CA2882817A1 - Resin-based sealant compositions comprising cement kiln dust and methods of use - Google Patents
Resin-based sealant compositions comprising cement kiln dust and methods of use Download PDFInfo
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- CA2882817A1 CA2882817A1 CA2882817A CA2882817A CA2882817A1 CA 2882817 A1 CA2882817 A1 CA 2882817A1 CA 2882817 A CA2882817 A CA 2882817A CA 2882817 A CA2882817 A CA 2882817A CA 2882817 A1 CA2882817 A1 CA 2882817A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/14—Polyepoxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/16—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00043—Anhydrous mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
Methods and compositions are provided that relate to resin-based sealant compositions comprising cement kiln dust. An embodiment discloses a method comprising: providing a resin-based sealant composition comprising a liquid hardenable resin component and kiln dust; and allowing the resin-based sealant composition to harden.
Description
RESIN-BASED SEALANT COMPOSITIONS COMPRISING CEMENT KILN
DUST AND METHODS OF USE
B AC KG ROUND
[00011 The present invention relates to resin ,based sealant ciompositionS.
and, particularly, in cemin embodiments, to re-base d seidant compoSitions -that.
comprise 'cement kiln dust ("CICD".) and associated methods oft.tse serviCingvell bores.
[00021 Sealant compositions may be used in a variety of subterranean application's.
For example, in subterranean well construction, iconduit (e.g., pipe string, ensingõ líners expandable tubularsõ etc.) .nay be run into a rell hor iril cemented in place.
The process of cementing the pipe .string in .place is commonly referred. to .as 4'primary cementing," In a .typical primary;-eerrienting method, a 'sealant .composition may be pumped into an annulus between the. walls. oî the well bore and the exterior surface .of the pipe String disposed therein. The sealant composition mayset in the annular spat, thereby forming an annular sheath of hardened, substantially impermeable 'seal (i.e. a sealant sheath) that may support and .position the pipe string in the well bore and may bond the .exterior surface of the pipe string to the.subterranean formation or the inside of a. larger conduit. Among other .things, the sealant sheath surrounding the pipe string I-Unctions to prevent the mieration of fluids ìri the annulus, as well as protecting the pipe string from corrOsion. .Sealant compositionS also may he used in remedial-cementing methods, fOr example...to seal voids in pipe strings or
DUST AND METHODS OF USE
B AC KG ROUND
[00011 The present invention relates to resin ,based sealant ciompositionS.
and, particularly, in cemin embodiments, to re-base d seidant compoSitions -that.
comprise 'cement kiln dust ("CICD".) and associated methods oft.tse serviCingvell bores.
[00021 Sealant compositions may be used in a variety of subterranean application's.
For example, in subterranean well construction, iconduit (e.g., pipe string, ensingõ líners expandable tubularsõ etc.) .nay be run into a rell hor iril cemented in place.
The process of cementing the pipe .string in .place is commonly referred. to .as 4'primary cementing," In a .typical primary;-eerrienting method, a 'sealant .composition may be pumped into an annulus between the. walls. oî the well bore and the exterior surface .of the pipe String disposed therein. The sealant composition mayset in the annular spat, thereby forming an annular sheath of hardened, substantially impermeable 'seal (i.e. a sealant sheath) that may support and .position the pipe string in the well bore and may bond the .exterior surface of the pipe string to the.subterranean formation or the inside of a. larger conduit. Among other .things, the sealant sheath surrounding the pipe string I-Unctions to prevent the mieration of fluids ìri the annulus, as well as protecting the pipe string from corrOsion. .Sealant compositionS also may he used in remedial-cementing methods, fOr example...to seal voids in pipe strings or
2( cement sheaths, to seal highly permeable formation zones or fractures, to place a cement plug,. .and the like., As used herein the term "void" refers to any type of space, including fractures,. boles, cracks. channels., spaces, and the like. Such voids may include,: holies or cracks in the pipe strings; holes., crack, spaces, or channicla. in the sheath; and very ..small spaces (coMmonly referred tdaS "Miero-annuli") between the :interior surface of the sealaut sheath and the exterior surface of the conduit or between the outer surface of the .sealant sheath and the ton.11.000 or inside surface Of a :larger .conduit, Sealing:
such voids may prevent the undesired flow of fluids. (e.g,., gas, water, etc.). and/or tine solids into, or trOm, the Well bore. Sealant compositions also May be used in .surface appiicatiottS, for example, construction cementing.
[000M A variety of differeta sealant compositions, including. non-cementitious sealants,. such as resin-based sealant compositions haw beth: used in these primafy- and secondary-cementing methods. Resin-based sealant compositions may comprise, for example, a liquid hardenable ageat compondit and a hardening ogent COMpOrIpt BOC4thie7 resin-based sealant compositions may have increased flexibility and toughness as. compared to conventional cement compositions, the resin-based sealant COaiposition nay be=used, f.or example, :in applications 'Acre inereased =Stresses andlor increased numbcr (if stres.$ cycles may be encotmtered. For owmole, resin-based sealant compositions rttay have applicability in cementing methods performed in shale fOrtnations as wells drilled in these types of formations flaay require multiple fracturing stages requiring the sealant compositions to have =sufficient flexibility and toughrios to withstand repeated hydraulic stress and themial cycles.
In addition, resased sealant cotripositioOS may alSo be placed into the I
bore:to plug a void in the conduit (e.g., the pipe: stritig)Hor cetnent sheath or a void that may have fOrmed between the sheath and a wall of the well bore or the. conduit. While resin-based sealant compositions may be, used instead of conventional cementitions-based se.alant compositions certaill applications, drawbacks exiSt with use of snob sealant coinpositions, includin g the high cost of the resins, for example.
SUMMARY
[00041 An e.mbodiment of the present invention provides a method comprising providing a resin-based sealant composition:comprising a liquid hardenahle resin: component and kiln dust; and allovAtig the min-based sealant composition to harden.
110005] Another .embodiment of the present invention provides.a method of forming astal in a subterranean :formation comprising: introducing a resin-based sealant composition into a subterranean formation, wherein the resin-based sealant composition comprises a liquid hardenable resin component and cement kiln dust; and allowing the resin-based 'sealant composition to harden in the stibtedanean formation, 1.0 [00061 Another mbodiment of the present inventiOn-provides a resin-based sealant .eomposition comprisin a liquid. hardenabieresin component and cement .kiln dust.
[OWY71 The teatures.and advantages of the present :invention NVill be readily apparent to those skilled in the art. While numerous changes may be made by those.skilled in the art, such changes .are within the spirit ofthe invention, DESCRIPTiON OF PREFERRED EMBODIMENTS
[0008] The present invention relateS to resin-based .Sealant compositions Hand,. More particularly, in certain embodiments., to resin-based :sealant compositions that comprise cenient kiln dust..("CKD").and.aSsociated met hodS=of use in servicing well bores. One o.f the many potential advantages of the methods and compositions .of the present .invention is that the CKD may be Used as a non-hydratine filler material to IoWer. the consumption of the moreexpensive.components (e.g:õ hardenable resin component, etc.) -that are typic a y used ìr resit-based. sealant compositions. Yet another potential advantag.e is that the CKD .may aid the sealing of voids .such as cracks that may form in the hardened sealant composition.
I 0 :By way of e.xtimple. the CKD may hydrate and harden upon .contact with waterõ for example, counteract the potential fort -nation of voldS (e.g., cracks, Micro-annuli, etc%) that may form in the hardened sealant composition:, [000)] Embodiments of the present invention disclose: resin-based Sealant compositions: Comprising a liquid hardenable resin. .component and CKI").. in some 1.5 embodiments, the resin-based sealant coinposition -may further comprise. a. liquid hardening agent component for facilitating the set :of the hardenable resin component.
In other embodiments, the liquid hardenable resin component may auto-cataly4e and not require the hardenable .resin component for Setting. The. resirt,hased. Sealant cOttmositions may be used in a .nutnber clifTeiviat stibterrantan .apptication$ iiAlth kb the sealant composition may be .introduced .into a subterranean formation and allowed .to harden, One .example of a .subterratean application includes primary-cementing methods in which the resin-based Iieplant composition may be allowed to harden in a well-bore annulus.. Another exatnple. of a subterranean application includes remediakeernenting methods ii'i. which the resin-based .sealant cOmposition May be allowed, for example, to .harden and seal Voids in pipe strings Or cement sheaths, to seal highly permeable formation zones or fractures, .to place a cement plug, and the like;
[0010] in some embodiments, the liquid hardenahle resin component of the resin-based 'Sealant composition may comprise a hardenable resin, an optional solvent, and :an optional aqueous diluentor carrier fluid. As used herein, the term ''resin"
refers to any of a = 39. number.oU ph ysical ly siMilar polymerized Synthetics or.
chemically niodified natural resins .including thermoplastic materials and thermosetting material& Examples of hz.,Irdenable resins that may be. used in the liquid hardenable reSiti component -include:, hut are not limited .to, epoxy-based resins, novolak resins, .pOlyepoxide resins, phonot-aldehyde resins,. urea aldehyde resins, urethane resins, phenolic resins, loran resins, furanArtitryl alcohol resins, :35 phenolicilatex reSins, phenol formaldehyde resins, hisphenol A
diglycidyl ether reSins, butoXythethyl. butyl .glycidyi ether regins, bisphental A-epiehlorohydrin resinS.õ biaphenot resins glyeidyl ether resins, polyester mains and hybrids and copol.yrnera thereof, polyurethane resins and hybrids and copolymers thereof; acrylate resins, and mixtures thereof. Some suitable resins, such as epoxy resins, may be cured µvith an internal catalyaror activator sia :that .when pumped dmanhol.e. they allay be cured using only tirne and .temperature. Other .sultable resins,. suchas furan msins .generally require a tine-ddayCO
Catalyst or an external catalyst to help activate the polymerization of the resins if the cure temperature s low (i.e., less. than 2.50'.1), but will awe under the effect of time and 'teinperature if the formation temperature is above. about 250T, preferably 'above about 10. 300F. 'ft is within the abil.it.y of one skilled in the artõ with the benefit of this diac1osurt4 to select a :Suitable resin fr uae in embodiments Of the present invention and to determine whether a Catalyst is required to trigger curing. One main that may be used in particular embodiments of .the present .invention is the consolidation agent commercially available from.
