WO2015183319A1

WO2015183319A1 - Resin compositions used with alkali metal salts

Info

Publication number: WO2015183319A1
Application number: PCT/US2014/040385
Authority: WO
Inventors: Paul Joseph Jones; Gregory Robert HUNDT; Jeffery Dwane Karcher; Lucas David ALBRIGHTON; Brittney Nicole GUILLORY
Original assignee: Halliburton Energy Services, Inc.
Priority date: 2014-05-30
Filing date: 2014-05-30
Publication date: 2015-12-03
Also published as: AR100275A1

Abstract

Disclosed are methods for use of resin compositions in conjunction with spacer fluids. An example embodiment comprises introducing a spacer fluid into a wellbore, wherein the spacer fluid comprises a group I alkali metal salt and water; and introducing a resin composition into the wellbore after the spacer fluid, wherein the resin composition comprises a resin and a hardening agent.

Description

RESIN COMPOSITIONS USED WITH ALKALI METAL SALTS

BACKGROUND

[0001] Embodiments relate to resin compositions and spacer fluids for use in subterranean operations and, more particularly, in certain embodiments, to resin compositions and spacer fluids comprising alkali metal salts and methods of use in subterranean formations.

[0002] In well operations, such as well construction and remedial cementing, cement compositions are commonly utilized. Cement compositions ma be used in primary cementing operations whereby pipe strings, such as casing and liners, are ceniented in weilbores. In a typical primary cementing operation, a cement composition may be pumped into an annulus between the exterior surface of the pipe string disposed therein and the walls of the wellbore (or a larger conduit in the wellbore). The cement composition may set in the annular space, thereby forming an annular sheath of hardened, substantially impermeable material (i.e., a cement sheath) that may support and position, the pipe string in the wellbore and may bond the exterior surface of the pipe string to the wellbore wails (or the larger conduit). Amongst other things, the cement sheath surrounding the pipe string should function to prevent the migration of fluids in the annuliis. as well as protect the pipe string from corrosion. Cement compositions also may be used in remedial cementing methods, such as in squeeze cementing for sealing voids in. a pipe string, cement sheath, gravel pack, subterranean formation, and the like. Cement compositions may also be used in surface applications, for example, construction cementing.

[0003] Other types o compositions, including non-eenientitious settabSe sealant compositions, such as resin-based sealants, may be used in the primary and/or remedial cementing operations described above. These compositions may be circulated through the well bore to plug a void or crack in the conduit or cement sheath or an opening between the two. Proper placement of the resin composition is controlled in part by the thickening time of the resin, if the resin, composition begins to harden, too quickly it may be placed in the wrong location in a wellbore leading to poor zonal isolation, ineffective remediation, or unintended plugging of the well . Amongst, the many uses for resins, applications in the oi l and gas industr are unique in their demand for Song resin pot life and controlled density.

[0004] It is well known that the kinetics of resin curing can be impacted b water. For example, resin compositions may undergo a vigorous exothermic reaction in the presence of water. Such resin compositions ma be difficult to place in a wellbore as aqueous fluids are commonly used for well control and displacement Resin compositions with water insoluble components are generally less susceptible to the effects of water. However, at elevated temperatures, the reaction rate may still be accelerated by water. BRIEF .DESCRIPTION OF THE DRAWINGS

[0005] These drawings illustrate certain aspects of some of the embodiments of the present invention, and should not be used to limit or define the invention.

[0006] F G. I is a schematic illustration of an example system for the preparation and deli very of a resin composition and/or a spacer fluid into a wellbore.

[0007] FIG. 2 is a schematic illustration of example surface equipment tha may be used in the piacenient of a resin composition and/or a spacer fluid into a wellbore.

[0008] F 3. 3 is a schematic illustration of an example in which a resin composition is used In a primary cementing application.

[0009] FIG. 4 is a schematic illustration showing the presence of a small perforation in a casing and cement sheath in a wellbore.

[0010) FIG. 5 is a schematic i llustration of an example in which a resin composition is used in a remedial cementing application.

[001 1] FIG, 6 is a schematic illustration of another example in which a resin composition is used in a remedial cementing application.

DETAILED DESCRIPTION

j00! 2] Embodiments relate to resin compositions and spacer fluids for use in subterranean operations and, more particularly, io resin compositions and spacer fluids comprising alkali metal salts and methods of use in subterranean formations, in accordance with present embodiments, the spacer fluids comprising alkali metal salts may not reduce the thickening times of the resin compositions as compared to other aqueous spacer -fluids. One of the many potential advantages to these methods and compositions is. the improvement of placement effic iency. Another potential advantage of these methods and compositions is that the cost of subterranean operations may be reduced by using less of the .resin since it may be placed more- accurately if the thickening time is better controlled.

[001.3] Embodiments of the resin composition may generally comprise a resin. Optional embodiments of the resin composition may comprise a diluent. The resin composition may thicken to develop compressive strength and/or to form a seal when placed in a void or crack. Accordingly, the resin composition may function to provide a substantially impermeable barrier to sea! off formation fluids and gases and consequently prevent potential fluid and gas migration into the anmilus or the interior of the casing.

[001 As used herein, the term "resin" refers, to an of a number of physically similar polymerized synthetics or chemically modified, natural resins including thermoplastic .materials and thermosetting materials. Example of resins, that may be used in the resin composition include, but are not limited to, epoxy-based resins, novolac resins, polyepoxide resins, phenol- aldehyde resins, urea-aldehyde resins, urethane resins, phenolic resins, furan/furfuryl alcohol, resins, phenolic/latex resins, phenol formaldehyde resins, bisphenol A diglycidy! ether resins, butoxymethyl butyl glyeidyl ether resins, bisphenol A~epichIorohydrin resins, bisphenol F resins, glycidyl ether resins, polyester resins and hybrids and copolymers thereof, polyurethane resins and hybrids and copolymers thereof, ac-rylaie resins, and mixtures thereof. Some suitable resins, such as epoxy resins, may be cured with a hardening agent, so that when pumped downhole, they may be cured using only time and temperature. Other suitable resins, such as ftiran .resins generally require a time-delayed hardening agent to help activate the polymerization of the resins if the formation temperature- is low (i.e., less than 250 °F), but will cure under the effects of time and temperature if the formation temperature is above about 250 °F. One resin that may be used in embodiments is the Well .Lock ¹ resin system, available from Halliburton Energy Services, Inc., of Houston, Texas.

