a fatty acid, a fatty acid derivative, maleic anhydride, acrylic acid, a polyester, a polycarbonate, a polycarbamate, an aldehyde, formaldehyde , a dialdehyde, glutaraldehyde, a hemiacetal, an aldehyde-releasing compound, a diacid halide, a dihalide, a dichloride, a dibromide, a polyacid anhydride, citric acid, an epoxide, furfuraldehyde, an aldehyde condensate, a polyamide modified with silyl and a condensation reaction product of a polyacid and a polyamine.
[0073] In some embodiments, the curable composition, curable organic resin or thermostable polymer may include an amine-containing polymer. In some embodiments, the curable organic resin or thermostable polymer may be hydrophobically modified. In some embodiments, the curable organic resin or thermostable polymer may include at least one of a polyamine (e.g., spermidine and spermine), a polyimine (e.g., poly(ethyleneimine) and poly(propyleneimine)), a polyamide, poly( 2-(N,N-dimethylamino)ethyl methacrylate), poly(2-(N,N-diethylamino)ethyl methacrylate), poly(vinyl imidazole) and a copolymer including monomers of at least one of the above and monomers of at least one a non-amine containing polymer such as at least one of polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyvinylpyridine, polyacrylic acid, polyacrylate and polymethacrylate. The hydrophobic modification can be any suitable hydrophobic modification, such as at least one (C4-C30)hydrocarbyl including at least one of a straight chain, a branched chain, a C-C unsaturated bond, an aryl group and any combination thereof.
[0074] In some embodiments, the curable resin or curable composition may include a curing agent. The curing agent may be any suitable curing agent. For example, the curing agent can include at least one of an amine, an aromatic amine, an aliphatic amine, a cycloaliphatic amine, polyamines, an anhydride, amides, polyamides, a polyethyleneimine, piperidine, triethylamine, benzyldimethylamine, N, N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, piperazine, piperazine derivatives (e.g. aminoethylpiperazine), pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine , quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, carbazole, carbazole, phenanthridine, acridine, phenatroline, phenazine, imidazolidine, phenoxazine, cinnoline, pyrrolidine, pyrroline, imidazoline, piperidine, indoline, isoindoline, quinuclindin and, morpholine, azocine, azepine, 1,3,5-triazine, thiazole, pteridine, dihydroquinoline, hexamethyleneimine, indazole, 2-ethyl-4-methyl imidazole, 1,1,3-trichlorotrifluoroacetone and combinations thereof. The curing agent can form any suitable weight % of the curable organic resin, thermosetting polymer or curable composition, such as about 0.001 weight % to about 50 weight %, about 0.01 weight % to about 20 % by weight or about 0.001% by weight or less or about 0.01% by weight, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45 or about 50% by weight or more.
[0075] In various embodiments, the curable organic resin includes at least one of an epoxy-amine resin (e.g., having an epoxy component and an amine component, such as an amine curing agent component) and a resin epoxy-anhydride (e.g., having an epoxy component and an anhydride component, such as an anhydride curing agent component). For example, the curable organic resin may include at least one epoxide component which is a polyepoxide substituted mono- or poly(C5-C20)aryl compound, wherein the (C5-C20) is substituted or unsubstituted aryl, wherein the polyepoxide substituted mono- or poly(C5-C20)aryl compound is any suitable proportion of the curable resin, such as about 10% by weight to about 95% by weight, about 60% by weight to about 90% by weight, about 10% by weight or less, or about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or about 95 % by weight or more. Here, an epoxide-substituted or amine-substituted organic group wherein the organic group is substituted or unsubstituted may have an epoxide or amine substituted on either of the substituents of the organic group or substituted directly on the organic group itself. The epoxide component may be a diepoxide-substituted phenyl(C1-C10)hydrocarbylphenyl, wherein the phenyl and (C1-C10)hydrocarbyl are each independently substituted or unsubstituted. The epoxide component may be a diglycidyl ether of bisphenol A (2-[[4-[2-[4-(oxirano-2-ylmethoxy)-phenyl]-propan-2-yl]phenoxy]methyl]oxirane).
[0076] The curable organic resin may include at least one component which is an epoxide-substituted (C1-C10)hydrocarbyl compound, wherein the (C1-C10)hydrocarbyl may be independently substituted or unsubstituted, wherein the (C1-C10)hydrocarbyl compound may be independently substituted or unsubstituted. -C 10 )hydrocarbyl substituted by epoxide is any suitable proportion of the curable resin, such as about 5% by weight to about 60% by weight, 10% by weight to about 30% by weight, or about 5% by weight, or less, or about 10% by weight, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60% by weight or more. In some embodiments, the epoxide component can be a (C1-C10)hydrocarbylglycidyl ether, such as butylglycidyl ether.
[0077] The curable organic resin may include at least one epoxide component which is a polyepoxide-substituted (C5-C20)cycloalkyl compound, wherein the (C5-C20)cycloalkyl is substituted or unsubstituted, wherein the (C5-C20)cycloalkyl compound is -C20) cycloalkyl substituted by polyepoxide is any suitable proportion of the curable resin, such as about 5% by weight to about 60% by weight, about 10% by weight to about 30% by weight, or about 5% by weight. weight or less or about 10% by weight, 15, 20, 25, 30, 35, 40, 45, 50, 55 or about 60% by weight or more. The epoxide component may be hexanedimethanol diglycidyl ether. In various embodiments, the resin includes a combination of a polyepoxide-substituted (C5-C20) and a polyepoxide-substituted mono- or poly(C5-C20) compound, such as a combination of cyclohexanedimethanol diglycidyl ether and bisphenol diglycidyl ether. A. In some embodiments, the resin includes a combination of a polyepoxide-substituted (C5-C20)cycloalkyl compound, a polyepoxide-substituted mono- or poly(C5-C20)aryl group, and a epoxide-substituted (C1-C10) compound. , such as a combination of cyclohexanedimethanol diglycidyl ether, bisphenol A diglycidyl ether and butyl glycidyl ether.
[0078] The curable organic resin or curable composition may include at least one amine component which is a polyamine-substituted (C1-C30)hydrocarbyl, wherein the (C1-C30)hydrocarbyl and each amine are independently substituted or unsubstituted. substituted, in any suitable proportion of the curable composition, such as about 5% by weight to about 50% by weight, about 10% by weight to about 30% by weight, about 5% by weight or less, or about of 10% by weight, 15, 20, 25, 30, 35, 40, 45 or about 50% by weight or more. The amine component may be a bis(amino(C0-C5)hydrocarbyl)(C6-C20)aryl compound, wherein the (C6-C20)aryl, (C0-C5)hydrocarbyl and each amine are each substituted or unsubstituted. independently. The amine component may be diethyltoluenediamine. The curable organic resin or curable composition may include at least one amine component which is a polyamine substituted poly((C2-C5)hydrocarbyloxy), wherein each (C2-C5)hydroxycarbyloxy and each amine are substituted or unsubstituted. independent. The amine component may be polyoxypropylene diamine. The curable organic resin or curable composition may include an amine component which is a mono- or polyamino(C0-C10)hydrocarbyl(C6-C20)aryl, wherein the (C0-C10)hydrocarbyl, (C6-C20)aryl and each amine are each independently substituted or unsubstituted. The amine component may be a tris(amino(C1-C3)hydrocarbyl)benzene, wherein the (C1-C3)hydrocarbyl, the benzene and each amine are independently substituted or unsubstituted. The amine component may be 2,4,6-tris(dimethylaminomethyl)phenol.
[0079] The curable resin or curable composition may include an anhydride component, such as an anhydride curing agent. The anhydride can be any suitable compound which includes an anhydride moiety and which can function as a curing agent with a curable organic resin in the curable composition. The anhydride component may be a maleic anhydride or a succinic anhydride which is fused to a substituted or unsubstituted (C5-C20)hydrocarbon ring or a plurality of said fused maleic or succinic anhydrides linked together via a (C0-C30) substituted or unsubstituted hydrocarbyl interrupted by 0, 1, 2 or 3 oxygen atoms. For example, the anhydride may be an aromatic anhydride, such as a 3,3',4,4'-phenyltetracarboxylic anhydride or several such molecules linked together at any suitable position via a substituted or unsubstituted C0 hydrocarbyl linker. -C30 optionally interrupted by 0-3 oxygen atoms, such as bisphenol A dianhydride (BPADA, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride), biphenyl dianhydride (BPDA dianhydride, 3.3 ',4,4'-biphenyltetracarboxylic acid) or benzophenone-3,3',4,4'-tetracarboxylic dianhydride. For example, the anhydride may be a five-membered cyclic anhydride fused to another ring (e.g., a maleic or succinic anhydride fused to a substituted or unsubstituted aliphatic or aromatic C5-C10 ring), such as methyl-5 -norbornene-2,3-dicarboxylic, methyltetrahydrophthalic anhydride or methylhexahydrophthalic anhydride. The anhydride component can form any suitable weight % of the curable resin or curable composition, such as about 0.001 weight % to about 50 weight %, about 0.01 weight % to about 20 weight %, or about of 0.001% by weight or less or about 0.01% by weight, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45 or about 50% by weight or most. Organophilically modified clay.
[0080] The curable composition may also include an organophilically modified clay. The organophilically modified clay can be any clay that has a hydrophilic character (for example, at least a partially hydrophilic clay or a hydrophilic clay). In some embodiments, the method further includes organophilically modifying a clay to provide the organophilically modified clay, while in other embodiments the clay is modified prior to performing the method. Organophilic modification can occur at least partially above the surface and can occur at least partially in the underground formation.