:11alliburton EnergyServices, Inca of Dunean. Okla., under the trade name."EXPED1TEOW..."
[0011.:j Selection of a suitable resin may be affected by the temperature of the .subterranean formation to which the composition will be introduced. By Way:
of example.
for subterranean. fortitations having a bottom hole static temperature Crif151.7') ranging from .about 60T to .about 25OF two-Omponent cp4y-bpsed resiris comprising a hardenable .i.csin component and a hardening .agent component containingspeeifie :hardening agents may be preferred. For subterranean forthationa .having a BUST ranging from about 30097 to about .600" F. A fitranabased resin may=be preferred, For SUbtararlean formations having a MST ranging from .about 200cF to about 400v.F, either a phenolic-based .resin or a one-component HT epoxy-based resin may be suitable. For subterranean formations having a MIST of at least about 175T, a phenol/phenol thrmaidehydeffurfuryl alcohol resin tnay also be. sulta.ble.
R/0121 Generally, the hardenable resin may .be= included in the liquid .hardenable 'resin component in an amount in a range of. from about 5% to about 100% by volume of the :liquid hardenable resin component. in particular embodiments, .the hardenable resin may be included in the liquid hard.enable resin .ciampenent in an amount in a range of fro. m about .75% to about '10.01- by volume of the liquid h.ardenable resin component it iS within the :ability of one skilled in the art with the benefit of .this disclosure to determine how .tnuch of the hardenable. resin may be needed to itchieve. the desired results. Factors that may .affect this detisiim. include the type of :hardenable resin and liquid hardening agent: used in a particular application.
[001.31 In some embodiment*, a. solvent iriay be added to :the resin to reduce its viscosity for ease= of handling, mixing and transfetring.
However, in particular embodiments,. :it may be desirable not to use. such .a solvent for 'environmental or safety :masons. lt is. within the ability of one skilled in the art with the benefit of this disclosure to determine if and how much .solvent may be: needed to Itehievea viseosity suitable to the subterranean conditions a a particular a.pplication. Factors that :may affect this deeiSiOn include geographic location of the well, the surrounding weather conditions, and thedesited long-term s.tty of the resin-based sealant:composition.
[00141 Clienerally, any Solvent that. Is compatible \kith the hide:m:1111e resin and that achieves the desired viscosity effect may be suitable for use in the liquid hardenable resin component of the resin-based sealant. composition. Suitable solvents may include, but are not limited to, .polyethylene glycol, butyl lactate, dipropylene glycol methyl ether,.
&propylene glycol dimethyl ether, .dimethyl formamide, diethyleneglycol methyl ether, .ethyleneglycol 'butyl ether, diethyleneglycol 'butyl ether, propylene carbonate,. Olimonene., fatty acid methyl esters, and combinations thereof. Selection :of an appropriate .solvent may be dependein on the hardenable resin ebOsen. With the benefit of this disolosttre, the selection of an appruriate solvent should be within 'the ability of one:
skilled ìn the art. 1n some embodiments, the- amount of the solvent used i.n the liquid hardenable resift. component .may be in the rangeof about 0.1.% to about 30% by weight of the liquid hardenable resin .20 'component. Optionally, the liquid hardenable resin component in.ay be heated to reduce. its viscosity, in place of, or inaddition to, usinea solvent.
[0015] Generally., the liquid hardenable resin. compo.nent .may be included in embodiments of the resin-based sealant composition in an .amount in a range from about 5%
toabont 90%. by volume .of the rosin-based sealant composition, .In particular embodiments, the liquid hardenable resin co.mponent may be included in the resin-based..
sealant composition in an amount it-La .range of -from about 509Ai to about. 75% by volume Of the tesin-baSed Sealant composition, [00161tn SOMe embodiments, the resin-based sealant composition may- further Comprise a liquid hardeningagent component coMprising a hardening.agent and an. optional.
silane eouplíng agent. As used herc.in, "hardening agent". refers to any substance capable of transforming the 1-ta.rdenable resin into a hardened, consolidated -mass.
Examples of suitable hardening .agents include, but are not limited to, aliphatic amines ,.aliphatic tertiary amines, aromatic amines, CyclOaliphatie amines,. heterocyclie amines, .amido amino, polyamides, polyethyl amines, polyether amities, poryoxyalkyittle catboxyk anhydrides,.
.35. triethylenetetmamineõ ethylene diamineõ. N=cocealkyltrimethylene, isophorone aminophenyl piperazine, im idazO line, 1õ2.--di am inocyelohexaneõ polyetheram diethyltoluenedne, ,4 -d iam inodi phenyl methane, Methyl tetmhyd roph t ha I
ic anhydride, hexahydrophthalie anhydride, mai*: anhydride, .polyazetai.c potyanhydride, phthalic anhydride, and combinations thereof. Specific examples ofsuitable hardening agents tnay include,. but are not limited .to, ETHACURE* 100, available from Albemarle Corp, of Baton Rotn.-te, La,,. and SEFFAMINe D-230, :available from Huntsman Corp, of The Woodlands, Tex. The hardening agent may be: included in the liquid hardening agent eon-iponeiu in an.
amount sufficient to at least partially harden the :resin composition, lit some: embodiments .of the present it the hardening 'agent Used may be included it the liquid hardening 10. agent component- in an amount in a rangeof from ibout 5% to about.
1.00?,-/0 by volume of the liquid hardening- agent component, hi other embodiments, the hardening agent used may be included in the liquid hardening :agent component in an amount in a range of from about .5(% to about 75% by volume of the liquid hardening agent coMporient, 100171 hi some embodiments the hardening agent may comprise a mixture of hardening. agents -selected .to impart particular qualities to the resin-based sealant composition. For example, in particular embodiments, the hardening- agent may comprise a fast-setting hardening agent and a slow-setting hardening agent. A.s used 'herein, "thst-setting hardening agent" and ¶ssetting hardening agent" do not imply any specific rate at .which the agents set a hardenable resin; instead, the .terms merely indicate the relative rates ..at which .the hardening agents i.nitiate 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, .1n a. particular embodiment. ETHACURe. 100 may be used as a .slow-setting hardening agent and JEFFAMINE''' 1-230, may be used as a fast-setting hardening. agent. In some .eiribodiments, the ratio of .1iist-sottin,g hardening agent to slow-setting hardening agent may be selected to achieve a desired behavior of liquid hardening agent component. For example, ìïSome embodi.Ments, the last-setting. hardening agent may-be included in the :liquid hardening fluent. component in a ratio of approximately 1:5, by 'volume, with the slow-setting hardening. agent. 'With the benefit Of this disclosure, .one of ordinary skili in the .art should be able -to select the appropriate ratio Of hardening agents .ibr use in a particular application.
[001 Si The liquid hardening agent component of the resin-based sealant composition may also inciudean optional siiane coupling agent The silane coupling agent may b.e used, .among other thing* to act as .a mediator to help bond tbd -eosin to CKD, the surface of the subterranean formation., and/or the .surface: of the well bore. Examples of suitable Oahe coupling agents ill:etude, but :are. Itot limited. to, N-2-(rantinoethyiY:3-aminnpropyltrimethoxyglane; 3-g/ ycidoxyprnpyltri mothozysilane ;
gamma-amino propyltri elhOxySi lane ; N-beta.(amMoethyl).Ornma-aminopmpyitri meth()); ys lanes;
am inoethyl. N-heta4 ami oethyl )-ga mma-arninopropy -trimethoxysilarces;
gamma-ure dopropyl-tri ethoxysil an es ; be t4-(3 -4 epoxy-eye I oh:ex yl-tri me th oxysi lane; gamin a-glyeidOxypropyhrimethoxys lane s;= vinyl triehl oros lane; (beta -me thoxy oxy) si lane; vinyltr iethoxyWone; yiny tri me thoxysi tane;. 3.-metacrYlox yp ropy Itrimethoxysi lane;
beta-(3,41 epoxycyelohexy1)-ethyltrimethoxysilane;
t.glyeidoxypropyltrimethoxysilarte; r-glyeidox ypropylme thy i dietboxysi lane; N-be ta-(am Moe thyD-r-athino p ropy I -trimethoxysilane, N-beta,(amitioethylt-r-aminopropyl methyld methoXySi lane; .