[0015] The selection of a suitable resin may be affected by the temperature of the subterranean formatio to which the resin composition will be introduced. By way of example, tor subterranean formations having a bottom hole static temperature ("BHST") ranging from abou 60 °F to about 250 °F, two-component epoxy-based resins comprising a resin component and a hardening agent may be preferred. For subterranean formations ^'having a BHST ranging from about 300 °F to about 600 "F. a furaa-based resin may be preferred, for subterranean formations having a BHST ranging from, about 200 °F to about 400 °F, either a phenolic -based resin or a one-component HT epoxy-based resin may be suitable. For subterranean formations having a BHST of at least about 175 °F, a phenol/phenol tormaldehyde urfuryl alcohol resin may also be suitable. Those of ordinary skill in the art, with the benefit of this disclosure, should be able to select a resin for a particular application.

[0016] Generally, the resin ma be included in the resin composition in an amount in the range of about 5% t about 100% by volume of the resin composition, in particular embodiments, the resin may be included in the resin composition in an amount of about 60% to about 100% by volume of the resin composition. Factors that may affect this determination include the type of resin and potential hardening agent desired for a particular application. Those of ordinary skill in the art. with the benefit of this disclosure, should be able to select an amount. of a resin for a particular application.

[0017] The resin composition generally should have a density suitable for a particular application as desired by those of ordinary skill in the art. Without being limited by theory, the density of the resin composition may be adjusted to achieve the proper density hierarchy for placement of the resin. In some embodiments, the resin composition may ha ve a density in the range of from about 5 pounds per gallon fppg*^*) to about 17 ppg. in other embodiments, the resin composition may have a density in the range of about S ppg to about 14 ppg. In yet other embodiments, the resin composition may have a density in the range of about 10 ppg to about 12 ppg. Further, filler particles may be chosen which modify the mechanical properties of the set resin composition or the fluid properties of the liquid, (uncured) resin composition. Such filler particles may have the same density as the resin composition so that the bulk density is not changed. Examples of suitable filler particles may include, but are not limited to, aluminum oxide, a aruite, barium carbonate,, barium oxide, harite, calcium carbonate, calcium oxide, ceoospheres, chromite, chromium oxide, copper, copper oxide, dolomite, galena, hematite, hollow glass microspheres, ilmenite, iron oxide, siclerite, magnetite, magnesium oxide, manganese carbonate, manganese dioxide, manganese (I V) oxide, manganese oxide, manganese tetraoxide, manganese (11) oxide, manganese (HI) oxide, molybdenum (IV) oxide, molybdenum oxide, molybdenum trioxide, Portland cement, pumice, pyrite, sphereiite, silica, silver, tenorite, titania, titanium (II) oxide, titanium (III) oxide, titanium (IV) dioxide, zirconium, oxide, zirconium silicate, zinc oxide, cement-kiln dust, unexpanded and expanded perllte, attapulgite, bentomte, zeolite, elastomers, sand, micro tzed polymers, waxes, polymer fibers, inorganic fibers and any combination thereof, ft should be noted that the foregoing list encompasses a!! crystal forms of any material. ^'Those of ordinary skill in the art, with the benefit of this disclosure, should recognize the appropriate density of the resin composition for a particular application,

[00 8] fn optional embodiments, a diluent may be added to the resin composition to reduce the viscosity of the resin composition for ease of handling, mixing, and transferring. However, in some embodiments, it may be desirable to not use a diluent (e.g., for environmental or safety reasons). Factors that may affect this decision include geographic location of the well, the surrounding weather conditions, and the desired long-term stability of the well bore servicing fluid. Those of ordinary skill in the art, with the benefit of this disclosure, should he able to determine whether to use a diluent for a particular application.

[001 ] Generally, any diluent thai is compatible with the resin and that achieves the desired viscosity effect may be suitable for use in the resin composition. Some diluents may be reactive, in that they are incorporated into the resin. Diluents that are reactive may comprise amine or epoxide functional groups. Suitable diluents may include, but are not limited to, butyl giycidyl ether, cyeiohexane dimetiianol dlglycidyl ether, polyethylene glycol, butyl lactate, dipropySene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl fbrmamide, diethyleneglycol methyl ether, ethyleneglycol. butyl ether, diethyleneglycol butyl ether, propylene carbonate, d'limonene, fatty acid methyl esters, or any combinations thereof. Selection of an appropriate diluent may be dependent on the resin composition chosen. In some embodiments, the amount of the diluent used in the resin composition may be in the range of about 0.1 % to about 30% by weight of the resin composition. Optionally, the resin composition may be heated to reduce its viscosity, in place of, or in addition to. using a diluent Those of ordinary skill in the art, with the benefit of this disclosure, should be able to select a type of and the amount of a diluent for a particular application.

[0020] Optional embodiments may comprise a hardening agent. As used herein, "hardening agent" ' refers to an substance capable of transforming the resin into a hardened, consolidated mass. Examples of suitable hardening agents include_* but are not limited to, aliphatic amines, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, amido amines, polyamides, poSyethyl amines, polyether amines, polyoxyalky!ene amines, earboxylic anhydrides, tricthylenetetraarnme, ethylene diamine, N- cocoalkyStriniethyieiie, isophorone diamine, N-ammopbenyl piperazine, imidazoline, 1 ,2- diammocyelohexane, polytheramine, diethyltoluenediamine, 4,4'~diammodipheny! methane, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleie anhydride, polyazelaic poiy nhydricte, phthalie anhydride, and combinations thereof. Commercial examples of hardening agents may include, but are not limited to, ETHACUR.E*^' 100 curative, available from Albemarle Corp, of Baton Rouge, Louisiana, and JEFF AMINE*' D-230 polyetheraniins, available from Huntsman Corp. of The Woodlands, Texas, The hardening agent ma be included in the resi composition in an amount sufficient to at least partially harden the resin composition. In some embodiments, the hardening agent may be included in the resin composition in the range of about 5% to about 100% by volume of the resin composition. In other embodiments, the hardening agent may b included in the resin, composition in an amount of about 50% to about 75% by volume of the resin composition, in still other embodiments, the hardening agent may be included in the resin composition in an amount of about 62.5% by volume of the resin composition. Those of ordinary skill in the art, with the benefit of this disclosure, should be able to select a type of hardening agent and amount of hardening agent for a particular application.

[0021] In some embodiments, the amount of hardening agent may be sel ected to i mpart a desired elasticity or compressibility. Without limitation, generally, the Sower the amount of hardening agent present in the resin composition, the greater the elasticity or compressibility will be. With the benefit of this disclosure, those of ordinary skill in the art should be able to select an appropriate amount of hardening agent to achieve a desired elasticity or compressibility for a particular application.