[0081] The organophilically modified clay may be present in the curable composition at a concentration such that the curable composition has a higher yield strength than a corresponding curable composition having substantially none of the organophilically modified clays in it. Any suitable proportion of the curable composition may include the organophilically modified clay, such as about 0.01% by weight to about 50% by weight of the curable composition, about 1% by weight to about 20% by weight, or about 0.01% by weight or less or about 0.01, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 25, 30, 35 , 40, 45 or about 50% by weight or more.
[0082] The organophilically modified clay may include any one or more suitable clays. For example, the organophilically modified clay may include at least one of a kaolinite (e.g. kaolinite, nacrite, diquite and halloysite), montmorillonite (e.g. montmorillonite, montmorillonite-smectite, bentonite, saponite, nontronite, hectorite or sauconite) , an illite (e.g. illite, hydrobiotite, glauconite, bramallite) and chlorite (e.g. chlorite or chamosite). Organophilically modified clay may include vermiculite, attapulgite or sepiolite. Other mineral components may still be associated with the clay. In some embodiments, the organophilically modified clay will include montmorillonite.
[0083] The organophilic modification of the clay can be any acceptable organophilic modification which provides the clay more hydrophilic than the corresponding clay which lacks the organophilic modification or which has less organophilic modification. The organophilic modification can be a surface modification or a modification that also occurs in non-surface regions. Organophilic modification can be an ion exchange with cationic surfactants that have hydrophobic or organophilic groups. The organophilic modification may be an electrostatic bonding of the surfactant. The organophilic modification can be at least one of cationic substitution, physisorption (eg, substantially no change in bonds) and chemisorption (eg, change in bonds). A cation can replace other cations in the clay to form the organophilic modification. An anion can coordinate one or more cations in the clay to form the organophilic modification.
[0084] The organophilically modified clay may include at least one organophilic modification compound or an ion thereof (e.g., the organophilic modified compound is a salt or a pair of ions that form the neutrally charged compound and the clay includes at least minus one salt ion). At least one organophilically modified compound or ion thereof can be any suitable proportion of the organophilically modified clay, such as about 0.01% by weight to about 80% by weight of the organophilically modified clay or about 10% by weight to about 50% by weight, or about 0.01% by weight or less, or about 0.1% by weight, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16 , 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or about 80% by weight or more.
[0085] In various embodiments, the organophilic-modifying compound is at least one of a substituted or unsubstituted (C10-C50) fatty acid or salt thereof, a tri- or tetra-(C1-C50)hydrocarbylammonium salt, and a tri- or tetra-(C1-C50)hydrocarbylphosphonium salt, wherein each (C1-C50)hydrocarbyl is independently selected, substituted or unsubstituted, and interrupted by 0, 1, 2 or 3 atoms chosen from -O-, - S-, and substituted or unsubstituted -NH-.
[0086] The organophilic modification compound may include a fatty acid salt (C10-C50), such as magnesium stearate. The organophilic-modifying compound may include at least one of a (C1-C50)hydrocarbylammonium salt and a tri- or tetra-(C1-C50)alkyl- or alkenylphosphonium salt, wherein each (C1-C50)hydrocarbyl is independently selected. The organophilic modifying compound can include at least one of a stearyl trimethyl ammonium salt, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide and tetraphenylphosphonium bromide.
[0087] Organophilically modified clay can have any suitable density. The organophilically modified clay may have a density from about 50 kg/m3 to about 5000 kg/m3 about 200 kg/m3 to about 500 kg/m3 or about 50 kg/m3 or less or about 100 kg/m3 m3, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1,100, 1150, 1200, 1250, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, 2000, 2100, 2200, 2300, 2400, 2500, 2,600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3,800, 3900, 4000, 4,250, 4500, 4750 or about 5000 kg/m3 or more.
[0088] The organophilically modified clay can have any suitable particle size (e.g., the largest particle size), such as about 1 nm to about 10 mm, about 100 nm to about 5 mm, about 300 nm to about 600 nm or about 1 nm or less, about 5 nm, 10, 20, 25, 50, 75, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900 nm, 1 mm, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or about 10 mm or more.
[0089] For salts described herein, a positively charged counterion (e.g. in a fatty acid salt) can be any positively charged counterion, such as ammonium(NH4+), or an alkali metal, such as sodium (Na+ ), potassium (K + ) or lithium (Li+ ). In some embodiments, the counterion may have a positive charge greater than +1, which may, in some embodiments, complex various ionized groups, such as Zn2+, Al3+ or alkaline earth metals such as Ca2+ or Mg2+.
[0090] In various embodiments, a negatively charged counter ion (e.g. in an ammonium salt with a hydrophobic ammonium ion) can be any suitable negatively charged counter ion, such as a halide (e.g. fluoride, chloride , iodide or bromide), nitrate, hydrogen sulfate, dihydrogen phosphate, bicarbonate, nitrate, perchlorate, iodate, chlorate, bromate, chlorite, hypochlorite, hypobromite, cyanide, amide, cyanate, hydroxide, permanganate, a conjugate base of any carboxylic acid (eg acetate or formate). In some embodiments, a counter ion may have a negative charge greater than -1, which may in some embodiments complex with various ionized groups, such as oxide, sulfide, nitride, arsenate, phosphate, arsenite, hydrogen phosphate, sulfate, thiosulfate, sulfite, carbonate, chromate, dichromate, peroxide or oxalate. Other Components
[0091] The curable composition including the curable resin and the organophilically modified clay or a mixture including the curable composition may include any suitable additional component in any suitable proportion, such that the curable composition or mixture including the same may be used as described herein .
[0092] In some embodiments, the curable composition includes one or more viscosifiers. The viscosifier can be any suitable viscosifier. The viscosifier can affect the viscosity of the curable composition or a solvent that comes into contact with the curable composition at any suitable time and place. In some embodiments, the viscosifier provides a viscosity increase of at least one from before injection into the underground formation, at the time of injection into the underground formation, during passage through a tubular disposed in a borehole, as the curable composition reaches a specific underground location or some period of time after the curable composition reaches a specific underground location. In some embodiments, the viscosifier can be from about 0,000.1% by weight to about 10% by weight of the curable composition or the mixture containing the same, from about 0.004% by weight to about 0.01% by weight. or about 0.000.1% by weight or less, 0.000.5% by weight, of 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or about 10% by weight or more of the curable composition or a mixture including the same.
[0093] The viscosifier may include at least one of a substituted or unsubstituted polysaccharide and a substituted or unsubstituted polyalkene (e.g. a polyethylene, in which the ethylene moiety is substituted or unsubstituted, derived from the corresponding substituted or unsubstituted ethylene substituted), wherein the polysaccharide or polyalkene is crosslinked or uncrosslinked. The secondary viscosifier may include a polymer that includes at least one repeating unit derived from a monomer selected from the group consisting of ethylene glycol, acrylamide, vinyl acetate, 2-acrylamidomethylpropane sulfonic acid or its salts, trimethylammonium methyl acrylate halide and trimethylammonium methyl methacrylate halide. The viscosifier may include a crosslinkable gel or a crosslinkable gel. The viscosifier may include at least one of a straight polysaccharide and a poly((C2-C10)alkene), wherein the (C2-C10)alkene is substituted or unsubstituted. The dary viscosifier may include at least one of poly(acrylic acid) or (C1-C5)alkyl esters thereof, poly(methacrylic acid) or (C1-C5)alkyl esters thereof, poly(vinyl acetate), poly(vinyl alcohol), poly(ethylene glycol), poly(vinyl pyrrolidone), polyacrylamide, poly(hydroxyethyl methacrylate), alginate, chitosan, curdlan, dextran, emulsan, a galactoglycopolysaccharide, gellan, glucuronan, N-acetyl- glucosamine, N-acetyl heparosan, hyaluronic acid, kefiran, lentinan, levan, maurane, pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan, xanthan, diuthane, welan, derivatized starch, tamarind, gum tragacanth, guar gum, derivatized guar (e.g. hydroxypropyl guar, carboxymethyl guar or hydroxypropyl carboxymethyl guar), gum ghatti, gum arabic, locust bean gum and derivatized cellulose (e.g. carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose se or hydroxyl methyl ethyl cellulose).