10. aminopropyl-triethpxysilane; N -ph en yl-r-am nopropyl m ethoxysil am; r-etetiptop ropy 1 tri m ethoxy.: ii afle; r-c h loropropy trimethoxysi ailQ; nyitri e h oro s Lute;
ny tris. (beta4nethoxyethoxy) vinyltrimethoxysilane; r-tnet4cryloOpropyi trimethoxy0lane; bet3,4 epoxycyc oh exyl)-e t hyl tri methoxy a; r-glycidoxypropyltrimethoxysilane; r-g lycidoxyp ro py meth yli di ethoxysilane; N-beta-(aminoethyl)4-aminopropyltri meth oxy:5 lane; N-bet.(aminoethyl)-r-am i nopropyi m ethy id imettioxysilatie;= r-am inopropyltrie thox5si lane; N-pheityl-r-aininopropyitriniethoxysiltme; r-mercaptopropy tri Me thoxy s ane; r-oropropyitri meth oxysil a ne ; Nl 3 -(trimethoxysilyl )propyi I-et ene d am i ne; substituted Silanes .here one or more of the substitutions contains a different fimetional groap; and .Combinations thereof. Generally, the silane coupling agent may be ineluded in the liquid hardening. agent component in an amount= capable of sufficiently bonding the resin to particulate. hi sotne embodiments .0' the present invention, the silanecoupling- .agent may be included in the liquid hardening. agent 'component in an amnunt in a range. of from. about to about 95%. by volume of the liquid hardening agent component. 'In ter embodiments, the silane coupling agent may be included in the liquid hardening agent component in an amount in a range of from about PAi) to about 50% by volume of the liquid hardening agent component.
[0019] A. liquid carrier fluid may also be used in the liquid .hardening .agent component to, arnong other things, reduce, the viscosity of the liquid hardening agent CoMponent for ease Of handling, mixing and tranSferring. 1-:-.1w$veyer,. in someembodiments, it may be desirable,. for environmental or safety Nasom, not to use .a liquid carrier fluid, Any suitable carrier fluid that is. compatible with the liquid hardening agent component and .aehieves the desired Viscosity effects may be suitable fir use. in the .present. invention. Some .suitable liquid carrier fluids are those having high flash points. (e.g.:, above: about 1259,F) 35.
because of, amotv .other thìns,etkviromentat and $afety conceinS; .Sueb solvents may include, but are not. limited to, polyethylene glycol, butyl. lactate,.
butylglyeidyl ether, &propylene glycol inethyl ether, dipropylene glycol imethyl ether,. &Methyl form= ide, diethyleneglycol: nethyl ether, ethyleneglycol butyl ether, diethyleneglycol 'butyl. ether, prOpylene carbonate, d'limonene, tInty acid methyl esters., and .combinations thereof. hi.
particular embodiments,:selection (if an appropriate liquid carri er fluid may be dependent on, inter aliaõ.the resin composition chosen.
[0020] Generally, the liquid hardening agent COInponent may be included in the resin-based sealant composition in an amount in a range of from about. 1%. to about :50% by volume of the resin-based sealant composition. In particular embodiments, the liquid hardening ..agent component -may be included in the resin,based sealant .composition in an, amount ...in 0: range. of front .about 5 to: about 25?.A. by volume of the :resin-based sealant composition. In particular embodiments, the amount of liquid hardening :agent compoSition may he Selected to impart ia: desired elasticity or coMpresSibility.to a resulting .well-borescal.
Generally., the lower the amount of hardening agent present in the resinrbased sealant composition, the greater the elasticity oreompressibility of a resulting well-boreseal. With the benefit of this disclosure, it should be within the skill of one or ordinary skill in the art to .select an a.ppropriate amount of hardening .agent to .aehieve. a desired.
elasticity or co m pressi bi ty for' a particUlar application.
[0021] In some embodiments, the resin-based :sealant com.positions may limber .20 :compriseCKD, which is a material generated in the manuthcture of cement. CKD, as that term is used herein, refers to a partially calcined kiln feed which is removed _from the gas.
stream and collected, for example, in a dust collector during the manufacture of cement.
Usually, large quantities. .of CKD are collected in the produotiOn of Cement that are .commonly disposed of as.waste. Disposal :of the CKD as waste can add undesirable costs i0 the manufacture of the cement, as .well as the environmental concerns associated with its disposal:. The chemical analysis of CKD from various Cement manufaetures varies 'depending on a number of factors, including the particular kiln feed, the efficiencies of the cement production operation, and the associated dust collection systems, 'CKD
.generally may comprise 'a :variety Of oxides, stich as SiOlõAl2O Fe203, Ca0:, MgQ, SO3, Na), and K20. The term "CK.D" i uSed herein to Mean. cement .kiin dust made as described above and equivalea forms of cement kiln dust made in other ways.
1100221 'In accordance .with embodiments of the pre-sein invention, the CKD
may be used,. among other things, as a...non-hydrating filler material to lower the .consuroptioi of the .more expensive components :hardenable resins, .that are used in the resin-based sealant compositions. 'While the CKDís a cenientitious 0.0111 po.nent that sets and h.ardens in the =preSence Of water, the CKD shOuld be -non-hydrated When mixed the liquid.
hardenable resin component and o.ptionally .the liquid hardening .atlent component as the resin-based sealant composifion -may be non-aqueous, !Or .example. In this manner, the.resin, based sealant eoinposition may be placed into a subterranean formation and allowed .to harden therein with the CKD..remaining rlijil-hydraktd.. Because theCKD is present in the hardened composition, it is loelieyed that the CKD .may help counteract the potential formation i-rif cracks in the hardened composition .andlor micro-annulus that may form.
between the hardened composition.and the pipe string. or the 'well-bore wall.
In general, the CKD is capable of setting and hardening when contacted by aqueous fluids to inhibit fluid U. flow through the (-Tarok .andlor micro-annulus. Accordingly, the CKD may prevent andfor reduce the loss olzonal isolation in spite of the formation Of cracks and/or miCro-annulus, potenti al ly resulting in an .imprOved annular seal for ernbodiments of the Wsin-baSed. sealant composi.tions.
100231 Generally, the CD .m ay be included in the. resin-based sealant compositions in an amount in a range of-from about 1% to. about 60% by vOIUMe of the reSin-based sealant composition. In particular embodiments, the CKD may be included in the resin-based sealant compositions in an, amount in a range of from about .20% to about 40%
by volume of the .resin-based sealant composition. 1.n specific embodiments, the CKD .may be present in an amount =ging between any of andfor including:any of about of about 1.%.õ
about 10%., about 20%, .about 30%, about 40%, about 50%, or about 6.0% by .volume of the resin-based sealant composition.. One of ordinary skill 'lathe airt, -with the benefit of this disclosure, -will recognize the appropriate amount of CKD to include fbr a chosen application.
100241 While the procednig description describes. CKD, the= present. invention iS
broad. enough to encompass the use of other partially .ealeined kiln feeds.
For example, embodiments o.f the resin-based sealant compositions may comprise lime kiln dust, µvhich is a material. that is generated during the manufacture of lime* 'The term "lime kiln dust"
typically refers to a partially calcined kiln feed.. which can be removed from the gas stream.
and collected, ibr. example., in. a dust collector during the manufacture of bine. The.chemical analysis of lime kiln dust fro. in various lime manufactures=varies depending on a number of factOrs., including the particular [limestone or dolomitic limestone feed, the type of kiln, the mode of operation of the kiln, the efficiencies of the lime productio.n operation,. and the associated dust collection .systems. Lime kiln dust generally may comprise N.,arying amounts of tìee lime and free .magnesium, lime stone, and/Or dolomitic limestone and a variety of oxides, such as SiD2õ. M203, C40., Mg0., SC, Na2.0,, and :K20, and other components, .stich as. ch foil des.
1.0 1-.00251 In some embodiments,. the resin-based. sealant compositions may .further comprise weighting material. As uSed herein, the term. "weighting Material"
iefers tO any particulate matter added to the resin-based sealant composition to inere.aSe rh)Wer clensity..
Examples of weighting .materialss fOr lowering density include, but are not limitedta hollow microsphereS. Examples ctf suitable hollow mierospheres include, but are not limited to, lvilow mineral glass spheres;.suCh as "S.P1-IERELITEMI". available. from 14a1liburion .Energy :Services of DWICali. Okla.; silica and alurniTia certo spheres, such. as "CENOLIfE.v"
from Mierospheres. SA. a South Africa; hollow glass microspheres, such as "SCOTCHLITErw available from the 3M Company of St. Patti, Minn.; eeramic microspheres, suett as ."1,-ILICilf SPHERESTmw :available. from the .3M
Cornpany of S.
Paul, Minn,; polymeric thicrosphereS .such as"EXPANCEL4.1'" available front Akzo Nobel .0 The Netherlands; and plastic microspheres,. such as. "IIIBRA-BEADS4'" avdi fable frtm flialliburtou Energy Services, Inc. :of Duncan, Okla. Examples Of suitable Weighting -materials. for increasing density include., hut are not limited to, silica, ilmenite, hematite, barite, Portland cem.ent, -manganese .letraoxideõ and combinations thereof.