[0022] in some embodiments the hardening agent may comprise a mixture of hardening agents selected to impart particular qualities to the resin composition. For example, in particular embodiments, the hardening agent may comprise a fast-setting hardening agent and a slow- setting hardening agent. As used herein, "fast-setting hardening agent" and "slow-setting hardening agent" do not imply any specific rate at which the agents set a resin; instead, the terms ^•merely indicate the relative rates at which the hardening agents initiate hardening of the resin. Whether a particular hardening agent is considered fast-setting or slow-setting may depend on the other hardening agent(s) with which it is used. In a particular embodiment, ETFiACURB* 100 may be used as a slow-setting hardening agent, and JEFFA INB*" D-230 may be used as a fast-setting hardening agent. In some embodiments, the ratio of fast-setting hardening agent to slow-setting hardening agent may be selected to achieve a desired behavior of the hardening agent. For example, in some embodiments, the fast-setting hardening agent may be included in a. ratio of approximately 1:5, by volume, with the slow-setting hardening agent. Those of ordinary skill in the art, with the benefit of this disclosure, should be able to select a mixture oFhardeniug agents for a particular application.

[00231 The hardening agent may also comprise an optional si^'lane coupling agent. The si lane coupling agent may be used, among other things, to act as a mediator to help bond the resin to the surface of the subterranean formation and/or the surface of the well bore. Examples of suitable silane coupling agents include, but are not. limited to_* N-2-(aminoethyl)-3- aminop.ropyltrimethoxysilane; 3-glycidoxypropyItrisnethoxysila.ne; gan.it.na- aminopropyltriethoxvsilane; - ete-Caminoethy -gamma-an inopTOpyUrimethoxysiianes; ammoethyK -beta^ minoe^ gamma-ureidopropyl- triethoxysiSanes; heta-(3-4 epo.xy-eyciohex i)-eih i-tfimeihoxysilane; gamma- glycidoxypropyltriroeihoxysilanes; vinyUrichlorosUane; vinyhris (beia-metboxyethoxy) silane; vinyitrieihoxysilane; vinyitrimethoxysilane; 3-nietacryioxypropyltrimelhoxysslane; beia-(3,4 epoxycyclohexyl)~ethyltrimethoxysilane; r-glyc oxypropy!irimet^'hoxysi!ane; r- glycidoxypropylmethylidiethoxysUane; -t«ta-(aminoethyl)-r-ammopropyl>trimethoxys!lane; N-beta^amlnoethy.l)-r-amlnopRpylm^hyldimethoxysiIane; 3-animopropyl-iri.et ioxysilane; - p^'henyl-f-ansmopropyltrifoethoxysilane; r-mercaptoprapyltrimethoxysifane; r-

^•chlofopropyl rimethoxysilane; vinyitrichksrosiiane; vinyl tris (beta-methoxyethoxy) silane; vmylirhnethoxysilane; r-metacryk>xyp^'rop>4trimethoxysiIane; beta-(3,4 epoxycyclohexyl}- ethyltriniethoxysHa; r-glyctdoxypropyltrimetJioxysiiane; r- giycidoxypropylmethyiidletboxysfiane; N-beia-(aminoethyl)-r-am nopropy{t ^"methoxysi.ian.e; N- beta^aminoeti.yl)-r-anunopTOpyl.metbyldimeiboxysilai.e; r-aminopropyltrieAoxysikne; N- phenyl-f-aminopropyltrimethoxysilane; r-mereaptoprapyltrimetboxysilane; r- chloiOpropyliriiTiethoxysi!ane; K^![3~(irimethox.ysjSyl}propy1 j-eth> enedianiine; substituted si lanes where one or more of the substitutions contains a different functional group; or any combinations thereof. Generally, the silane coupling agent may be included in the hardening agent in an amount capable to sufficiently bond the resin. In some embodiments, the silane coupling agent may be included in the hardening agent in the range of about 0.1 % to about 95% by volume of the ^'hardening agent Those of ordinary skill in the art. with the benefit of this disclosure, should be able to select a silane coupling agent fo a particular application..

[0024] Embodiments of the resin composition may be prepared in accordance with any suitable technique, in some embodiments, the desired quantity of resin may be .introduced into a mixer (e.g., a batch mixer) prior to or -followed by the addition of any optional hardening agent and/or diluent. Additional additives, if any, may be added to the mixer as desired prior to, or after, the addition of the resin to the mixer. This mixture mav be agitated for a sufficient period of time. By way of example, pumps may be used for delivery of the resin composition into the weSlhore. As will be appreciated by those of ordinary skill in the art, with the benefit of this disclosure, other suitable techni ues for preparing the resin composition may be used in accordance with embodiments.

[0025] Without being limited by theory, resin compositions exposed to water in the wellbore may have accelerated thickening times. This may be of special concern in high- temperature applications. The accelerated thickening effect may be due to the water opening the epoxide rings in the resin. Thus, it may be desirable to isolate the resin composition from water in the vveilbore so as to not accelerate the thickening time and lead to a preroaiure placement of the resin. Generally, a spacer fluid may be employed to separate one fluid from another; however typical spacer fluids are aqueous. Advantageously, it has been discovered that aqueous spacer fluids comprising salts of Group Ϊ alkali metals (i.e., lithium_* sodium, potassium, rubidium, cesium) may have a reduced accelerating effect on the resin composition, such that the resin composition may be placed without prematurely setting.

[0026] Embodiments of the spacer fluid may comprise water and salts of Group Ϊ alkali metals. The spacer fluids may be pumped into the wellbore Immediately prior to and immediately subsequent to pumping the resin composition in the wellbore. Therefore, in embodiments, the resin composition may have no contact or reduced contact with any other wellbore fluid.

[0027] The spacer fluids generally should have a density suitable for a particular application as desired b those of ordinary skill in the art. fn some embodiments, the space fluids may have a density in the range of from about 4 poitnds per gallon C'ppg") to aboitt 24 ppg. In other embodiments, the spacer fluids may have a density in the range of about 4 ppg to about 17 ppg. In yet other embodiments, the spacer fluids may have a density in the range of about 8 ppg to about 13 ppg. In still other embodiments, the spacer fluids may have a density of about 9 ppg to aboitt 10 ppg. in some embodiments, the spacer fluids (whether pumped prior to or subsequent to the resin composition) may be denser than the resin composition. Alternatively, in some embodiments, the spacer fluids (whether pumped prior to or subsequent to the resin, composition) may be less dense than the resin composition. Embodiments of the spacer fluids may comprise a means to reduce the density of their densi ty, such as hollow microspheres, low- density elastic beads, or other density-reducing additives known in the art. In some embodiments, weighting agents may be used to increase the density of the spacer fluids. Those of ordinary skill in the art, with the benefit of this disclosure, should recognize the appropriate density of a spacer fluid for a particular application.