[0094] In some embodiments, the viscosifier may include at least one of poly(vinyl alcohol) homopolymer, poly(vinyl alcohol) copolymer, a crosslinked poly(vinyl alcohol) homopolymer, and a crosslinked poly(vinyl alcohol) copolymer. ). The secondary viscosifier may include a poly(vinyl alcohol) copolymer or a cross-linked poly(vinyl alcohol) copolymer including at least one linear, branched, block and random graft vinyl alcohol copolymer and at least one of (C2- substituted or unsubstituted C50)hydrocarbyl having at least one unsaturated aliphatic CC bond therein and one substituted or unsubstituted (C2-C50)alkene. The secondary viscosifier may include a polyvinyl alcohol copolymer or a crosslinked poly(vinyl alcohol) copolymer including at least one linear, branched, block and random graft vinyl alcohol copolymer and at least one of vinyl phosphonic acid, acid Diphosphonic vinylidene, substituted or unsubstituted 2-acrylamido-2-methylpropanesulfonic acid, a substituted or unsubstituted (C1-C20) alkenoic acid, propenoic acid, butenoic acid, pentenoic acid, hexenoic acid, octenoic acid, nonenoic acid, decenoic acid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid, acrylamide, fumaric acid, methacrylic acid, vinyl phosphonic acid, vinylidene diphosphonic acid, itaconic acid, crotonic acid, mesoconic acid, citraconic acid, styrene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid , vinyl sulfonic acid and a substituted or unsubstituted (C1-C20) alkyl ester thereof. The viscosifier may include a crosslinked poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymer including at least one of a linear, branched, random block grafted vinyl alcohol copolymer and at least one of vinyl acetate, a substituted or unsubstituted (C1-C20)alkanoic anhydride, a substituted or unsubstituted (C1-C20)alkenoic anhydride, and a substituted or unsubstituted (C1-C20)alkenoic anhydride, propenoic acid anhydride, butenoic acid anhydride, acid anhydride of pentenoic acid, hexenoic acid anhydride, octenoic acid anhydride, nonenoic acid anhydride, decenoic acid anhydride, acrylic acid anhydride, fumaric acid anhydride, methacrylic acid anhydride, d and hydroxypropyl acrylic acid, vinyl phosphonic acid anhydride, vinyl diphosphonic acid anhydride, itaconic acid anhydride, crotonic acid anhydride, mesoconic acid anhydride, citraconic acid anhydride, styrene sulfonic acid anhydride, allyl sulfonic acid anhydride , methallyl sulfonic acid anhydride, vinyl sulfonic acid anhydride and an N-(C1-C10) alkenyl nitrogen containing (C1-C10) substituted or unsubstituted heterocycle. The viscosifier may include a polyvinyl alcohol copolymer or a poly crosslinked (vinyl alcohol) copolymer including at least one of a linear, branched, block graft, and random copolymer that includes a poly(vinyl alcohol/acrylamide) copolymer, a poly(vinyl alcohol/2-acrylamido-2-methylpropanesulfonic acid), poly(acrylamide/2-acrylamido-2-methylpropanesulfonic acid) copolymer or a poly(vinyl alcohol/N-vinylpyrrolidone) copolymer. The viscosifier may include a crosslinked poly(vinyl alcohol) homopolymer or copolymer including a crosslinking agent including at least one of chromium, aluminum, antimony, zirconium, titanium, calcium, boron, iron, silicon, copper, zinc, magnesium and an ion of the same. The viscosifier may include a crosslinked polyvinyl alcohol homopolymer or copolymer including at least one of aldehyde, aldehyde forming compounds, carboxylic acid or an ester thereof, sulfonic acid or an ester thereof, phosphonic acid or an ester thereof. , an acid anhydride and an epihalohydrin.
[0095] In various embodiments, the curable composition may include one or more cross-linking agents. The cross-linking agent can be any suitable cross-linking agent. In some examples, the cross-linking agent may be incorporated into a cross-linked viscosifier, and in other examples, the cross-linking agent may cross-link a cross-linkable material (e.g., downhole). The crosslinking agent may include at least one of chromium, aluminum, antimony, zirconium, titanium, calcium, boron, iron, silicon, copper, zinc, magnesium and an ion thereof. The crosslinking agent may include at least one of boric acid, borax, a borate, a hydrocarbylboronic acid (C1-C30), a hydrocarbyl ester of a hydrocarbylboronic acid (C1-C30), a hydrocarbylboronic acid-modified polycrylamide (C1-C30). ), a (C1-C30), ferric chloride, disodium octaborate tetrahydrate, sodium metaborate, sodium diborate, sodium tetraborate, disodium tetraborate, pentaborate, ulexite, colemanite, magnesium oxide, zirconium lactate, zirconium triethanol amine , zirconium lactate triethanolamine, zirconium carbonate, zirconium acetylacetonate, zirconium malate, zirconium citrate, zirconium diisopropylamine lactate, zirconium glycolate, zirconium triethanol amine glycolate, zirconium lactate glycolate, titanium lactate, titanium malate, titanium citrate titanium, titanium ammonium lactate, titanium triethanolamine, titanium acetylacetonate, aluminum lactate and aluminum citrate. In some embodiments, the crosslinking agent can be a (C1-C20)alkylenebisacrylamide (e.g., methylenebisacrylamide), a mono- or poly(C1-C20)alkyl ether substituted poly((C1-C20)alkenyl) (e.g. for example, allyl pentaerythritol ether), and a poly(C2-C20)alkenyl (for example, divinylbenzene). In some embodiments, the crosslinking agent can be at least one of alkyl diacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, ethoxylated polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, bisphenol A dimethacrylate ethoxylated, ethoxylated trimethylol propane triacrylate, ethoxylated trimethylol propane trimethacrylate ethoxylated, ethoxylated glyceryl triacrylate, ethoxylated glyceryl trimethacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexacrylate, polyglyceryl polyacrylate monoethylene oxide, polyglyceryl polyethylene glycol polyacrylate, polyglyceryl polyethylene glycol hexacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol, neopentyl glycol diacrylate, pentaerythritol triacrylate dimethacrylate, pentaerythritol trimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, tricyclodecane dimethanol diacrylate, t ricyclodecane dimethanol, 1,6-hexanediol diacrylate dimethacrylate, and 1,6-hexanediol dimethacrylate. The crosslinking agent can be from about 0.000.01% by weight to about 5% by weight of the curable composition, or the mixture containing the same, from about 0.001% by weight to about 0.01% by weight, or about of 0.000.01% by weight or less, or about 0.000.05% by weight, 0.000.1, 0.000.5, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, or about of 5% by weight or more.
[0096] In some embodiments, the curable composition may include one or more disintegrants. The disintegrant can be any suitable disintegrant, so the surrounding fluid (e.g., a fracturing fluid) can be at least partially broken down for fuller and more efficient recovery of the same, such as upon completion of hydraulic fracturing treatment. In some embodiments, the disintegrant may be encapsulated or formulated to provide a delayed release or release time of the disintegrant so that the surrounding liquid can remain viscous for a suitable period of time before breaking down. The disintegrant may be any suitable disintegrant; for example, the disintegrant may be a compound that includes a Na+, K+, Li+, Zn+, NH4+, Fe2+, Fe3+, Cu1+, Cu2+, Ca2+, Mg2+, Zn2+, and an Al3+ a salt of chloride, fluoride, bromide, phosphate or a sulfate ion. In some examples, the disintegrant may be an oxidative disintegrant or an enzymatic disintegrant. An oxidative disintegrant can be at least one of Na+, K+, Li+, Zn+, NH4+, Fe2+, Fe3+, Cu1+, Cu2+, Ca2+, Mg2+, Zn2+ and an Al3+ persulfate salt, percarbonate, perborate, peroxide, perphosphosphate, permanganate, chlorite or hypochlorite ion. An enzyme disintegrant can be at least one of alpha or beta amylase, amyloglucosidase, oligoglucosidase, invertase, maltase, cellulase, hemi-cellulase and mannanohydrolase. The disintegrant can be from about 0.001% by weight to about 30% by weight of the curable composition or the mixture containing the same or about 0.01% by weight to about 5% by weight, or about 0.001% by weight or less or about 0.005% by weight, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or about 30% by weight or more.
[0097] The curable composition or a mixture including the curable composition may include any suitable fluid. For example, the fluid may be at least one of petroleum, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl formamide, diethylene glycol methyl ether, diethylene glycol butyl ether butyl ether, butylglycidyl ether, propylene carbonate, D-limonene, a C2-C40 fatty acid C1-C10 alkyl ester (e.g. a fatty acid methyl ester), tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxyethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethyl sulfoxide, dimethyl formamide, a petroleum fraction distillation product (e.g. diesel, kerosene, naphthas and the like) mineral oil, a hydrocarbon oil, a hydrocarbon, including an aromatic carbon-carbon bond (e.g. benzene, toluene), a hydrocarbon, including an alpha-olefin, xylenes, an ionic liquid, methyl ethyl ketone, an oxale ester lic, maleic or succinic acid, methanol, ethanol, propanol (iso- or normal), butyl alcohol (iso-, tert- or normal), an aliphatic hydrocarbon (e.g. cyclohexanone, hexane), water, saline, produced water, backflow water, brackish water and sea water. The fluid can form from about 0.001% by weight to about 99.999% by weight of the curable composition or a mixture containing the same or about 0.001% by weight or less than 0.01% by weight, 0.1, 1, 2 , 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97 , 98, 99, 99.9, 99.99, or about 99.999% by weight or greater.
[0098] The curable composition including the curable resin and the organophilically modified clay or a mixture including the same may include any suitable downhole liquid. The curable composition including the curable resin and the organophilically modified clay may be combined with any suitable downhole fluid before, during or after placing the curable composition in the subsurface formation or contacting the curable composition and subsurface material. In some examples, the curable composition including the curable resin and the organophilically modified clay is combined with a downhole fluid above the surface, and then the combined composition is placed in an underground formation or in contact with a material. underground. In another example, the curable composition including the curable resin and the organophilically modified clay is injected into the underground formation to combine with a downhole fluid and the combined composition is contacted with an underground material or is considered to be placed in the formation. underground. Placing the curable composition in the underground formation may include bringing the underground material and the mixture into contact. Any suitable weight percent of the curable composition or mixture including the same that is placed in the underground formation or contacted with underground material may be the downhole fluid, such as about 0.001% by weight to 99.999% by weight. weight, about 0.01% by weight to about 99.99% by weight, about 0.1% by weight to about 99.9% by weight, about 20% by weight to about 90% by weight weight or about 0.001% by weight or less, or about 0.01% by weight, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70 , 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99% by weight or about 99.999% by weight or more of the curable mixture or composition including the same.