Specific. examples a weighting materials for increasing density include, hut are not limited to, MICROSANDrm., a crystalline .silica .weighting material, and 14I-DENSet, a hematite weighting material, both available .from flalliburton Energy ServiCeS, tyf Duncan, Okla, [0026] The mean particulate sizes of the weighting Material may generally range' .20 front about 2. nanometers to about 3000 mierons. in diameter; however, in certain eircum.stances,.:other mean particulate sizes may be desire'1. and will be entirely suitable for practice of the present invention. It should be undenitood that the term "particulate," as uSei.
in this disclosure, includes alI known shapes of materials, including substantially spherical materials, 'fibrous materials; polyeonal materials (such as cubic materialS), .and mixtures.
thereof In particular embodiments, the particulate 'size of Elie weighting material .m.ay be .selected to impart. a. desired viscosity to the resin-based sealant composition. Moreover, in particularembodimentsõweightingmaterials having .different particulate Si2OS
may be mixed to achieve a desired viscosityofthe resin -based sealant composition.
[0027] Generally, the weighting material may- be included in th.e resin-based sealant .30 composition in an amount in a range. of from. about I.% to about 60% by volume of the resin-based sealant composition. In particular embodiments,. the weianing material may be included if./ the resin-based .sealant composition in an amount in a range of from about 20%
to about 40% by volume of the resin.7based sealant:composition, [0028] in .same embodiments, the resased sealant cOmpositions may further .35. comprise sweilahle particles. As used herein, the term "swellable particle'! refers to .any particle that swells upon Contact with. oil, ':gas, a combination of oil and gaS, andlor an aqueous Ii (e.g., wnter). Swellable particles suitable for use in einbodiments i..)47 the present invention may generally -swell by- tip to about 5M of their :original size at the surface. Under downhole conditions, the amount Of.swelling may Vary depending on the conditions presented, For example, ìn SOlte embodiments, the amount or.Swelling may be at least 10%. !..inder downhole conditions. In particular embodiments, the amount of swelling may be up to about 50% under downhole conditions. Howeveryas those: of Ordinary skill in the art, with the benefit :of this disclosure, ìi appreelate, the actual innount of swelling when 'the.sWtliable partieles .are included in. a :resin-baSed: Sealant Omposition may depend 10. on the concentration of the swellable particles included in the composition., among other factofg. In accordance with particular embodiments Of 'the present nrverition, the swellable particles; may be 'included in the resin-based: sealant composition, for example, .to eounteract the formation of cracks in a resultant well-bore: seal undior 'micro-annulus between the welt.
bore plug and the pipe string or the formation. In general, the swellable partieles are capable ofswelling when contacted b:y one or more of the previously 'mentioned fluids to .inh lbit fluid flow through the crack. ad/or tnicro-annuluS, .Accordinglyõ the sWellabic partieleS. may prevent andfor reduce .the loss of :o.ttal isolation in spite of the formation of cracks .andfor micro-annulusõ.potentially resulting iì an improved annular seal for the resin-based sealant compositions:
1,t)029] Sortie :specific: examples of suitable .gwellable elastomers include, hut are not limited to, natural rubber, .actylate hutadiene rubber, polyacrylate rubber, isoprene rubber, eholoroprene rubber, butyl rubber (UR), brominated butyl .rubber (131.1.R.)õ
chlorinated butyl rubber (CEIR), chlorinated. poiyei'hytene.t.C.WCPE), neoprene rubber (CR), styrene butadiene copolymer robber (SBIZ)õ. SUIphonated polyethylene (C$M), ethylene acrylate 'rubber (EAMIAElvi), .epiehlorohydrin ethylene oxide copolymer (.CO', E.00),. ethylene-propylene rubber (EPM and EDPM), ethylene-propylene-dient terpolyther rubber (EPT), ethylene vinyl acetate. copolymer, fluorosilicone rubbers: (INIVIQ), silicone rubbers' :(VM.Q)õ poly 21 -bicycle) heptene (polynorborneand), end alkylstyrerte. One example- .of a suitable swellable elastotner comprises :a block'copolymer.of a Stytetie butadiene rubber. 'Examples of suitable elaStoniers that swell when contacted .by oil incl ado., but are not limited to, nitrite rubber (NBR), hydrogpnated nitrile rubber (HN BR, Moro rubbers perfluoro rubbers. (EF.KM), tetrall uorethylenefpropylene (r.FE//4 isobutylene maieie.
anhydride, .0ther swellable elastomers that behave 'in a similar fashion With respect to oil or aqueous fluids also may be suitable- for use in particular embodiments o.r the .present invention, Furthermore, conibinations of :suitable swellable elastOmers :may:also be used in particular embodiments of the pres:ent [00301 Some .specific. examples of 'suitable water-swel table polymers, include. but are not !United, to starch-poi yacrYlate acid graft opolynter and. salts thereof,. polyethylene 'oxide polymer, carboxymethyl cellulose type .polymers, polyamlarnide, poly(a.erylic acid) end .salts thereof, poly(acrylic.zicid-co-.a.crylainide) and salts th.eitof, .g,raft-poly(etbylene oxide) .of poly(aerylie acid) and salts thereof; poly(2-hydroxYethyl methaerylate), poly(2-hydroxypropyl methacrylate), .and combinations thereof. Other water-swellable polymers that behave. :in a similar fashion with respect to aqueous fluids also may be 8uitable fc:sruse in particular embodiments of the present invention. In certain embodiments, the water-swellable :polymers may be crosalinked andior ight1y crosslinked. Those of erdinary.:skill the art, with the benefit of this disclosure,. will be able to select an appropriate sWell.able elastorner and/or water-sWellable pOlyrner Or Use. in partiettlar embodiments of the resin-based sealant compositions of the present invention based on vaiiety of faetors,: including the particular :application in .which the composition µvill be Used and the desired .swelling charaCteristics.
[.0031-1 Generally, the:swellable panicles may be included in the. min-bas.ed sealant eompositions. in an amount sufficient to provide the deSited mechaniedTproperties. Insome embodirnents, the swellable panicles may be present in the resin-based.sealant compositions .20 in an amount up to about 25.% by weight of the hardena.ble'' resin: In sorneemboditnents, the swellable particles may be present in the resin-based sealan compositions in a raw of about .51.'") 'to about 25% by weight of the hardenable resin. In sonte ethbodiments: the sellable particles. may be present in the resin-based sealant compositions in .4. range .of about 15% to about 20% by. weigh t of the hardenable resin, [00321 In addition, the= sellable panicles that may be utilized may have a wide variety of shapes and sizes of individual particles suitable for use in accordance .with embodiments Of the preset invention. B y. way of example, the. swell able -particles may have µvell-delined physical shapeas well as. an irregular .geometry, including. the physical. shape of platelets,. shavings, fibers, flakes, ribbons,..rodS, strips, spheroids,.
heads, pellet*, tablets, or .30 any other physical shape. In some embodiments,. the .swellable particles may ha' e a mean panicle size in the range of about 5 microns to about 1,500 microns. In some embodiments, the slyellable particles may have a mean particle sizo in the rang o :of about .20 microns. :to about .500 micrOrts. However, 'particle sizes outside these defined ranges also may be suitable fryr particular applications., I.
[00331 ht some embodiments of the present invention, additional solid.
materials May also be included in the Mitt...based Sealant composition to enhance the strength, hardness,. and/or toughness of the resuiting well-bore seal, The solid materials may include both natural .and man-ntade .materials, and may have: any shape, including, but not limited. to, beaded, cubic, bar-shaped, cylindrical, or mixtures thereof, and may be in any form. including, but not limited to flake or fiber thrm. Suitable materials may include, but are not limited' to, cellulose :Om, carbon fibers; glass fibers, minemi fibers!, plastic fibers (e4, .polypropylene and polyacrylic nitrile .fibers).,. metallic fibers, metal shavings, .Kcvlar fibers,. basalt fibers, wollastonite, micas (e.g., phlogopiteS and .muscoVites), and mixtures thereo1 ln soine embodiments, nanopartieles andior nanolibers may also be ineluded in the resin-based sealant composition, wherein the nanoparticles and/or nanofibers have at least one dimension less than .1 micron and, alternatively, less than about 1.00 nanometers, 110034j Carbon fibers. suitable for use in particular embodiments of the present invention include high tensile modulus carbon fibers which. have. a high tensile. strength. In some embodiments, the tensile modulus of the carbon libers may exceed 1.80 GPaõ and the tensile strength of the carbon fibers May exceed 3000 NIPa.. Generally. the fibers-may baVe mean length of about 1. Mill or. less. In some embodiments, the mean length :of the carbon fibers is from about 50 to about 500 microns. .111 jriarticulat embodiment, the carbon fibers have .a mean length in the range of fm.in about 100 to about 200 microns. in particular .20 einbodiments, the carbon fibers May be milled carbon .fibers. Suitable, commercially available earbon fibers include, but are not limited. to, ".AGIVI-94" a.nd.