[0028] The water may be included in an amount sufficient to form a pumpable slurry. For exanipie. the water may be included in the spacer fluids in an amount, in the range of from about 0.5% to about 99.5% by weight of the spacer fluid and, alternatively, in an amount in a range of from about 25% to about 75% by weight of the spacer fluid. By way of further example, the water may be present in an amount ranging between any of and/or including any of about 45% to about 65% by weight of the spacer fluid. One of ordinary skill in the art, with, the benefit of this disclosure, should recognize the appropriate amoun of the water to include for a chosen application.

[0029] Embodiments of the spacer fluids comprise salts of Group I alkali metals. Examples of Group 1 alkali metals include lithium, sodium, potassium, rubidium, cesium. Salts of Group 1 alkali metals may include any such salt sufficient for mitigating the catalytic effect of water on the resin composition including, but not limited to, lithium fluoride, lithium chloride, lithium bromide, lithium Iodide, lithium nitrate, lithium formate, lithium acetate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium formate, sodium acetate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium formate, potassium acetate, rubidium fluoride, rubidium chloride,, rubidium bromide, rubidium iodide, rubidium nitrate, rubidium formate, rubidium acetate, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, cesium nitrate, cesium formate, cesium acetate, or any combinations thereof. The alkali metal salts may be included in the spacer fluids in an amount in the range of from about 0,5% to about 99.5% by weight of the spacer fluid and, alternatively, in an amount in a range of from about 25% to about 75% by weight of the spacer fluid. By wa of further example, the alkali metal salts may be present in an amount ranging between any of and/or incl uding any of about 45% to about 65% by weight of the spacer fluid. One of ordinary skill in the art, with the benefit of this disclosure, should recognize the appropriate amount of alkali metal salts to include for a chosen application. Without limitation, the ratio of water to alkali metal salt i application and component specific. In some cases water ma be the major component, in some cases it may be the salt, factors important in deciding the ratio and amounts of water and alkali metal, salt include the choice of salt (e.g., and thus the maximum salt solubility) and the needs of the well.

[0030] A wide variety of additional additives may be included in the spacer fluids as deemed appropriate by one skilled in the art, with, the benefit of this disclosure. Examples of such additives include, but are not limited to: supplementary settable or cementitious materials, weighting agents, viscosifying agents (e.g., clays, hydratable polymers, d.iutan. xanthan gum. guar and guar derivatives, and cellulose derivatives or an combination thereof), fluid loss control additives, lost circulation materials, filtration control additives, d persants, foaming additives, defoamers, corrosion inhibitors, scale inhibitors, formation conditioning agents, and water- wetting surfactants. Water- wetting surfactants may be used to aid in removal of oil from surfaces in the wellbore (e.g., the casing) to enhance cement and resin bonding. Specific examples of these, and other, additives include: organic polymers, biopo!yroers, latex, ground rubber, surfactants, crystalline silica, amorphous silica, silica flour, fumed silica, nano-eSays (e.g., clays having at. least one dimension less than 100 n.m), salts, fibers, hydratable clays, microspheres, rice husk ash. micro-fine cement (e.g., cement having an average particle size of from about 5 microns to about 10 microns), nietakaolin, zeolite, shale, Portland cement, Portland cement interground with pumice, periite, barite, slag, lime (e.g., bydrated lime), gypsum, and any combinations thereof, and the like, A person, having ordinary skill in the art, with the benefit of this disclosure, should readily be able to determine the type and amount of additive useful for a particular application and desired result.

[0031 J Weighting agents are typically materials that weigh more than water and may be used to increase the density of the spacer fluids. By way of example, weighting agents may have a specific gravity of about 2 or higher (e.g. , about 2, about 4, etc. ). Examples of weighting agents that may be used include, but are not limited to, hematite, hausmanntte, barite, and combinations thereof. Specific examples of suitable weighting agents include HI-DENSE* weighting agent, available from Halliburton Energy Services, Inc.

[{KB 2 J lightweight additives may be included in embodiments of the spacer fluids to, for example, decrease the density of the spacer fluids. Examples of suitable lightweight additives include, but are not limited to, hentoniie, coal, diatomaeeous earth., expanded periite, fly ash, giisonite, hollow microspheres, low-density elastic beads, nitrogen, pozzoian-be.ntonite, sodium silicate, combinations thereof or other lightweight additives known in the art,

[0033] Embodiments of the spacer fluids may be prepared in accordance with any suitable technique. In some embodiments, the desired quantity of water may be introduced into a. mixer (e.g., a batch mixer) followed by the dry blend. The dry blend may comprise the alkali metal salts and any additional solid additives. Additional liquid additives, if any, may be added to die water as desired prior to, or alter, combination with the dry blend, the mixture may be agitated for a sufficient period of time. By way of example, pumps may be used for delivery of the spacer fluid into the welibore. As will be appreciated by those of ordinary skill in the art, with the benefit of this disclosure, other suitable techniques for preparing the spacer fluids may be used in accordance with embodiments,

[0034] An example method may comprise pumping a spacer fluid comprising alkali metal salts into a welibore penetrating a subterranean formation. The method additionally comprises pumping a resin composition alter the spacer fluid into the welibore penetrating a subterranean formation. Lastly, the method comprises pumping another spacer fluid comprising alkali metal salts into the welibore penetrating a subterranean formation after the resin composition, One or more optional additives may be included in the resin composition as discussed herein. One or more optional additives may be included in the spacer fluids a discussed herein. [0035 ] As will be appreciated by those of ordinary skill in the art, embodiments of the resin composition may be used in a variety of subterranean operations, including primary and ^•remedial cementing, in some embodiments, a resin composition may be provided that comprises resin, and optionally a hardening agent and/or diluent. The resin composition ma e introduced into a subterranean formation and allowed to set therein. As used herein, introducing the resin composition into a subterranean formation includes introduction into any portion of the subterranean formation, including, without limitation, into a wellbore drilled into the subterranean formation, into a near well bore region surrounding the wellbore, or into both.

[0036] in primary cementing embodiments, for example, the resin composition may be introduced into an annular space between a conduit located in a wellbore and the wails of a wellbore (and/or a larger conduit in the wellbore), wherein the wellbore penetrates the subterranean, formation. The resin, composition may be allowed, to set in the annular space to form an annular sheath of hardened resin. The resin composition ma form a barrier that prevents the migration of fluids in the wellbore. The resin composition may also, for example, support the conduit in the wellbore.