[0099] In some embodiments, the curable composition, or a mixture including the same, may include any appropriate amount of any suitable material used in a downhole fluid. For example, the curable composition or a mixture including the same may include water, saline, an aqueous base, acid, oil, organic solvent, the synthetic fluid oil phase, aqueous solution, alcohol or polyol, cellulose, starch, alkalinity control, o acidity control agents, density control agents, density modifier, emulsifiers, dispersants, polymeric stabilizers, crosslinking agents, polyacrylamide, a polymer or combination of polymers, antioxidants, heat stabilizers, control agents foam, solvents, thinners, plasticizer, filler or inorganic particle, pigment, colorant, precipitating agent, rheology modifier, petroleum wetting agents, setting retarding additives, surfactants, gases, weight reduction additives , heavy weight additives, circulation loss materials, filtration control additives, salts (e.g. any suitable salt such as salts of potassium such as potassium chloride, potassium bromide, potassium formate, calcium salts such as calcium chloride, calcium bromide, calcium formate, cesium salts such as cesium chloride, cesium bromide, cesium formate or a combination thereof), fibers, thixotropic additives, disintegrants, crosslinking agents, rheology modifying agents, curing accelerators, curing retarders, pH modifiers, chelating agents, scale inhibitors, enzymes, resins, water, oxidants, markers, Portland cement, pozzolan cement, gypsum cement, high alumina cement cement, slag cement, silica cement, ash, metakaolin, shale, zeolite, a compound of crystalline silica, amorphous silica, clays moisturizers, microspheres, limestone or a combination thereof. In various embodiments, the curable composition or a mixture including the same may include one or more additive components, such as: COLDTROL®, ATC®, OMC 2™, and OMC 42™ finer additives; RHEMOD™ viscosifier and suspending agent; Temperus™ and VIS-PLUS® additives to provide temporary viscosity increase; TAU-MOD ™ viscosifying/suspending agent; Adapta®, DURATONE® HT, THERMO TONE™, BDF™-366 and BDF™-454 filtration control agents; LIQUITONE™ viscosifying and polymeric filtering agents; FACTANT™ emulsion stabilizer; LE SUPERMUL™, EZ MUL® NT and FORTI-MUL® emulsifiers; wetting agent for heavy fluids DRIL TREAT®; BARACAB® drilling fluid; BAROID® weighting agent; BAROLIFT® hole scanning agent; SWEEP-WATE® sweep weighting agent; BDF-508 rheology modifier; and organophilic clay GELTONE® II. In various embodiments, the curable composition or a mixture including the same may include one or more additive components, such as: X-TEND® II, PACTM-R, PACTM-L, LIQUI-VIS® EP, BRINEDRIL-VISTM, BARAZAN® , N-VIS®, and AQUAGEL® viscosifiers; THERMA-CHEK®, N-DRILTM, N-DRILTM HT PLUS, IMPERMEX®, FILTERCHEKTM, DEXTRID®, CARBONOX®, and BARANEX® filtration control agents; PERFORMATROL®, GEMTM, EZ-MUD®, CLAY GRABBER®, CLAYSEAL®, CRYSTAL-DRIL®, and CLAY SYNCTM II shale stabilizers; NXS-LUBETM, EP MUDLUBE®, and DRIL-N-SLIDETM lubricants; QUIK-THIN®, IRON-THINTM, and ENVIRO-THINTM diluents; SOURSCAVTM remover; BARACOR® corrosion inhibitor; and WALL-NUT®, SWEEP-WATE®, STOPPITTM, PLUG-GIT®, BARACARB®, DUO-Squeeze®, BAROFIBRE™, STEELSEAL® and HYDRO-PLUG® circulation loss management materials. Any suitable proportion of the curable composition or mixture including the curable composition can include any optional component listed in this paragraph, such as about 0.001% by weight to about 99.999% by weight, about 0.01% by weight to about 99.99 % by weight, about 0.1% by weight to about 99.9% by weight or about 20% by weight to about 90% by weight or about 0.001% by weight or less or about 0.01 % by weight, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 by weight or about 99.999% by weight or more of the composition or mixture.
[00100] A pill is a relatively small amount (e.g. less than about 500 bbl or less than about 200 bbl) of drilling fluid used to perform a specific task that regular drilling fluid is not able to perform. For example, a pill could be a high viscosity pill to, for example, help lift debris out of a vertical exploration pit. In another example, a pill can be a fresh water pill to, for example, dissolve a salt formation. Another example is a pipe release pill to, for example, destroy filter residue and alleviate differential adhesion forces. In another example, a pill is a pill of leakage material to, for example, plug a porous formation zone. A pill can include any component described herein as a component of a drilling fluid.
[00101] A cement fluid may include an aqueous mixture of at least one of cement and cement kiln powder. The curable composition including the curable resin and the organophilically modified clay can form a useful combination with cement or cement kiln powder. The cement kiln powder may be any suitable cement kiln powder. Cement kiln dust can be formed during the manufacture of cement and can be partially calcined kiln material that is removed from the gas stream and collected in a dust collector during a manufacturing process. Cement kiln powder can be used advantageously in a cost efficient manner as kiln powder is often considered a low value waste product of the cement industry. Some embodiments of cement fluid may include cement kiln powders but not cement, cement kiln powder and cement, or cement but not cement kiln powder. The cement may be any suitable cement. The cement can be a hydraulic cement. A variety of cements can be used in accordance with embodiments of the present invention; for example, including calcium, aluminum, silicon, oxygen, iron or sulfur, which can set and harden by reaction with water. Suitable cements may include Portland cements, pozzolan cements, gypsum cements, high alumina cements, slag cements, silica cements and combinations thereof. In some embodiments, Portland cements that are suitable for use in embodiments of the present invention are classified as Class A, C, H, and G cements, according to the American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Edition, Jul. 1, 1990. A cement can generally be included in the cementing fluid in an amount sufficient to provide the desired compressive strength, density, or cost. In some embodiments, the hydraulic cement may be present in the cementing fluid in an amount ranging from 0% by weight to about 100% by weight, about 0% by weight to about 95% by weight, about 20 % by weight to about 95% by weight or about 50% by weight to about 90% by weight. A cement kiln powder may be present in an amount of at least 0.01% by weight or about 5% by weight to about 80% by weight or about 10% by weight to about 50% by weight.
[00102] Optionally, other additives may be added to a cement-containing or kiln-powder composition of embodiments of the present invention as deemed appropriate by a person skilled in the art for the benefit of this disclosure. Any optional ingredient listed in this paragraph may or may not be present in the curable composition. For example, the composition may include fly ash, metakaolinite, shale, zeolite, set-retarding additive, surfactant, a gas, accelerators, weight-reducing additives, heavy-weight additives, lost circulation materials, filtration control additives, dispersants and combinations thereof. In some examples, the additives may include crystalline silica compounds, amorphous silica, salts, fibers, hydratable clays, microspheres, pozzolan lime, thixotropic additives, combinations thereof, and the like.
[00103] In various embodiments, the curable composition or mixture may include a proppant, a resin-coated proppant, an encapsulated resin, or a combination thereof. A proppant is a material that maintains hydraulically induced fracturing at least partially open during or after fracturing treatment. Propants can be transported into the underground formation (eg from the wellbore) upon fracturing using fluid such as fracturing fluid or other fluid. A high-viscosity fluid transports proppants more effectively to a desired location in a fracture, especially larger proppants, keeping the proppants in a suspended state in the fluid more effectively. Examples of proppants may include sand, gravel, glass granules, polymer granules, crushed shell and seed products such as walnut husk, and synthetic materials such as ceramic proppant, bauxite, tetrafluoroethylene materials (e.g. TEFLONTM polytetrafluoroethylene), fruit stone materials, processed wood, composite particles prepared from a binder and fine-grained particles such as silica, alumina, smoked silica, carbon black, graphite, mica, titanium dioxide, metasilicate, calcium, kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres, solid glass or mixtures thereof. In some embodiments, the proppants may have an average particle size, where the particle size is the largest dimension of a particle, from about 0.001 mm to about 3 mm, from about 0.15 mm to about 2 mm. .5 mm, from about 0.25 mm to about 0.43 mm, from about 0.43 mm to about 0.85 mm, from about 0.85 mm to about 1.18 mm, from about 1.18 mm to about 1.70 mm, or from about 1.70 to about 2.36 mm. In some embodiments, the proppants may have a particle size distribution clustered around multiple averages, such as one, two, three, or four different average particle sizes. The composition or mixture may include any suitable amount of proppant, such as from about 0.01% by weight to about 99.99% by weight, from about 0.1% by weight to about 80% by weight, or from about 0.1% by weight to about 80% by weight. about 10% by weight to 60% by weight or about 0.01% by weight or less or about 0.1% by weight, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9% by weight or about 99.99% by weight or more. system or device
[00104] In various embodiments, the present invention provides a system. The system may be any suitable system which may utilize or which may be generated using an embodiment of the curable composition described herein in an underground formation or which may perform or be generated by the performance of a method for utilizing the curable composition described herein document. The system may include a curable composition that includes at least one of a curable organic resin and a thermostable polymer. The curable composition may also include an organophilically modified clay. The system may also include an underground formation that includes the curable composition therein. In some embodiments, the curable composition in the system may also include a downhole fluid, or the system may include a mixture of the curable composition and downhole fluid. In some embodiments, the system may include a tubular and a pump configured to pump the curable composition in the underground formation through the tubular.