"A1ìM-99". carbon fibers both available from Asbury Graphite :Mills, Inc,õ of Asbury, N.J.
[00351 .M.etallit fibers suitable. fbr .use irt particular embodiments of the present invention may include non-amorphous (Leõõ .crystalline) metallic fibers. in particular embodiments, the ion-amorphous metallic fibers may be obtained by cold drawing steel wires (Le., .steel. wool). Suitable metallic fibers include, but are not limited to, steel fibers,.
Gotteridly, the length and kliameter of the metallic fibers .may be adjusted such that the fibers are flexible and easily dispersible in the resin-based sealant composition, and the resin-based .sealatit cotnpOsition is easily .pumpable.
1(0361. These: additionai solid materials may be present in the resin-based sealant composition fthe present invention individually or in combination_ Additionally, the solid materials of the present invention may be present in the resin-based sealant compOSition in a variety of lengths. andlor aspect ratioS. A .persou having ordinary skill in.
the art, with the benefit .of this .diselosure,. will recognize the mixtures. of type, length,.
andfor aspect. ratio to 1.4 use AO achieve the desired properties of a resin-based sealant composition fur a. particular application.
[0037] In particular embodiments of the present .invention, the liquid hardenable :resin component, optional liquid hardening. agent component, and. CtiD, as well as any of the additional optional additives te.,g., weighting nteraI seIJahle particles,.
additional solid materials) inay he either batch-mixed o.r mixed on-the-fly. As used. herein, the term "on-the-fly"
tiwi herein to .inean that a flowing Stream IS continuously introduced. into another flowing stream so that the streams are combined and mixed while continuing to.
now as .a single'Strearn as part of the on-going treatment. Such miXing may 'also be described as 1 time" miking. On-the-fly mixing,..asopposed to batch or partial batch mixing, may reduce waste and :simplify subterranean treatments:: This is due,. in part,. to the fact that, in particular embodiments, if .the components are Mixed and then circumstances dictate that the subterranean treatment 'be. stopped or postponed, the mixed components May b.e.eorne.
unusable. By having the ability to rapidly Shut down the mixing .of stream.s:
(m-the-fly ìn :such embodiments, mmecessary waste may be avoided, resulting in, inter alia, increased efficiency and etist. savings.. However, other embodiments of the present invention .may uiIuv fur batch mixing of the resin-based sealant composition. In these embodiments, the resin-based. .sealant composition may he sufficiently stable to allow the composition to be prepared in advance of its introduction .into the well bore without the composition becoming unusable if not promptly introduced. into the well bore.
[0038] Generally, embodi Men ts of the resin-based sealant eornpositions of the .present invention .inay be used for any of a. variety different purposes in .which the resin-baSed .:Sealant: eompoSition may be prepared and al loWtd to harden, lit 'Sprite embodiments, the resin-based sealant composition rma.y be introduced into a subterranean form.ation and .allowed to harden. As used herein, introducing the resin-based sealant composition into a subterranean formation includes: introduction intaany portiOn of the:
subterranean formation, including, 'without limitation, into a well bore drilled into the subterranean formation,. into a near well 'bore region surrounding the well bore, .or into both. The resin-based sealant composition may be allowed to harden in the subterranean formation for a number of purpOses including, without limitation: to isolate the subterranean tbrmation from a portion of the well. bore; to support a conduit in the well bore;. tO plug a void:in the conduit; plug a void in a cement .sheath disposed in an annulus of the .well bore; to plug a perforation; to plug void micro-annulus): betWeen the cement sheath and .the conduit; to pre-vent the loss of aqueous or nonaqueous drilling fluids into loss .circulation zones such as a void, .vtigular zone,. or frieture; to plug a well for abindonment purposes; to 'form a temporary plug to. divert Ueatment flttids;.a8.a chemical packer to be Used as a fluid in front.of cement slurry in cementing operations; or to seai an annulus betWeen the :well bore and a.n ekpandable pipe or pipe stritta. For instance, the :resin-based sealant composition fltay withstand substantial amounts Of .pressure, .e.g.õ the hydrostatic- pressure of a drilling -fluid or cement slurry, without being dislodged or extruded. The resin-based sealant composition may set into a.
flexible, resilient and tough .material, which may prevent further fluid losses when circulation 1.S.reSumed, The resitt-baSed Sealant compoition mart-II-so form a non-flowing, intact tnass inside the loss-circulation .zone, This .mass plugs the Zone and inhibits loss of subsetlitently pumped drilling fluid, which alloWs few liirt her (hitting, [0039] In primary-cementing etnbodiments, .for example, embodiments :of the resin-based .sealant composition may be introduced into: a well-bore annulus .such :as a space betw.een a wail of a well bore and 4 conduit (Op, pipe strings, liners) located in the well bore or between the: conduit and a larger conduit in the well bore. The resin-based sealant composition may be allowed to harden to form an annular sheath of the hardened composition in the well-bore annulus. Among other things,. the hardened compoSition fOrrned by the res.in,7based sealant composition may ibrin a barrier, preventing the Migration of fluids in the well bore. The hardened composition also may, .for .example, support the conduit in the well bore andfor form a bond 'between the :Nvell-bore.wall and the conduit.
[0040] In some em.bodiments, the conduit rnay also be cemented into a well-bore .20 annulus by utilizing what is blown as a reverse-cementing method. The reversecementing method comprises: displacing the. resin-based sealant composition into the annulus between the conduit and the annulus between an iSting string, or an open hole :section a the wellbore, As the resin-based .sealant composition is ptmipeddoWn the annular spare, drilling fluids ahead of the resin-based ..sealant composition are displaced .around the lower ends of the conduit and up the inner diameter of the conduit and out at the !..a.trface. The fluids ahead of the resin-based sealant composition may also be displaced upwardly through a workstring that has -been run into the inner diameter of the conduit and sealed MT at its lower end..
:Because the work stringhas:a smaller inner diameter, fluid velocities ìii.
the work string will be higher and will Mire .effiCiently transfer the cuttings washed out of the .annulus during placement of the resin-based sealant. coinposition.. In an embodiment, a small amount of resin-based sealant co.mposition will be pumped into the conduit and the work string. .As soon .as a desired a:mount o.f resin-baõsed sealant composition has been pumped into the .annulus, the work string may be pulled out of its Seal receptacle and excess resin-lased sealant composition that has entered the work string can be reverse-circulated out the lower end of the work .string to .the surface, 1.6 I00411 nremedial-cernenting embodiments, a resin-based.sealant composition may be Used, for example, in scpiecze-eementing operations or in the .piacetnent dement plugs.
By way of example, the resin-based 'sealant compositio.ri may be placed in .a.well bore to .plug voids, such as holes or cracks. in the Pipe stringS; holes, cracks, spaces, or channels in the sheath; and very .small spaces (com.monly tafetted to as "Micro-annuli") between the sheath and the exterior surface of the pipe or well-bore wal [0042] It should be understood that the compositions and methods..are described in terms of "comprising," containing," or "including" various COMpOrteritS Or steps, the tonipositiOnS and methods can= alSo "cobsist essentiallY or 1--ny "consist Or the 'various compone.nts and steps. Moreover, the indefinite artieles'4`a" :or "an," .as used in the claims, are defined herein to mean oneor more than one of the element that it intro.duces.
[00431 For the = sake of brevity, only certain ranges are. explicitly :diSclosed herein.
However, ranges front any lower limit ittay .be Combined with any upper limit to. recite a range not explicitly -recite& as. well as, ranges from any lower limit .may be combined with.
any other lower limn to recite a range not explicit1y. recited, in the same way, ranges from any upper limit may.'he combined with any other upper limit to recite a range not explicitly reeitett Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, .any number and tiny included range. -falling within the range are specifically disclosed. In particular, every range of values (of the form, "from about a..
to:about b," or, equivalently, "from approximately a to b," ór. eiiva1rnt1 from approximately a-h") disclosed he-rein is to 'be understood to setforth every number and range encompassed Nvithin the broader range of values even if not explicitly recited. Th.U.Sõ eveq point or individual value may serve as its.oWn lower of upper limit combined with any other point or individual value or any other lower or upper limit,. to recite a range not.explicitlyrecited.
[0044] Therefore, 'the present .invention is well adapted to attain .the endsrnd advantages mentioned ass wallas those that are inherent therein.. The particular embodiments disclosed.aboye ore illustrative only, as the present. invention may be modified and pradticed in different but equivalent manners 'apparent .to those:skilled in the art having the benefit of the .teachings. herein. Although individual onibodiments are discusw4, the invention co*ers all combinations =i-)..f all thoseembodiments. Furthermore, no limitations are intended to the details. .of COnStrtMi011 or.design herein .sbown, other than as described in tbe claims below;
MS , the terms in the claims hava their plain, ordinary meaning unless-othenise explicitly and ejeady defined by. the patentee.. It is therefore vvident that the particular illustrative embodithents .disclosed above may be altered' :or modified and all such variatiOns are .35. :considered .within the scope and spirit of the -present iriVentiOri, if there is any conflict in the =USageS= of a word or term in this speeificatiot and one or more patent(s) Or other documenti that may be ineortxyrated herein by teferetWe, the definitions that are cOnsisient with thi.
specification should be adopted,
such voids may prevent the undesired flow of fluids. (e.g,., gas, water, etc.). and/or tine solids into, or trOm, the Well bore. Sealant compositions also May be used in .surface appiicatiottS, for example, construction cementing.