[0037] in remedial cementing embodiments, the resin composition may be used, for example, in. squeeze-cementing operations. By way of example, the resin composition may be placed in a wellbore to plug a void or crack in the formation, in a grave! pack, in the conduit, in the cement sheath, and/or in a icroannnSus between the cement sheath and the conduit

[0038] Another example method comprises sealing a portion of a gravel pack or a portion of a subterranean formation. The method may comprise providing a resin composition; introducing the resin composition into the portion of the gravel pack or the portion of the subterranean formation; and allowing the resi compositio to form a hardened mass in said portion. The portions of the subterranean formation may include permeable portions of the formation, fractures (natural or otherwise) in the formation, and other portions of the formation that may allow the undesired flow of fluid into, or from, the wellbore. The portions of the gravel pack include those portions of the gravel, pack, wherein it is desired to prevent the undesired flow of fluids into, or from, the wellbore. Among other things, this method may allow the sealing of the portion of the gravel pack to prevent the undesired How of fluids without, requiring the grave! pack's removal.

[0039] Another example method may comprise sealing voids located in a pipe string (e.g., casing, expandable casings, liners, etc.) or in a cement sheath. Generally, the pipe string will be disposed in a wellbore, and the cement sheath may be located in the annn!us between the pipe string disposed in the well bore and a wall of the well bore. An example of such a method may comprise providing a resin composition; introducing the resin composition into the void; and allowing the- resi composition to set to form a hardened mass in the void.

[0040] When sealing a void in a pipe string, some embodiments may comprise locating the void in the pipe string; and isolating the void by defining a space within the pipe string in communication with the void; wherein the resin composition may be introduced into the void ^•from the space. The void may be isolated using any suitable technique and/or apparatus, including bridge plugs, packers, and the like. The void in the pipe string may he located using any suitable technique,

[004 ! ] When sealing a void in the cement sheath, some embodiments may comprise locating the void in the cement sheath; producing a perforation in the pipe string that intersects the void; and isolating the void by defining a space within the pipe string in communication with the void via the perforation, wherein the resin composition is introduced into the void via the perforation. The void in the pipe string may he located using any suitable technique. The perforation may be created in the pipe string using any suitable technique, for example, perforating guns. The void may he isolated using any suitable technique and/or apparatus, including bridge plugs, packers, and the like.

[0042] In some embodiments, the resin compositions may have desirable thickening times after exposure to a spacer fluid comprising a Group I alkali metal. Thickening time typically refers to the time a fluid, such as a resin composition, remains in a fluid state capable of being pumped. A number of different laboratory techniques may be used to measure thickening time. A pressurized consistometer, operated in accordance with the procedure set forth in API R.P Practice i OB-2, Recommended Practice for Testing Weil Cements, First Edition, July 2005, may he used to measure whether fluid is in. a pumpable fluid state. The thickening time may be the time for the fluid to reach 100 8c and may be reported as the time to reach 100 Be. In some embodiments, the resin, compositions may have a thickening time of greater than about 1 ,5 hours, alternatively, greater than about 3 hours, and further alternatively greater than about 3.5 hours at 3,000 psi and temperatures in a range of from about 50 °F to about 400 °F, alternatively, in a range of from about 80 °.F to about 250 ^CF, and alternatively at a temperature of about 140 ^■°F.

[0043] An example embodiment comprises introducing a spacer fluid into a wei.lbo.re, wherein the spacer fluid comprises a group 1 alkali metal salt and water; and introducing a resin composition into the wellbore after the spacer fluid, wherein the resin composition comprises a resin and a hardening agent.

[0044] Another example embodiment comprises pumping a first spacer fluid into a wellbore and into a perforation in a cement sheath, wherein the cement sheath is cemented to walls of the wellbore, wherein the first s acer fluid comprises a group I alkali metal salt and water; pumping a resin composition into the wellbore and into a perforation in the cement sheath, wherein the resin composition is allowed to harden in the perforation, wherein the hardened resin composition prevents the migration of fluids through the perforation, and wherein the resin composition comprises a resin and a hardening agent; and pumping a second spacer fluid into the wellbore, wherein the second spacer fluid comprises the group I alkali metal salt and water.

[0045] An additional example embodiment comprises a resin placement system comprising a spacer fluid which comprises a group I alkali metal and water; a resin composition comprising a resin and a hardening agent; mixing equipment capable of mixing at least one of the spacer fluid or the resin composition; and pumping equipment capable of delivering at least one of the spacer fluid or the resin composition into a wellbore.

[0046] Example methods of using the resin composition and the spacer fluids will now be described in more detail with reference to FIGs. 1-6, Any of the previous embodiments of the resin composition and space fluid may apply in the context of FIGs. 1 -6, Referring now to FIG. 1, the preparation of a resin composition or a spacer fluid in accordance with example embodiments will now be described. FIG. 1 illustrates a system 2 for the preparation of either a. resin composition or a spacer fluid and subsequent delivery of the resin composition and/or the spacer fluid, to a wellbore in accordance with certain embodiments. As shown, the resin ^•composition or the spacer fluid may be mixed in mixing equipment 4, such as a jet mixer, recirculating mixer, or a batch mixer, for example, and then pumped via pumping equipment 6 to the wellbore. In. some embodiments, the mixing equipment 4 and the pumping equipment 6 may be disposed on one or more cement trucks as will be apparent to those of ordinary skill in the art.

[0047] An example primary cementing technique using a resin composition will now be described with reference to FIGs. 2 and 3. FIG, 2 illustrates surface equipment 10 that may be used in the placement of a resin composition in accordance with certai embodiments, it should be noted that while FIG. 2 generally depicts a land-based operation, those skilled in the art will readil recognize that the principles described, herein are equally applicable to subsea operations that employ floating or sea-based platforms and rigs, without departing from the scope of the disclosure. As illustrated by FIG. 2, the surface equipment Ϊ0 may include a cementing unit 12, which may include one or more cement trucks. The cementing unit 12 may include mixing equipment 4 and pumping equipment 6 (e.g., FIG. I) as will be apparent to those of ordinary skill in the art. Cementing unit 12, or multiple cementing units 12, may pump a first spacer fluid 13, a resin composition 14, and/or a second spacer fluid 1 (as shown in FIG. 3) through a feed pipe 16 and to a cementing head 18 which conveys the first spacer fluid 13, resin composition 14, and/or a second spacer fluid 15 downhole.