[00105] Various embodiments provide systems and apparatus configured to deliver the curable composition described herein to an underground location and for use of the curable composition herein, such as, by a cementing operation, a repair operation (e.g. , repair), an abandonment operation, a consolidation operation, or a fracturing operation. In various embodiments, the system or apparatus may include a pump hydraulically coupled to a tubular (e.g., any suitable type of oilfield pipe, drill pipe, production pipe, and the like), with the tubular containing a composition, including the curable resin and organophilically modified clay described herein. In some embodiments, the system or apparatus may include a casing tube, wherein the curable composition is between the casing tube and the exploration well, or between the casing tube and another casing tube prior to being allowed to weather. handle. The curable composition may be placed between the casing tube and the exploration well or between the casing tube and another casing tube in any suitable manner, such as, but pumping into the downhole and allowing the curable composition to flow into the well. up through the annular space or by pumping from above into the annular space.
[00106] In some embodiments, the system may include a drillstring disposed in a well, with the drill assembly including a bit at one downhole end of the drillstring. The system may also include an annular space between the drill string and the exploration well. The system may include a pump configured to circulate the curable composition through the drill string, through the drill bit and back up the surface through the annular space. In some embodiments, the system may include a fluid processing unit configured to process the composition exiting the annular space to generate clean drilling fluid for recirculation through the exploration well.
[00107] The pump may be a high pressure pump in some embodiments. As used herein, the term "high pressure pump" refers to a pump that is capable of delivering a fluid to an underground formation (eg, downhole) at a pressure of about 1000 psi or greater. A high pressure pump may be used when it is desired to introduce the curable composition into an underground formation at or above a fracturing gradient of the underground formation, and may also be used in cases where fracturing is not desired. In some embodiments, the high pressure pump may be capable of fluidly transmitting particulate matter, such as proppant particulates, to the underground formation. Suitable high pressure pumps will be known to those skilled in the art and may include floating piston pumps and positive displacement pumps.
[00108] In other embodiments, the pump may be a low pressure pump. As used herein, the term "low pressure pump" refers to a pump that operates at a pressure of about 1000 psi or less. In some embodiments, a low pressure pump may be hydraulically coupled to a high pressure pump which is hydraulically coupled to the tubular. That is, in such embodiments, the low pressure pump may be configured to transport the curable composition to the high pressure pump. In such embodiments, the low pressure pump may "step up" the pressure of the curable composition before it reaches the high pressure pump.
[00109] In some embodiments, the systems or apparatus described herein may additionally include a mixing tank which is upstream of the pump and in which the curable composition is formulated. In various embodiments, the pump (e.g., a low pressure pump, a high pressure pump, or a combination thereof) can transmit the curable composition from the mixing tank or other source of the curable composition to the tubular. In other embodiments, however, the curable composition may be formulated off-site and transported to a job site, in which case the curable composition may be introduced into the tubular via the pump directly from its transport container (e.g., a truck). , a wagon, a barge or the like) or from a transport pipeline. In either case, the curable composition can be drawn into the pump, raised to an appropriate pressure, and then introduced into the tubular for distribution to the underground formation.
[00110] FIG. 1 shows an illustrative schematic of systems and apparatus that can deliver embodiments of the curable compositions of the present invention to an underground location, in accordance with one or more embodiments. It should be noted that while FIG. 1 generally represents a land-based system or apparatus, it should be recognized that similar systems and apparatus may also be operated in locations under the sea. Embodiments of the present invention may be scaled different from that shown in FIG. 1. As depicted in FIG. 1, the system or apparatus 1 may include a mixing tank 10, in which an embodiment of the curable composition may be formulated. The curable composition may be transported via line 12 to the wellhead 14, where the curable composition enters the tubular 16, with the tubular 16 extending from the wellhead 14 into the underground formation 18. tube 16, the curable composition may subsequently penetrate underground formation 18. Pump 20 may be configured to raise the pressure of the curable composition to a desired degree prior to its introduction into tubular 16. It should be recognized that system or apparatus 1 is merely exemplary in nature and several additional components may be present that have not necessarily been depicted in FIG. 1 for reasons of clarity. In some examples, additional components that may be present include, fill funnels, valves, condensers, adapters, linkages, gauges, sensors, compressors, pressure controllers, pressure sensors, flow rate controllers, flow rate sensors, temperature sensors and the like. Although not shown in FIG. 1, at least a portion of the curable composition may, in some embodiments, backflow into the wellhead 14 and exit the underground formation 18.
[00111] It should also be recognized that the disclosed composition may also directly or indirectly affect the various underground equipment and downhole tools that may come into contact with the curable composition during operation. Such equipment and tools may include casing pipes, liners, completion string, insertion strings, drill string, coiled tubing, slickline cable, profiling cable, drill pipe, drill collars, mud motors, and/or motors. or downhole pumps, surface mounted motors and/or pumps, centralisers, turbolizers, scrapers, floats (e.g. shoes, collars, valves and the like), logging tools and related telemetry equipment, drives (e.g. electromechanical devices and the like), sliding sleeves, production sleeves, bushings, filters, screens, flow control devices (e.g. inlet flow control devices, stand-alone inlet flow control devices, flow control device output and the like), couplings (e.g. electro-hydraulic wet connection, dry connection, inductive coupler and the like), control lines (e.g. o, electrical, fiber optic, hydraulic and the like) surveillance lines, drill bits and reamers, sensors or distributed sensors, downhole heat exchangers, valves and corresponding actuation devices, tool seals, shutters, cement, bridge bushings and other well insulating devices or components and the like. Any of these components may be included in the systems and apparatus generally described above and shown in FIG. 1. Composition for the treatment of an underground formation
[00112] Various modalities provide a composition for treating an underground formation. The curable composition can be any suitable composition that can be used to carry out an embodiment of the method for treating an underground formation described herein. For example, the curable composition can include at least one of a curable organic resin and a thermostable polymer. The curable composition includes an organophilically modified clay. The curable organic resin can be an epoxy resin, such as an epoxy-amine resin or an epoxy-anhydride resin. The organophilically modified clay may be an organophilically modified montmorillonite clay. Various embodiments provide a cured product of one embodiment of a curable composition described herein.
[00113] In some embodiments, the curable composition further includes a downhole fluid. The downhole fluid may be any suitable downhole fluid. In some embodiments, the downhole fluid may be a cementing fluid, a fracturing fluid, abandonment fluid, a consolidation fluid, or a remedial treatment fluid. Method for preparing a composition for the treatment of an underground formation
[00114] In various embodiments, the present invention provides a method for preparing a composition for treating an underground formation. The method may be any suitable method that produces a composition described herein. For example, the method may include forming a curable composition that includes at least one of a curable organic resin and a thermostable polymer, also including an organophilically modified clay. Examples
[00115] Various embodiments of the present invention may be better understood by reference to the following Examples, which are presented by way of illustration. The present invention is not limited to the Examples provided herein. Example 1
[00116] The ability of organically modified clays to modify rheological properties was investigated using Nanomer® I.28E Nanoclay (NI28E) from Nanocor Inc., a wholly owned subsidiary of AMCOL International Corporation, Hoffman Estates, IL, which included approximately 25- 30% by weight trimethyl steryl ammonium ion, had a density of about 200 to about 500 kg/m 3 , and had an average particle size of about 8-10 microns. The rheologies of the epoxy resin system, including C1 (about 60% by weight to about 90% by weight bisphenol A diglycidyl ether and about 10% by weight glycidyl butyl ether about 30% by weight) , C2 (hexanedimethanol diglycidyl ether) and C3 (diethyltoluenediamine) and organophilically modified clay were investigated using a FANN® 35 rheometer with a Fann elastic limit adapter (FYSA) connection. The results obtained are shown in Table 1. In each case where organophilically modified clay was used, a yield point (YP) was observed in the rheological profile. Additionally, it is shown in FIG. 2 the ability of the resulting epoxy resin/clay blend system to suspend large size particles. Table 1 Rheologies of Organophilically Modified Resin/Clay Systems The 439+ measurement was at the high end of the instrument.