[000M A variety of differeta sealant compositions, including. non-cementitious sealants,. such as resin-based sealant compositions haw beth: used in these primafy- and secondary-cementing methods. Resin-based sealant compositions may comprise, for example, a liquid hardenable ageat compondit and a hardening ogent COMpOrIpt BOC4thie7 resin-based sealant compositions may have increased flexibility and toughness as. compared to conventional cement compositions, the resin-based sealant COaiposition nay be=used, f.or example, :in applications 'Acre inereased =Stresses andlor increased numbcr (if stres.$ cycles may be encotmtered. For owmole, resin-based sealant compositions rttay have applicability in cementing methods performed in shale fOrtnations as wells drilled in these types of formations flaay require multiple fracturing stages requiring the sealant compositions to have =sufficient flexibility and toughrios to withstand repeated hydraulic stress and themial cycles.
In addition, resased sealant cotripositioOS may alSo be placed into the I
bore:to plug a void in the conduit (e.g., the pipe: stritig)Hor cetnent sheath or a void that may have fOrmed between the sheath and a wall of the well bore or the. conduit. While resin-based sealant compositions may be, used instead of conventional cementitions-based se.alant compositions certaill applications, drawbacks exiSt with use of snob sealant coinpositions, includin g the high cost of the resins, for example.
SUMMARY
[00041 An e.mbodiment of the present invention provides a method comprising providing a resin-based sealant composition:comprising a liquid hardenahle resin: component and kiln dust; and allovAtig the min-based sealant composition to harden.
110005] Another .embodiment of the present invention provides.a method of forming astal in a subterranean :formation comprising: introducing a resin-based sealant composition into a subterranean formation, wherein the resin-based sealant composition comprises a liquid hardenable resin component and cement kiln dust; and allowing the resin-based 'sealant composition to harden in the stibtedanean formation, 1.0 [00061 Another mbodiment of the present inventiOn-provides a resin-based sealant .eomposition comprisin a liquid. hardenabieresin component and cement .kiln dust.
[OWY71 The teatures.and advantages of the present :invention NVill be readily apparent to those skilled in the art. While numerous changes may be made by those.skilled in the art, such changes .are within the spirit ofthe invention, DESCRIPTiON OF PREFERRED EMBODIMENTS
[0008] The present invention relateS to resin-based .Sealant compositions Hand,. More particularly, in certain embodiments., to resin-based :sealant compositions that comprise cenient kiln dust..("CKD").and.aSsociated met hodS=of use in servicing well bores. One o.f the many potential advantages of the methods and compositions .of the present .invention is that the CKD may be Used as a non-hydratine filler material to IoWer. the consumption of the moreexpensive.components (e.g:õ hardenable resin component, etc.) -that are typic a y used ìr resit-based. sealant compositions. Yet another potential advantag.e is that the CKD .may aid the sealing of voids .such as cracks that may form in the hardened sealant composition.
I 0 :By way of e.xtimple. the CKD may hydrate and harden upon .contact with waterõ for example, counteract the potential fort -nation of voldS (e.g., cracks, Micro-annuli, etc%) that may form in the hardened sealant composition:, [000)] Embodiments of the present invention disclose: resin-based Sealant compositions: Comprising a liquid hardenable resin. .component and CKI").. in some 1.5 embodiments, the resin-based sealant coinposition -may further comprise. a. liquid hardening agent component for facilitating the set :of the hardenable resin component.
In other embodiments, the liquid hardenable resin component may auto-cataly4e and not require the hardenable .resin component for Setting. The. resirt,hased. Sealant cOttmositions may be used in a .nutnber clifTeiviat stibterrantan .apptication$ iiAlth kb the sealant composition may be .introduced .into a subterranean formation and allowed .to harden, One .example of a .subterratean application includes primary-cementing methods in which the resin-based Iieplant composition may be allowed to harden in a well-bore annulus.. Another exatnple. of a subterranean application includes remediakeernenting methods ii'i. which the resin-based .sealant cOmposition May be allowed, for example, to .harden and seal Voids in pipe strings Or cement sheaths, to seal highly permeable formation zones or fractures, .to place a cement plug, and the like;
[0010] in some embodiments, the liquid hardenahle resin component of the resin-based 'Sealant composition may comprise a hardenable resin, an optional solvent, and :an optional aqueous diluentor carrier fluid. As used herein, the term ''resin"
refers to any of a = 39. number.oU ph ysical ly siMilar polymerized Synthetics or.
chemically niodified natural resins .including thermoplastic materials and thermosetting material& Examples of hz.,Irdenable resins that may be. used in the liquid hardenable reSiti component -include:, hut are not limited .to, epoxy-based resins, novolak resins, .pOlyepoxide resins, phonot-aldehyde resins,. urea aldehyde resins, urethane resins, phenolic resins, loran resins, furanArtitryl alcohol resins, :35 phenolicilatex reSins, phenol formaldehyde resins, hisphenol A
diglycidyl ether reSins, butoXythethyl. butyl .glycidyi ether regins, bisphental A-epiehlorohydrin resinS.õ biaphenot resins glyeidyl ether resins, polyester mains and hybrids and copol.yrnera thereof, polyurethane resins and hybrids and copolymers thereof; acrylate resins, and mixtures thereof. Some suitable resins, such as epoxy resins, may be cured µvith an internal catalyaror activator sia :that .when pumped dmanhol.e. they allay be cured using only tirne and .temperature. Other .sultable resins,. suchas furan msins .generally require a tine-ddayCO
Catalyst or an external catalyst to help activate the polymerization of the resins if the cure temperature s low (i.e., less. than 2.50'.1), but will awe under the effect of time and 'teinperature if the formation temperature is above. about 250T, preferably 'above about 10. 300F. 'ft is within the abil.it.y of one skilled in the artõ with the benefit of this diac1osurt4 to select a :Suitable resin fr uae in embodiments Of the present invention and to determine whether a Catalyst is required to trigger curing. One main that may be used in particular embodiments of .the present .invention is the consolidation agent commercially available from.
:11alliburton EnergyServices, Inca of Dunean. Okla., under the trade name."EXPED1TEOW..."
[0011.:j Selection of a suitable resin may be affected by the temperature of the .subterranean formation to which the composition will be introduced. By Way:
of example.
for subterranean. fortitations having a bottom hole static temperature Crif151.7') ranging from .about 60T to .about 25OF two-Omponent cp4y-bpsed resiris comprising a hardenable .i.csin component and a hardening .agent component containingspeeifie :hardening agents may be preferred. For subterranean forthationa .having a BUST ranging from about 30097 to about .600" F. A fitranabased resin may=be preferred, For SUbtararlean formations having a MST ranging from .about 200cF to about 400v.F, either a phenolic-based .resin or a one-component HT epoxy-based resin may be suitable. For subterranean formations having a MIST of at least about 175T, a phenol/phenol thrmaidehydeffurfuryl alcohol resin tnay also be. sulta.ble.
R/0121 Generally, the hardenable resin may .be= included in the liquid .hardenable 'resin component in an amount in a range of. from about 5% to about 100% by volume of the :liquid hardenable resin component. in particular embodiments, .the hardenable resin may be included in the liquid hard.enable resin .ciampenent in an amount in a range of fro. m about .75% to about '10.01- by volume of the liquid h.ardenable resin component it iS within the :ability of one skilled in the art with the benefit of .this disclosure to determine how .tnuch of the hardenable. resin may be needed to itchieve. the desired results. Factors that may .affect this detisiim. include the type of :hardenable resin and liquid hardening agent: used in a particular application.
[001.31 In some embodiment*, a. solvent iriay be added to :the resin to reduce its viscosity for ease= of handling, mixing and transfetring.
However, in particular embodiments,. :it may be desirable not to use. such .a solvent for 'environmental or safety :masons. lt is. within the ability of one skilled in the art with the benefit of this disclosure to determine if and how much .solvent may be: needed to Itehievea viseosity suitable to the subterranean conditions a a particular a.pplication. Factors that :may affect this deeiSiOn include geographic location of the well, the surrounding weather conditions, and thedesited long-term s.tty of the resin-based sealant:composition.
[00141 Clienerally, any Solvent that. Is compatible \kith the hide:m:1111e resin and that achieves the desired viscosity effect may be suitable for use in the liquid hardenable resin component of the resin-based sealant. composition. Suitable solvents may include, but are not limited to, .polyethylene glycol, butyl lactate, dipropylene glycol methyl ether,.
&propylene glycol dimethyl ether, .dimethyl formamide, diethyleneglycol methyl ether, .ethyleneglycol 'butyl ether, diethyleneglycol 'butyl ether, propylene carbonate,. Olimonene., fatty acid methyl esters, and combinations thereof. Selection :of an appropriate .solvent may be dependein on the hardenable resin ebOsen. With the benefit of this disolosttre, the selection of an appruriate solvent should be within 'the ability of one:
skilled ìn the art. 1n some embodiments, the- amount of the solvent used i.n the liquid hardenable resift. component .may be in the rangeof about 0.1.% to about 30% by weight of the liquid hardenable resin .20 'component. Optionally, the liquid hardenable resin component in.ay be heated to reduce. its viscosity, in place of, or inaddition to, usinea solvent.