[0048] F G. 3 generall depicts the placement of resin composition 14 into a subterranean formation 20 in accordance with example embodiments. As illustrated, a welJbore 22 may be drilled into the subterranean formation 20. While wej.ibo.re 22 is shown extending generally vertically into the subterranean formation 20, the principles described herein are also applicable to we!Jbores that extend at an angle through th subterranean formation 20, such as horizontal and slanted weilbores. As illustrated, the wellbore 22 comprises walls 24. In the illustrated embodiment, a surface casing 26 has been inserted into the wellbore 22. The surface easing 26 may be cemented in the wellbore 22 by a cement sheath 28. In alternative embodiments, surface casing 26 may be secured in the wellbore 22 by a hardened resin sheath in place of cement sheath 28. in the illustrated embodiment, one or more additional conduits (e.g., intermediate casing, production casing, liners, etc.}, shown here as casing 30 may also be disposed in the wellbore 22. As illustrated, there is a wellbore annul us 32 formed between the casing 30 and the walls 24 o the wellbore 22 and/or the surface casing 26. One or more oeniralizers 34 may be attached to the easing 30, for example, to centralize the casing 30 in the wellbore 22 prior to and during the cementing operation.

[0049] With continued reference to PIG, 3, a first spacer fluid 13 may be pumped down the interior of the casing 30, The first spacer fluid 13 may be allowed to flow down the interior of the casing 30 through the casing shoe 42 at the bottom of the easing 30 and op around the easing 30 into the wellbore annulus 32. After the .first spacer fluid 13 has been pumped into the casing 30, a resin composition 14 may be pumped into the easing 30, In a manner similar to pumping the first spacer fluid 13, the resin composition 14 may be allowed to flow down the interior of the casing 30 through the easing shoe 42 at the bottom of the easing 30 and up around the easing 30 into the wellbore annulus 3.2. After the resin composition 14 has been pumped int the easing 30, a second spacer fluid 15 may be pumped into easing 30 and allowed to flow down the interior of the casing 30. The first spacer fluid 13 and the second spacer fluid 15 may be used to separate the resin composition. 14 from fluids introduced into the wellbore 22 either in front of or behind the resin composition 14. Once the resin composition 14 has been placed into the desired position, in the wellbore annulus 32,. the resin, composition 14 may be allowed to set In the wellbore annulus 32, for example, to form a hardened .resin sheath that supports and positions the casing 30 in the wellbore 22. While not illustrated, other techniques may also be utilized for introduction of the resin composition 14. By wa of example, reverse circulation techniques ma be used that include introducing the resin composition 14 into the subterranean formation 20 by way of the wellbore annulus 32 instead of through the casing 30. These techniques may also utilize a first spacer fluid 13 and a second spacer fluid 15. As it is introduced, the resin composition 13 may displace the first spacer fluid 13. At least a portion of the first spacer fluid 13 may exit the wellbore annulus 32 via a flow line 38 and be deposited, for example, in one or more retention pits 40 (e.g., a mud pit), as shown on FIG. 2,

[0050] FIGs. 4-6 Illustrate methods of secondary cementing. Turning now to FIG, 4, there is shown a partial cross-section of a conventional producing wellbore 22 that has primary cementing of the casing 30, The cement sheath 28 around the casin 30 may have defects potentially caused by a variety of issues, such as improper curing of the cement sheath 28 while it was being formed. Alternatively, the primary cementing may have been successful, but due to adverse temperatures and pressures within the subterranean formation 20, the casing 30 and/or the cement sheath 28 surrounding the casing 30 may form cracks or other types of small perforations 44. The small perforations 4 may be problematic since they may facilitate the introduction of undesirable fluids into the easing 30. As shown in FIG. 4, a small perforation 44 has formed in the cement sheath 28 and the casing 30, potentially allowing the introduction of undesirable fluids into the i nterior of the casing 30.

[005 J ] Referring now to FIG. 5, a small perforation 44 may be filled or plugged by a resin composition 14. A plug 46 (the plug 46 may be any type of plug, e.g., bridge plug, etc.) may be initially placed adjacent and below the small perforation 44, to form a barrier to prevent .resin composition 1.4 from flowing down the wellbore ^"2^*2 and therefore allow resin composition 1.4 of the present disclosure to fill the small perforations 44 in the casing 30 and cement sheath 28. As shown in FIG. 5, tubing 48 (e.g., coiled tubing, drill pipe, etc.) may be lowered into wellbore 22. A first spacer fluid 13 may be pumped Into the weSlbore 22 via the tubing 48 and allowed to flow down the interior of the tubing 48 and into the blocked section of the wellbore 22 created by the plug 46. A portion of the first spacer fluid .13 may then flow through the small perforation 44 while another portion may reside in. the annulus 32. After pumping the first spacer fluid 13 through the tubing 48, the resin composition 14 may be pumped through the tubing 48. The resin composition 14 may be pumped down the Interior of the tubing 48 and into the blocked section of the wellbore 22 created by the plug 46. A portion of the resin composition 14 may then flow through the small, perforation 44 while another portion may reside in the annulus 32, The restn composition 1.4 may be allowed to set in the small perforation 44 and in a portion of the wellbore annulus 32, for example, to form a hardened resin that seals small perforation 44 to prevent the migration of undesirable fluids into the interior of the casing 30. Alter the resin composition. 14 has been pumped into the tubing 48, a second spacer fluid .15 ma be pumped into the tubing 48 and allowed to flow down the interior of the tubing 48 into the blocked section of the wel lbore 22 created fay the plug 46 and up around the tubing 48 into the wellbore annulus 32. The tubing 48 may then be removed, lire plug 46 may also be removed, in alternative embodiments, plug 46 may remain in the weilbore 22 and be drilled through. After tubing 48 is removed, the portion, of the hardened resin composition 14 remaining in the weHbore 22 (i.e., the portion not in the small perforation 44) may then be dri lled through.