Example 2
[00117] The ability of organically modified clays to modify rheological properties was further investigated using the NI28E of Example 1. The rheologies of the epoxy resin system including C2, C4 (polyoxypropylene diamine), C5 (2,4,6 tridimethylaminomethyl phenol) and organophilically modified clay were investigated using a FANN® 35 rheometer with a Fann Elastic Limit Adapter (FYSA) connection. The curable organic composition consisted of 500 g C2, 224 g C4, 10 g C5 and varying amounts of NI28E. FIG. 3 illustrates shear stress versus shear rate for the tested compositions. FIG. 4 illustrates the yield point as a function of the percent volume of NI28E. All percentages are expressed in percent by volume. It was observed in FIG. 4 that an apparent elastic limit was imparted between a volume percent of NI28E between 5.3 to 6.9.
[00118] The terms and expressions that have been used are used as terms of description and not of limitation and there is no intention that the use of such terms and expressions will exclude any equivalents of the characteristics shown and described or parts thereof, but it is acknowledged that various modifications are possible within the scope of embodiments of the present invention. Thus, it should be understood that while the present invention has been specifically disclosed for specific embodiments and optional features, modifications and variations of the concepts disclosed herein may be invoked by those skilled in the art, and that such modifications and variations are considered to be within the scope of the embodiments of the present invention. Additional Modalities
[00119] The following examples of modalities are provided, their numbering should not be interpreted as designating levels of importance:
[00120] Embodiment 1 provides a method for treating an underground formation, the method comprising: placing a curable composition in an underground formation comprising at least one of a curable organic resin and a thermostable polymer; and an organophilically modified clay.
[00121] Embodiment 2 provides the method of Embodiment 1, wherein the method further comprises obtaining or providing the curable composition, wherein the delivery or obtaining the curable composition occurs above the surface.
[00122] Embodiment 3 provides the method of any one of Embodiments 1-2, wherein the method further comprises obtaining or providing the curable composition, wherein the delivery or obtaining the curable composition occurs in the underground formation.
[00123] Modality 4 provides the method of any of Modalities 1-3, wherein the method comprises at least one of cementing and repairing a well in the underground formation.
[00124] Modality 5 provides the method of any of Modalities 1-4, wherein the method comprises consolidating the underground formation.
[00125] Modality 6 provides the method of any of Modalities 1-5, wherein the method comprises fracturing the underground formation.
[00126] Modality 7 provides the method of any of Modalities 1-6, wherein the method comprises performing a well abandonment procedure in the underground formation.
[00127] Embodiment 8 provides the method of any one of Embodiments 1-7, further comprising an organophilic modification of a clay to provide the organophilically modified clay.
[00128] Modality 9 provides the method of Modality 8, in which the organophilic modification occurs, at least partially, above the surface.
[00129] Modality 10 provides the method of Modality 8, in which the organophilic modification occurs, at least partially, in the underground formation.
[00130] Embodiment 11 provides the method of any one of Embodiments 1-9, further comprising curing the curable composition, to provide a cured product of the curable composition.
[00131] Mode 12 provides the method of Mode 11, where curing occurs, at least partially, above the surface.
[00132] Modality 13 provides the method of any of Modalities 11-12, wherein the curing takes place, at least partially, in the underground formation.
[00133] Embodiment 14 provides the method of any one of Embodiments 1-13, wherein the curable composition comprises a hydrophobic curable composition.
[00134] Embodiment 15 provides the method of any one of Embodiments 1-14, wherein about 1% by weight to about 99.99% by weight of the curable composition is the curable organic resin, the thermoset polymer, or a combination of the same.
[00135] Embodiment 16 provides the method of any one of Embodiments 1-15, wherein the curable organic resin or thermostable polymer comprises at least one of a shellac, a polyamide, a silyl-modified polyamide, a polyester , a polycarbonate, a polycarbamate, a urethane, a natural resin, an epoxy-based resin, a furan-base resin, a phenolic-based resin, a urea-aldehyde resin, and a furfuryl alcohol-phenol formaldehyde resin -phenol.
[00136] Embodiment 17 provides the method of any one of Embodiments 1-16, wherein the curable organic resin comprises at least one of an epoxy-amine resin and an epoxy-anhydride resin.
[00137] Embodiment 18 provides the method of any one of Embodiments 1-17, wherein the curable organic resin comprises at least one epoxide component which is a mono- or poly-substituted aryl (C5-C20) polyepoxide compound, wherein the (C5-C20)aryl is substituted or unsubstituted.
[00138] Embodiment 19 provides the method of Embodiment 18, wherein the epoxide component is a diepoxide-substituted (C1-C10)hydrocarbylphenyl, wherein the phenyl and (C1-C10)hydrocarbyl are each independently substituted or not replaced.
[00139] Embodiment 20 provides the method of any one of Embodiments 18-19, wherein the epoxide component is bisphenol A diglycidyl ether.
[00140] Embodiment 21 provides the method of any one of Embodiments 1-20, wherein the curable organic resin comprises at least one epoxide component which is a polyepoxide-substituted (C5-C20)cycloalkyl compound, wherein the ( C5-C20) cycloalkyl is substituted or unsubstituted.
[00141] Embodiment 22 provides the method of Embodiment 21, wherein the epoxide component is cyclohexanedimethanol diglycidyl ether.
[00142] Embodiment 23 provides the method of any one of Embodiments 1-22, wherein the curable composition comprises at least one amine component which is a polyamine-substituted (C1-C30)hydrocarbyl, wherein the (C1-C30) )hydrocarbyl and each amine are independently substituted or unsubstituted.
[00143] Embodiment 24 provides the method of Embodiment 23, wherein the amine component is a bis(amino(C0-C5)hydrocarbyl)(C6-C20)aryl compound, wherein the (C6-C20)aryl, (C0 -C5)hydrocarbyl, and each amine is each independently substituted or unsubstituted.
[00144] Embodiment 25 provides the method of any one of Embodiments 23-24, wherein the amine component is diethyltoluenediamine.
[00145] Embodiment 26 provides the method of any one of Embodiments 1-25, wherein the curable composition comprises at least one amine component which is a substituted poly((C2-C5)hydrocarbyloxy)polyamine, wherein each (C2 -C5 )hydrocarbyloxy and each amine are independently substituted or unsubstituted.
[00146] Embodiment 27 provides the method of Embodiment 26, wherein the amine component is polyoxypropylene diamine.
[00147] Embodiment 28 provides the method of any one of Embodiments 1-27, wherein the curable composition comprises an amine component which is a (C0-C10)hydrocarbyl(C6-C20)aryl mono- or polyamino group, in that the (C0-C10)hydrocarbyl, (C6-C20)aryl and each amine are each independently substituted or unsubstituted.
[00148] Embodiment 29 provides the method of Embodiment 28, wherein the amine component is a tris(amino(C1-C3)hydrocarbyl)benzene, wherein the (C1-C3)hydrocarbyl, the benzene, and each amine is independently substituted or not replaced.
[00149] Embodiment 30 provides the method of any one of Embodiments 28-29, wherein the amine component is 2,4,6-tris(dimethylaminomethyl)phenol.
[00150] Embodiment 31 provides the method of any one of Embodiments 1-30, wherein the curable composition comprises an anhydride component which is a maleic anhydride or a succinic anhydride, which is fused to a (C5-C20) ring of substituted or unsubstituted hydrocarbon or a plurality of said fused maleic or succinic anhydrides linked together through a substituted or unsubstituted (C0-C30)hydrocarbyl interrupted by 0, 1, 2 or 3 oxygen atoms.
[00151] Embodiment 32 provides the method of Embodiment 31, wherein the anhydride component is at least one of bisphenol A dianhydride, biphenyl dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, methyl- 5-norbornene-2,3-dicarboxylic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride.
[00152] Embodiment 33 provides the method of any one of Embodiments 1-32, wherein the organophilically modified clay is present in the curable composition at a concentration such that the curable composition has a higher yield point than a corresponding curable composition having substantially none of the organophilically modified clays therein.
[00153] Embodiment 34 provides the method of any one of Embodiments 1-33, wherein the organophilically modified clay is from about 0.01% by weight to about 50% by weight of the curable composition.