[0015] Generally., the liquid hardenable resin. compo.nent .may be included in embodiments of the resin-based sealant composition in an .amount in a range from about 5%
toabont 90%. by volume .of the rosin-based sealant composition, .In particular embodiments, the liquid hardenable resin co.mponent may be included in the resin-based..
sealant composition in an amount it-La .range of -from about 509Ai to about. 75% by volume Of the tesin-baSed Sealant composition, [00161tn SOMe embodiments, the resin-based sealant composition may- further Comprise a liquid hardeningagent component coMprising a hardening.agent and an. optional.
silane eouplíng agent. As used herc.in, "hardening agent". refers to any substance capable of transforming the 1-ta.rdenable resin into a hardened, consolidated -mass.
Examples of suitable hardening .agents include, but are not limited to, aliphatic amines ,.aliphatic tertiary amines, aromatic amines, CyclOaliphatie amines,. heterocyclie amines, .amido amino, polyamides, polyethyl amines, polyether amities, poryoxyalkyittle catboxyk anhydrides,.
.35. triethylenetetmamineõ ethylene diamineõ. N=cocealkyltrimethylene, isophorone aminophenyl piperazine, im idazO line, 1õ2.--di am inocyelohexaneõ polyetheram diethyltoluenedne, ,4 -d iam inodi phenyl methane, Methyl tetmhyd roph t ha I
ic anhydride, hexahydrophthalie anhydride, mai*: anhydride, .polyazetai.c potyanhydride, phthalic anhydride, and combinations thereof. Specific examples ofsuitable hardening agents tnay include,. but are not limited .to, ETHACURE* 100, available from Albemarle Corp, of Baton Rotn.-te, La,,. and SEFFAMINe D-230, :available from Huntsman Corp, of The Woodlands, Tex. The hardening agent may be: included in the liquid hardening agent eon-iponeiu in an.
amount sufficient to at least partially harden the :resin composition, lit some: embodiments .of the present it the hardening 'agent Used may be included it the liquid hardening 10. agent component- in an amount in a rangeof from ibout 5% to about.
1.00?,-/0 by volume of the liquid hardening- agent component, hi other embodiments, the hardening agent used may be included in the liquid hardening :agent component in an amount in a range of from about .5(% to about 75% by volume of the liquid hardening agent coMporient, 100171 hi some embodiments the hardening agent may comprise a mixture of hardening. agents -selected .to impart particular qualities to the resin-based sealant composition. For example, in particular embodiments, the hardening- agent may comprise a fast-setting hardening agent and a slow-setting hardening agent. A.s used 'herein, "thst-setting hardening agent" and ¶ssetting hardening agent" do not imply any specific rate at .which the agents set a hardenable resin; instead, the .terms merely indicate the relative rates ..at which .the hardening agents i.nitiate 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, .1n a. particular embodiment. ETHACURe. 100 may be used as a .slow-setting hardening agent and JEFFAMINE''' 1-230, may be used as a fast-setting hardening. agent. In some .eiribodiments, the ratio of .1iist-sottin,g hardening agent to slow-setting hardening agent may be selected to achieve a desired behavior of liquid hardening agent component. For example, ìïSome embodi.Ments, the last-setting. hardening agent may-be included in the :liquid hardening fluent. component in a ratio of approximately 1:5, by 'volume, with the slow-setting hardening. agent. 'With the benefit Of this disclosure, .one of ordinary skili in the .art should be able -to select the appropriate ratio Of hardening agents .ibr use in a particular application.
[001 Si The liquid hardening agent component of the resin-based sealant composition may also inciudean optional siiane coupling agent The silane coupling agent may b.e used, .among other thing* to act as .a mediator to help bond tbd -eosin to CKD, the surface of the subterranean formation., and/or the .surface: of the well bore. Examples of suitable Oahe coupling agents ill:etude, but :are. Itot limited. to, N-2-(rantinoethyiY:3-aminnpropyltrimethoxyglane; 3-g/ ycidoxyprnpyltri mothozysilane ;
gamma-amino propyltri elhOxySi lane ; N-beta.(amMoethyl).Ornma-aminopmpyitri meth()); ys lanes;
am inoethyl. N-heta4 ami oethyl )-ga mma-arninopropy -trimethoxysilarces;
gamma-ure dopropyl-tri ethoxysil an es ; be t4-(3 -4 epoxy-eye I oh:ex yl-tri me th oxysi lane; gamin a-glyeidOxypropyhrimethoxys lane s;= vinyl triehl oros lane; (beta -me thoxy oxy) si lane; vinyltr iethoxyWone; yiny tri me thoxysi tane;. 3.-metacrYlox yp ropy Itrimethoxysi lane;
beta-(3,41 epoxycyelohexy1)-ethyltrimethoxysilane;
t.glyeidoxypropyltrimethoxysilarte; r-glyeidox ypropylme thy i dietboxysi lane; N-be ta-(am Moe thyD-r-athino p ropy I -trimethoxysilane, N-beta,(amitioethylt-r-aminopropyl methyld methoXySi lane; .
10. aminopropyl-triethpxysilane; N -ph en yl-r-am nopropyl m ethoxysil am; r-etetiptop ropy 1 tri m ethoxy.: ii afle; r-c h loropropy trimethoxysi ailQ; nyitri e h oro s Lute;
ny tris. (beta4nethoxyethoxy) vinyltrimethoxysilane; r-tnet4cryloOpropyi trimethoxy0lane; bet3,4 epoxycyc oh exyl)-e t hyl tri methoxy a; r-glycidoxypropyltrimethoxysilane; r-g lycidoxyp ro py meth yli di ethoxysilane; N-beta-(aminoethyl)4-aminopropyltri meth oxy:5 lane; N-bet.(aminoethyl)-r-am i nopropyi m ethy id imettioxysilatie;= r-am inopropyltrie thox5si lane; N-pheityl-r-aininopropyitriniethoxysiltme; r-mercaptopropy tri Me thoxy s ane; r-oropropyitri meth oxysil a ne ; Nl 3 -(trimethoxysilyl )propyi I-et ene d am i ne; substituted Silanes .here one or more of the substitutions contains a different fimetional groap; and .Combinations thereof. Generally, the silane coupling agent may be ineluded in the liquid hardening. agent component in an amount= capable of sufficiently bonding the resin to particulate. hi sotne embodiments .0' the present invention, the silanecoupling- .agent may be included in the liquid hardening. agent 'component in an amnunt in a range. of from. about to about 95%. by volume of the liquid hardening agent component. 'In ter embodiments, the silane coupling agent may be included in the liquid hardening agent component in an amount in a range of from about PAi) to about 50% by volume of the liquid hardening agent component.
[0019] A. liquid carrier fluid may also be used in the liquid .hardening .agent component to, arnong other things, reduce, the viscosity of the liquid hardening agent CoMponent for ease Of handling, mixing and tranSferring. 1-:-.1w$veyer,. in someembodiments, it may be desirable,. for environmental or safety Nasom, not to use .a liquid carrier fluid, Any suitable carrier fluid that is. compatible with the liquid hardening agent component and .aehieves the desired Viscosity effects may be suitable fir use. in the .present. invention. Some .suitable liquid carrier fluids are those having high flash points. (e.g.:, above: about 1259,F) 35.
because of, amotv .other thìns,etkviromentat and $afety conceinS; .Sueb solvents may include, but are not. limited to, polyethylene glycol, butyl. lactate,.
butylglyeidyl ether, &propylene glycol inethyl ether, dipropylene glycol imethyl ether,. &Methyl form= ide, diethyleneglycol: nethyl ether, ethyleneglycol butyl ether, diethyleneglycol 'butyl. ether, prOpylene carbonate, d'limonene, tInty acid methyl esters., and .combinations thereof. hi.
particular embodiments,:selection (if an appropriate liquid carri er fluid may be dependent on, inter aliaõ.the resin composition chosen.
[0020] Generally, the liquid hardening agent COInponent may be included in the resin-based sealant composition in an amount in a range of from about. 1%. to about :50% by volume of the resin-based sealant composition. In particular embodiments, the liquid hardening ..agent component -may be included in the resin,based sealant .composition in an, amount ...in 0: range. of front .about 5 to: about 25?.A. by volume of the :resin-based sealant composition. In particular embodiments, the amount of liquid hardening :agent compoSition may he Selected to impart ia: desired elasticity or coMpresSibility.to a resulting .well-borescal.
Generally., the lower the amount of hardening agent present in the resinrbased sealant composition, the greater the elasticity oreompressibility of a resulting well-boreseal. With the benefit of this disclosure, it should be within the skill of one or ordinary skill in the art to .select an a.ppropriate amount of hardening .agent to .aehieve. a desired.
elasticity or co m pressi bi ty for' a particUlar application.