[0052] FIG. 6 describes another embodiment of filling a small perforation 44 with a resin composition 14. A plug 46 (the plug 46 may be my type of plug, e.g., bridge plug, etc.) may be initially placed adjacent and below the small perforation 44, to form a barrier that may allow pressurized pumping of a resin composition 14 of the present disclosure to fill any small perforations 44 in the casing 30 and cement sheath 28. As shown in FIG, 6, tubing 48 (e.g., coiled tubing, drill pipe, etc.) may be lowered into weilbore 22. Tubing 48 may be attached to a retainer 50 or ma be inserted into a retainer 50 alread placed into the weilbore 22. Retainer 50 ma allow for the pressurized pumping of the resin composition 1.4 into any small perforations 44. Retainer 50 must be placed adjacent to and above the small perforations 44 to be filled by resin composition 14. Retainer 50 may be any type of retainer, for example, a cement retainer. After plug 46, tubing 48, and retainer 50 are placed, a first spacer fluid 1.3 snay be pumped into the weilbore 22 via the tubing 48 and allowed to flow down the interior of the tubing 48 and into the blocked section of the weilbore 22 created by the plug 46. A portion of the first spacer fluid 1 may then flow through the small perforation 44. After pumping the first spacer fluid 13 through the tubing 48, the resin composition 14 may be pumped thmugh the tubing 48, The resin composition 14 may be pumped down the interior of the tubing 48 and into the blocked section of the weilbore 22 created by the plug 46. A portion of the resin composition 14 may then flow through the small perforation 44 while another portion may reside in the space formed between the plug 46 and retainer 50. The resin composition 14 may be allowed to set in the small perforation 44 and in the space formed between the plug 46 and retainer 50, ^"Hie resin composition 14 may then, harden to form a .hardened resin that seals small perforation 44 to prevent the migration of undesirable fluids into the interior of the casing 30, After the resin, composition .14 has been pumped into the tubing 48, a second spacer fluid 15 may be pumped into the tubing 48 and aliovved to flow down, the interior of the tubing 48 into the blocked section of the weilbore 22 created by the plug 46 and into the space formed between the plug 46 and retainer 50. The tubing 48 may then be removed. The plug 46 may also be removed. In alternative embodiments, plug 46 may remain in the weilbore 22 and be drilled through. Retainer 50 may also be removed. Conversely, in alternative embodiments, retainer 50 may be drilled through. After tubing 48 is removed, the portion of the hardened resin composition 14 remaining in the weilbore 22 (i.e., the portion not in. the small perforation 44) may then be drilled through. [0053] The exemplary resin composition and spacer fluids disclosed herein may directly or indirectly affect one or more components or pieces of equipment associated with the preparation, delivery, recapture, recycling, reuse, and/or disposal of the resin composition and associated spacer fluids. For example, the resin composition and spacer fluids may directly or indirectly affect one or more mixers, related mixing equipment, mud pits, storage facilities or units, composition separators, heat exchangers, sensors, gauges, pumps, compressors, and the like used generate, store, monitor, regulate, and or recondition the exemplary resin composition and spacer fluids containing the same. The disclosed resin composition and spacer fluids may also directly or indirectly affect any transport or delivery equipment used to convey the resin composition and spacer fluids to a well site or downhoie such as, for example, any transport vessels, conduits, pipelines, trucks, tubuiars, and/or pipes used, to compositionally move the resin composition and spacer fluids from one location to another, any pumps, compressors, or motors (e.g., topside or downhoie) used to drive the resin composition and spacer fluids, or fluids containing the same, into motion, any valves or related joints used to regulate the pressure or flow rate of the resin composition and spacer fluids (or fluids containing the same), and any sensors (i.e., pressure and temperature), gauges, and/or combinations thereof, and the like. The disclosed resin composition and spacer fluids may also directly or indirectly affect the various downhoie equipment and tools that may come into contact with the resin composition and spacer fluids such as, but not limited to, wellbore casing, we!lbore liner, completion string, insert strings, drill string, coiled tubing, sl.ickl.ine, wireline, drill pipe, drill collars, mud .motors, downhoie motors and/or pumps, cement pumps, surface-mounted motors and/or pumps, centralizers, turbolizers, seraiehers, floats (e.g., shoes, collars, valves, etc.), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromechanieal devices, etc), sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, etc), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive coupler, etc), control lines (e.g., electrical, fiber optic, hydraulic, etc), surveillance Sines, drill bits and reamers, sensors or distributed sensors, downhoie .heat exchangers, valves and corresponding actuation devices, tool seals, packers, cement plugs, bridge plugs, and other wellbore isolation devices, or components, and the like,

EXAMPLES

1005 To facilitate a better understanding of the present embodiments, the following examples of some of the preferred embodiments are given. In no way should such examples be read to limit, or to define, the scope of the disclosure. Example 1

[0055] A resin composition comprising 600g of Araldite* GY 506 resin and 195g of Ethaeure*^' 300 hardening agent was mixed in. a W ring*^' blender at 2000rpm for 3 minutes. Arafdite* GY 506 resin is a btsphenol A epoxy liquid resin available from Huntsman Corp, of Salt Lake City, Utah. Ethaeure* 300 hardening agent is an aromatic amine available from Albemarle Corp, of Baton Rouge, Louisiana, ?9.5g of a brine solution representing a different potential spacer fluid formulation was added to the resin composition. The spacer fluid formulations comprised water and either a Cjroup I alkali metal salt, Group II alkali earth metal salt, i' a transition metal salt. The mixture of the resin composition and each spacer fluid formulation was blended for an additional 3 minutes. The type and amount of salt was varied for each mixture, while the formulation of the .resin composition was the same for each sample. After blending, the thickening times of each mixture was measured using a high-pressure, high- temperature eonslsioraeter where the mixtures were heated to 250 °F at a pressure of 3000psi for 45 minutes, The thickening times were the times for the resin to reach S 00 Be. The results and the density of each mixture, is presented in Table 1 below.

Table 1. Thickening limes of Resin Composition with Added Spacer Fluid

[0056] The results indicate that exposure of the resin composition to a spacer fluid comprising Group 1 alkali metals increases the thickening time compared to exposure to spacer fluids comprising Group 11 alkali earth metals or transition metals. Moreover, the thickening time is also increased compared to exposure to water alone,

[0037] St should be understood that the compositions and methods are described in terms of "comprising " "containing," or "including" various components or steps, the compositions and methods can also "consist essentially of or "consist of the various components and steps. Moreover, the indefinite articles "a" or "an," as used in the claims,, are defined herein to mean one or more than one of the element that it introduces.

[0058] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any Sower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit ma be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitl recited. Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed. In particular, every range of values (of the form, "from about a to about V or, equivalent!}', "from approximately a to b," or, equivalently, "f om approximately a-b") disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values even if not explicitly recited. Thus, every point or individual value ma serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0059] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those thai are inherent therein, The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Although individual embodiments are discussed, the invention covers all combinations of all those embodiments. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. If there is any conflict In the usages of a word or terra in this specification and. one or more patent(s) or other documents that may be incorporated herein by reference, the definitions that are consistent with this specification should be adopted.