[00154] Embodiment 35 provides the method of any one of Embodiments 1-34, wherein the organophilically modified clay is from about 1% by weight to about 20% by weight of the curable composition.
[00155] Embodiment 36 provides the method of any one of Embodiments 1-35, wherein the organophilically modified clay comprises at least one of kaolinite, montmorillonite, illite, and chlorite.
[00156] Embodiment 37 provides the method of any one of Embodiments 1-36, wherein the organophilically modified clay comprises montmorillonite.
[00157] Embodiment 38 provides the method of any one of Embodiments 1-37, wherein the organophilically modified clay comprises an organophilic modification that is at least one of cationic substitution, physisorption, and chemossorption.
[00158] Embodiment 39 provides the method of any one of Embodiments 1-38, wherein at least one organophilic modifying compound or ion thereof is from about 0.01% by weight to about 80% by weight of the organophilically modified clay.
[00159] Embodiment 40 provides the method of any one of Embodiments 1-39, wherein at least one organophilic modifying compound or ion thereof is from about 10% by weight to about 50% by weight of at least an organophilically modified clay.
[00160] Embodiment 41 provides the method of any one of Embodiments 1-30, wherein the organophilically modified clay comprises at least one organophilic modification compound or an ion thereof, wherein the organophilic modification compound is at least one of a substituted or unsubstituted (C10-C50)fatty acid or a salt thereof, a tri- or tetra- (C1-C50)hydrocarbylammonium salt and a tri- or tetra- (C1-C50)hydrocarbylphosphonium salt, wherein each ( C1-C50)hydrocarbyl is independently selected, substituted or unsubstituted, and interrupted by 0, 1, 2, or 3 atoms chosen from -O-, -S-, and substituted or unsubstituted -NH-.
[00161] Embodiment 42 provides the method of Embodiment 41, wherein the organophilic modification compound comprises a (C10-C50) fatty acid salt.
[00162] Embodiment 43 provides the method of any one of Embodiments 41-42, wherein the organophilic modifying compound comprises magnesium stearate and zinc stearate.
[00163] Embodiment 44 provides the method of any one of Embodiments 41-43, wherein the organophilic modifying compound comprises at least one (C1-C50)tri- or tetra-hydrocarbylammonium salt, and one (C1-C50) )alkyl- or alkenylphosphonium salt, wherein each (C1-C50)hydrocarbyl is independently selected.
[00164] Embodiment 45 provides the method of any of Embodiments 41-44, wherein the organophilically modifying compound comprises at least one of a stearyl trimethyl ammonium salt, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and tetraphenylphosphonium bromide.
[00165] Embodiment 46 provides the method of any one of Embodiments 1-45, wherein the organophilically modified clay has a density of from about 50 kg/m3 to about 5,000 kg/m3.
[00166] Embodiment 47 provides the method of any one of Embodiments 1-46, wherein the organophilically modified clay has a density of from about 200 kg/m3 to about 500 kg/m3.
[00167] Embodiment 48 provides the method of any one of Embodiments 1-47, wherein the organophilically modified clay has a particle size of from about 1 nm to about 1 mm.
[00168] Embodiment 49 provides the method of any one of Embodiments 1-48, wherein the organophilically modified clay has a particle size of from about 1 micron to about 500 microns.
[00169] Embodiment 50 provides the method of any one of Embodiments 1-49, wherein the curable composition further comprises a weighting agent.
[00170] Embodiment 51 provides the method of Embodiment 50, wherein the weighting agent is from about 0.001% by weight to about 80% by weight of the curable composition.
[00171] Embodiment 52 provides the method of Embodiment 50, wherein the weighting agent has a particle size of from about 1 nm to about 10 mm.
[00172] Embodiment 53 provides the method of any one of Embodiments 1-52, wherein the curable composition has a pour point from about 1 lbf/100 ft 2 to about 10,000 lbf/100 ft 2 .
[00173] Embodiment 54 provides the method of any one of Embodiments 1-53, wherein the curable composition has a pour point of about 15 lbf/100 ft 2 to about 100 lbf/100 ft 2 .
[00174] Embodiment 55 provides the method of any one of Embodiments 1-54, wherein the curable composition has a shear stress at about 10°C to about 40°C and normal pressure at about 0. 5 s-1 to about 50 s-1 from about 10 lbf/100 ft 2 to about 300 lbf/100 ft 2 .
[00175] Embodiment 56 provides the method of any one of Embodiments 1-55, wherein the curable composition exhibits a shear stress at about 50°C to about 100°C and normal pressure at about 0. 5 at about 50 s -1 from about 10 lbf/100 ft 2 to about 100 lbf/100 ft 2 .
[00176] Embodiment 57 provides the method of any one of Embodiments 1-56, wherein the organophilically modified clay has a density of from about 50 kg/m3 to about 5,000 kg/m3.
[00177] Embodiment 58 provides the method of any one of Embodiments 1-57, wherein the curable composition has a density of from about 200 kg/m3 to about 3000 kg/m3 .
[00178] Embodiment 59 provides the method of any one of Embodiments 1-58, wherein the curable composition further comprises water, saline, aqueous base, oil, organic solvent, synthetic fluid oil phase, aqueous solution, alcohol or polyol, cellulose, starch, alkalinity control agent, acidity control agent, density control agent, density modifier, emulsifier, dispersant, polymeric stabilizer, cross-linking agent, polyacrylamide, polymer or combination of polymers, antioxidant, stabilizer heat sink, foam control agent, solvent, thinner, plasticizer, filler or inorganic particles, pigment, dye, precipitating agent, rheology modifier, oil wetting agent, tack retardant additive, surfactant, corrosion inhibitor, gas, additive weight reduction additive, heavyweight additive, loss of circulation material, filtration control additive, salt, fiber, thixotropic additive, disintegrant, agent crosslinking agent, gas, rheology modifier, curing accelerator, curing retardant, pH modifier, chelating agent, scale inhibitor, enzyme, resin, water control material, polymers, oxidant, a marker, Portland cement, cement pozzolan, gypsum cement, high alumina content cement, slag cement, silica cement, fly ash, metakaolin, shale, zeolite, amorphous silica, composed of crystalline silica, fibers, a hydratable clay, microspheres, pozzolan lime or a combination of them.
[00179] Embodiment 60 provides the method of any one of Embodiments 1-59, wherein placing the curable composition in the underground formation comprises fracturing at least part of the underground formation to form at least one underground fracturing.
[00180] Embodiment 61 provides the method of any one of Embodiments 1-60, wherein placing the curable composition in the underground formation comprises pumping the curable composition through a tubular disposed in an exploration well and into the formation underground.
[00181] Embodiment 62 provides the method of any one of Embodiments 1-61, wherein placing the curable composition in the underground formation comprises pumping the curable composition through a casing tube disposed in an exploration well and a annular space between casing tube and exploration well.
[00182] Embodiment 63 provides a system for performing the method of any one of Embodiments 1-62, the system comprising: a tubular disposed in the underground formation; and a pump configured to pump the curable composition into the underground formation through the tubular.
[00183] Embodiment 64 provides a method for treating an underground formation, the method comprising: placing a curable composition in an underground formation comprising a curable epoxy resin; and an organophilically modified montmorillonite clay.
[00184] Embodiment 65 provides a system comprising: a curable composition comprising at least one of a curable organic resin and a thermostable polymer; and an organophilically modified clay; and an underground formation comprising the curable composition therein.
[00185] Modality 66 provides the Modality 65 system, which also comprises a tubular arranged in the underground formation; and a pump configured to pump the curable composition into the underground formation through the tubular.
[00186] Embodiment 67 provides a curable composition for treating an underground formation, the curable composition comprising: at least one of a curable organic resin and a thermostable polymer; and an organophilically modified clay.
[00187] Embodiment 68 provides the curable composition of Embodiment 67, wherein the curable composition further comprises a downhole fluid.
[00188] Embodiment 69 provides a method of preparing a curable composition for treating an underground formation, the method comprising: forming a curable composition comprising at least one of a curable organic resin and a thermostable polymer; and an organophilically modified clay.
[00189] Embodiment 70 provides the composition, method or system of any or any combination of Embodiments 1-69 optionally configured so that all elements or options listed are available for use or selection.

权利要求:
Claims (20)
[0001]
1. A method for treating an underground formation, comprising: placing a curable composition in an underground formation, characterized in that the curable composition comprises: at least one of a curable organic resin and a thermostable polymer; and an organophilically modified clay comprising an organophilically modified compound or an ion thereof, wherein the organophilically modified compound is at least one of a substituted or unsubstituted (C10-C50) fatty acid or a salt thereof, a tri-salt or tetra-(C1-C50)hydrocarbylammonium and a tri- or tetra-(C1-C50)hydrocarbylphosphonium salt, or combinations thereof, wherein each tri- or tetra-(C1-C50)hydrocarbylammonium salt is a tri- or tetra -(C1-C50)hydrocarbylphosphonium, is independently selected, is substituted or unsubstituted and is interrupted by 0, 1, 2 or 3 atoms chosen from -O-, -S-, and -NH- substituted or unsubstituted, or combinations of the same.
[0002]
2. Method according to claim 1, characterized in that the organophilic-modified compound comprises a (C10-C50) fatty acid salt.
[0003]
3. Method according to claim 1, characterized in that the organophilic modification compound comprises magnesium stearate and zinc stearate.
[0004]
4. Method according to claim 1, characterized in that the organophilic modified compound comprises at least one (C1-C50) tri- or tetra-hydrocarbylammonium salt and one (C1-C50)alkyl- or alkenylphosphonium salt, in that each (C1-C50)hydrocarbyl is independently selected.
[0005]
5. Method according to claim 1, characterized in that the organophilic modification compound comprises at least one of a stearyl trimethyl ammonium salt, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide and tetraphenylphosphonium bromide, or combinations of the same.
[0006]
A method according to claim 1, characterized in that the curable composition comprises at least one amine component which is at least one of diethyltoluenediamine, polyoxypropylene diamine, 2,4,6-tris(dimethylaminomethyl)phenol, or combinations of the same.
[0007]
A method as claimed in claim 1, further comprising curing the curable composition to provide a cured product of the curable composition, wherein the curing occurs at least partially above the surface.
[0008]
A method as claimed in claim 1, further comprising curing the curable composition to provide a cured product of the curable composition, wherein the curing takes place at least partially in the underground formation.
[0009]
9. The method of claim 1, characterized in that the curable organic resin comprises a diepoxide-substituted (C1-C10)hydrocarbylphenyl, wherein the phenyl and the (C1-C10)hydrocarbyl are each independently substituted or not replaced.
[0010]
10. Method according to claim 1, characterized in that the curable organic resin comprises bisphenol A diglycidyl ether, cyclohexanedimethanol diglycidyl ether, or a combination thereof.
[0011]
11. Method according to claim 1, characterized in that the organophilically modified clay has a density in the range of 200 kg/m3 to 500 kg/m3.
[0012]
12. Method according to claim 1, characterized in that the organophilically modified clay has a particle size in the range of 1 micron to 500 microns.
[0013]
Method according to claim 1, characterized in that at least one organophilically modified compound or an ion thereof is from 10% by weight to 50% by weight of at least one organophilically modified clay.
[0014]
14. Method according to claim 1, characterized in that the organophilically modified clay has a density in the range of 200 kg/m3 to 500 kg/m3.
[0015]
15. Method according to claim 1, characterized in that the organophilically modified clay is from 1% by weight to 20% by weight of the curable composition.
[0016]
16. Method according to claim 1, characterized in that the organophilically modified clay comprises at least one of kaolinite, montmorillonite, illite and chlorite.
[0017]
17. Method according to claim 1, characterized in that it further comprises fracturing at least part of the underground formation with the curable composition to form at least one underground fracture.
[0018]
18. Method according to claim 1, characterized in that it also comprises the cementing or repair of an exploration well in the underground formation.
[0019]
19. System for the treatment of an underground formation, to carry out the method as defined in claim 1, characterized in that it comprises: a tubular disposed in the underground formation; and a pump configured to pump the curable composition into the underground formation through the tubular.
[0020]
20. A curable composition for the treatment of an underground formation, characterized in that it comprises: at least one of a curable organic resin and a thermostable polymer; and an organophilically modified clay comprising an organophilically modified compound or an ion thereof, wherein the organophilically modified compound is at least one of a substituted or unsubstituted (C10-C50) fatty acid or a salt thereof, a tri-salt thereof. or tetra-(C1-C50)hydrocarbylammonium and a tri- or tetra-(C1-C50)hydrocarbylphosphonium salt, or combinations thereof, wherein each tri- or tetra-(C1-C50)hydrocarbylammonium salt is a tri- or tetra -(C1-C50)hydrocarbylphosphonium is independently selected, substituted or unsubstituted, and interrupted by 0, 1, 2, or 3 atoms chosen from substituted or unsubstituted -O-, -S-, and -NH-, or combinations of the same.

类似技术:

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同族专利:

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公开号 | 公开日

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PH12017500012B1|2017-05-15|

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US20170247598A1|2017-08-31|

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WO2016048332A1|2016-03-31|

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GB201700349D0|2017-02-22|

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AU2014407118B2|2018-03-22|

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PH12017500012A1|2017-05-15|

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CA2958055A1|2016-03-31|

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SA517380927B1|2021-04-04|

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US10144858B2|2018-12-04|

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BR112017003050A2|2018-02-27|

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RU2668432C1|2018-10-01|

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GB2545110A|2017-06-07|

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MX2017002587A|2017-05-25|

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AU2014407118A1|2017-02-02|

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CA2958055C|2019-04-23|

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NO20170241A1|2017-02-17|

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CN106661440A|2017-05-10|

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GB2545110B|2022-02-23|

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2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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PCT/US2014/057510|WO2016048332A1|2014-09-25|2014-09-25|Composition including a curable resin and organophilically-modified clay for subterranean oil well applications|

---