Claims

What is claimed is;

1 . A method comprising;

introducing a spacer ^'fluid into a. we!lbore, wherein the spacer fluid comprises a group 1 alkali metal salt and water; and

introducing a resin composition into the we!ibore after the spacer fluid, wherein the resin composition comprises a resin and a hardening agent,

2. A method according to claim 1 wherein the group I alkali metal salt comprises a salt .selected from, the group consisting of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium formate, lithium acetate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium, formate, sodium aceiate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium formate, potassium acetate, rubidium, fluoride, rubidium, chloride, rubidium bromide, rubidium iodide, rubidium nitrate, rubidium formate, rubidium acetate, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, cesium nitrate, cesium. formate, cesium acetate, and any combinations thereof

3. A method according to claim .1 wherein the spacer fluid further comprises a viscosity ing agent selected from the group consisting of clays, hydratable polymers, diutan, xanthan gum, guar and guar derivatives, cellulose derivatives, and any combination thereof,

4. A method according to claim 1 wherein the spacer composition further comprises a weighting agent or lightweight additive.

5. A method according to any preceding claim wherein, the resin composition comprises a diluent.

6. A method according to claim 5 wherein the diluent is selected from the group consisting of butyl glyeidyl ether, cyclohexane ciimethanoi di glyeidyl ether, polyethylene glycol, butyl lactate, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl, formamide, diethyleneglycol methyl ether, ethyleneglyeol butyl ether, diethy!eneg!yeol butyl ether, propylene carbonate, d'liraonene, fatty acid methyl esters, and any combinations thereo

7. A method according to any preceding claim wherein the resin composition comprises a resin, selected from the group consisting of epoxy-based. resins, novolae resins, polyepoxide resins, phenol-aldehyde resins, urea-aldehyde resins, urethane resins, phenolic resins, furen/J rfcryl alcohol resins, phenolic/latex resins, phenol .formaldehyde resins, bisphenol A diglycidyl ether resins, butoxymethyl butyl glycidyl ether resins, bisphenol A-epichlorohydrin resins, bisphenol F resins, glycidyl ether resins, polyester resins and hybrids and copolymers thereof, poJyureihane resins and hybrids and copolymers thereof, aery!ate resins, and any com hin lions thereo .

8. A method according to any preceding claim wherein the resin composition comprises a hardening agent selected from the group consisting of aliphatic amines, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, amido amines, polyamides, polyethyl amines, poiyether amines, polyoxyalkylene amines, carboxylie anhydrides, triethylenetetraamine, ethylene diamine, N-cocoalkyltrimethyiene, isophorone diamine, - aminophen l piperazioe, imidazoline, 1 ,2-ditiminocycIohesane, polytheramine, diethy!tolueoediamine, 4,4'-diammodiphenyl methane, methyl tetrahydrophthalic anhydride, hexahydrophthalie anhydride, maleic anhydride, polyazelaic polyanhydride, phthalie anhydride, and any combinations thereof.

9. A method according to any preceding claim wherein the spacer fluid has a density between 5 ppg to 24 ppg.

10. A method according to any preceding claim wherein at least a portion of the resin composition is allowed to enter into and harden in a perforation in a casing within a weiibore.

1 1. A method according to any preceding claim wherein at least a portion of the resin composition is allowed to enter into and harden in. a perforation in a cement sheath within a weiibore.

12. A. method according to claim 10 or claim 1 1 further comprising allowing at least a portion of the spacer fluid to remain in the weiibore,

13. A method according to an preceding claim, further comprising introducing a second spacer fluid into the weiibore after the resin composition, wherein the second spacer fluid comprises a group I alkali metal salt and water.

1.4. A method according to an preceding claim wherein the resin composition has a thickening time in the weiibore of greater than or equal to I hour, wherein the thickening time is the time to ί 00 Be,

15. A method comprising; pumping a first spacer fluid into a welibore and into a perforation in a cement sheath, wherein the cement sheath is cemented to walls of the welibore, wherein the first spacer fluid comprises a group I alkali metal sail and water;

pumping a. resin composition into the welibore and into a perforation in the cement sheath, wherein the resin compositioti is allowed to harden in the perforation, wherein the hardened resin composition prevents the migration of fluids through the perforation, and wherein the resin composition comprises a resin and a hardening agent; and

pumping a second spacer fluid into the welibore_* wherein the second spacer fluid comprises the group 1 alkali metal salt and water.

16. A method according to claim 15 wherein the group I alkali metal salt is selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium .nitrate, lithium formate, lithium acetate, sodium fluoride, sodium chloride, sodium, bromide, sodium iodide, sodium nitrate, sodium formate, sodium acetate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium formate, potassium acetate, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, rubidium nitrate, rubidium formate, rubidium acetate, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, cesium nitrate, cesium formate, cesium acetate, and any combinations thereof

1 7. A method according to claim 15 or claim. .16 wherein the resin composition comprises a diluent.

I S. A method according to claim 1? wherein the diluent is selected from the group consisting of butyl glycidyJ ether, cyclohexane dimethanol diglycidyl ether, polyethylene glycol, butyl lactate, di ropylene glycol methyl ether, dipropy!ene glycol dimethyl ether, dimethyl fo.rmaniide, diethyienegiyeoi methyl ether, ethyleneglycoS butyl ether, diethyienegiyeoi butyl ether, propylene carbonate, dM.imone.ne, fatty acid methyl esters, and any combinations thereof.

19. system comprising;

a spacer fluid comprising a group ! alkali metal and water;

a resin composition comprising a resin and a hardening agent;

mixing equipment capable of mixing at least one of the spacer fluid or the resin composition; and

pumping equipment capable of delivering at least one of the spacer fluid or the resin composition into a welibore.

20. A system according to claim 19 wherein the group I alkali metal salt is selected from the group consisting of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate,, lithium formaie, lithium acetate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium formate, sodium acetate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium formate, potassium acetate, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, rubidium nitrate, rubidium formate, rubidium acetate, cesium fluoride, cesium chloride, cesium bromide, cesium iodide, cesium nitrate, cesium formate, cesium acetate, and any combinations thereof,

21. A system according to claim 19 or claim 20 wherein the resin composition comprises a diluent

22. A. system according to claim 21 wherein the diluent is selected from the group consisting of butyl gfycidyl ether, cyelohexane dimethanol digfyeidyi ether, polyethylene glycol, butyl lactate, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl forroamide, diethyleneg!ycoi methyl ether, elhyieneglycol butyl ether, diethyleneglycot butyl ether, propylene carbonate, d'limonene, fatty acid methyl esters, and any combinations thereof