[0021] In some embodiments, the resin-based :sealant com.positions may limber .20 :compriseCKD, which is a material generated in the manuthcture of cement. CKD, as that term is used herein, refers to a partially calcined kiln feed which is removed _from the gas.
stream and collected, for example, in a dust collector during the manufacture of cement.
Usually, large quantities. .of CKD are collected in the produotiOn of Cement that are .commonly disposed of as.waste. Disposal :of the CKD as waste can add undesirable costs i0 the manufacture of the cement, as .well as the environmental concerns associated with its disposal:. The chemical analysis of CKD from various Cement manufaetures varies 'depending on a number of factors, including the particular kiln feed, the efficiencies of the cement production operation, and the associated dust collection systems, 'CKD
.generally may comprise 'a :variety Of oxides, stich as SiOlõAl2O Fe203, Ca0:, MgQ, SO3, Na), and K20. The term "CK.D" i uSed herein to Mean. cement .kiin dust made as described above and equivalea forms of cement kiln dust made in other ways.
1100221 'In accordance .with embodiments of the pre-sein invention, the CKD
may be used,. among other things, as a...non-hydrating filler material to lower the .consuroptioi of the .more expensive components :hardenable resins, .that are used in the resin-based sealant compositions. 'While the CKDís a cenientitious 0.0111 po.nent that sets and h.ardens in the =preSence Of water, the CKD shOuld be -non-hydrated When mixed the liquid.
hardenable resin component and o.ptionally .the liquid hardening .atlent component as the resin-based sealant composifion -may be non-aqueous, !Or .example. In this manner, the.resin, based sealant eoinposition may be placed into a subterranean formation and allowed .to harden therein with the CKD..remaining rlijil-hydraktd.. Because theCKD is present in the hardened composition, it is loelieyed that the CKD .may help counteract the potential formation i-rif cracks in the hardened composition .andlor micro-annulus that may form.
between the hardened composition.and the pipe string. or the 'well-bore wall.
In general, the CKD is capable of setting and hardening when contacted by aqueous fluids to inhibit fluid U. flow through the (-Tarok .andlor micro-annulus. Accordingly, the CKD may prevent andfor reduce the loss olzonal isolation in spite of the formation Of cracks and/or miCro-annulus, potenti al ly resulting in an .imprOved annular seal for ernbodiments of the Wsin-baSed. sealant composi.tions.
100231 Generally, the CD .m ay be included in the. resin-based sealant compositions in an amount in a range of-from about 1% to. about 60% by vOIUMe of the reSin-based sealant composition. In particular embodiments, the CKD may be included in the resin-based sealant compositions in an, amount in a range of from about .20% to about 40%
by volume of the .resin-based sealant composition. 1.n specific embodiments, the CKD .may be present in an amount =ging between any of andfor including:any of about of about 1.%.õ
about 10%., about 20%, .about 30%, about 40%, about 50%, or about 6.0% by .volume of the resin-based sealant composition.. One of ordinary skill 'lathe airt, -with the benefit of this disclosure, -will recognize the appropriate amount of CKD to include fbr a chosen application.
100241 While the procednig description describes. CKD, the= present. invention iS
broad. enough to encompass the use of other partially .ealeined kiln feeds.
For example, embodiments o.f the resin-based sealant compositions may comprise lime kiln dust, µvhich is a material. that is generated during the manufacture of lime* 'The term "lime kiln dust"
typically refers to a partially calcined kiln feed.. which can be removed from the gas stream.
and collected, ibr. example., in. a dust collector during the manufacture of bine. The.chemical analysis of lime kiln dust fro. in various lime manufactures=varies depending on a number of factOrs., including the particular [limestone or dolomitic limestone feed, the type of kiln, the mode of operation of the kiln, the efficiencies of the lime productio.n operation,. and the associated dust collection .systems. Lime kiln dust generally may comprise N.,arying amounts of tìee lime and free .magnesium, lime stone, and/Or dolomitic limestone and a variety of oxides, such as SiD2õ. M203, C40., Mg0., SC, Na2.0,, and :K20, and other components, .stich as. ch foil des.
1.0 1-.00251 In some embodiments,. the resin-based. sealant compositions may .further comprise weighting material. As uSed herein, the term. "weighting Material"
iefers tO any particulate matter added to the resin-based sealant composition to inere.aSe rh)Wer clensity..
Examples of weighting .materialss fOr lowering density include, but are not limitedta hollow microsphereS. Examples ctf suitable hollow mierospheres include, but are not limited to, lvilow mineral glass spheres;.suCh as "S.P1-IERELITEMI". available. from 14a1liburion .Energy :Services of DWICali. Okla.; silica and alurniTia certo spheres, such. as "CENOLIfE.v"
from Mierospheres. SA. a South Africa; hollow glass microspheres, such as "SCOTCHLITErw available from the 3M Company of St. Patti, Minn.; eeramic microspheres, suett as ."1,-ILICilf SPHERESTmw :available. from the .3M
Cornpany of S.
Paul, Minn,; polymeric thicrosphereS .such as"EXPANCEL4.1'" available front Akzo Nobel .0 The Netherlands; and plastic microspheres,. such as. "IIIBRA-BEADS4'" avdi fable frtm flialliburtou Energy Services, Inc. :of Duncan, Okla. Examples Of suitable Weighting -materials. for increasing density include., hut are not limited to, silica, ilmenite, hematite, barite, Portland cem.ent, -manganese .letraoxideõ and combinations thereof.
Specific. examples a weighting materials for increasing density include, hut are not limited to, MICROSANDrm., a crystalline .silica .weighting material, and 14I-DENSet, a hematite weighting material, both available .from flalliburton Energy ServiCeS, tyf Duncan, Okla, [0026] The mean particulate sizes of the weighting Material may generally range' .20 front about 2. nanometers to about 3000 mierons. in diameter; however, in certain eircum.stances,.:other mean particulate sizes may be desire'1. and will be entirely suitable for practice of the present invention. It should be undenitood that the term "particulate," as uSei.
in this disclosure, includes alI known shapes of materials, including substantially spherical materials, 'fibrous materials; polyeonal materials (such as cubic materialS), .and mixtures.
thereof In particular embodiments, the particulate 'size of Elie weighting material .m.ay be .selected to impart. a. desired viscosity to the resin-based sealant composition. Moreover, in particularembodimentsõweightingmaterials having .different particulate Si2OS
may be mixed to achieve a desired viscosityofthe resin -based sealant composition.
[0027] Generally, the weighting material may- be included in th.e resin-based sealant .30 composition in an amount in a range. of from. about I.% to about 60% by volume of the resin-based sealant composition. In particular embodiments,. the weianing material may be included if./ the resin-based .sealant composition in an amount in a range of from about 20%
to about 40% by volume of the resin.7based sealant:composition, [0028] in .same embodiments, the resased sealant cOmpositions may further .35. comprise sweilahle particles. As used herein, the term "swellable particle'! refers to .any particle that swells upon Contact with. oil, ':gas, a combination of oil and gaS, andlor an aqueous Ii (e.g., wnter). Swellable particles suitable for use in einbodiments i..)47 the present invention may generally -swell by- tip to about 5M of their :original size at the surface. Under downhole conditions, the amount Of.swelling may Vary depending on the conditions presented, For example, ìn SOlte embodiments, the amount or.Swelling may be at least 10%. !..inder downhole conditions. In particular embodiments, the amount of swelling may be up to about 50% under downhole conditions. Howeveryas those: of Ordinary skill in the art, with the benefit :of this disclosure, ìi appreelate, the actual innount of swelling when 'the.sWtliable partieles .are included in. a :resin-baSed: Sealant Omposition may depend 10. on the concentration of the swellable particles included in the composition., among other factofg. In accordance with particular embodiments Of 'the present nrverition, the swellable particles; may be 'included in the resin-based: sealant composition, for example, .to eounteract the formation of cracks in a resultant well-bore: seal undior 'micro-annulus between the welt.
bore plug and the pipe string or the formation. In general, the swellable partieles are capable ofswelling when contacted b:y one or more of the previously 'mentioned fluids to .inh lbit fluid flow through the crack. ad/or tnicro-annuluS, .Accordinglyõ the sWellabic partieleS. may prevent andfor reduce .the loss of :o.ttal isolation in spite of the formation of cracks .andfor micro-annulusõ.potentially resulting iì an improved annular seal for the resin-based sealant compositions:
1,t)029] Sortie :specific: examples of suitable .gwellable elastomers include, hut are not limited to, natural rubber, .actylate hutadiene rubber, polyacrylate rubber, isoprene rubber, eholoroprene rubber, butyl rubber (UR), brominated butyl .rubber (131.1.R.)õ
chlorinated butyl rubber (CEIR), chlorinated. poiyei'hytene.t.C.WCPE), neoprene rubber (CR), styrene butadiene copolymer robber (SBIZ)õ. SUIphonated polyethylene (C$M), ethylene acrylate 'rubber (EAMIAElvi), .epiehlorohydrin ethylene oxide copolymer (.CO', E.00),. ethylene-propylene rubber (EPM and EDPM), ethylene-propylene-dient terpolyther rubber (EPT), ethylene vinyl acetate. copolymer, fluorosilicone rubbers: (INIVIQ), silicone rubbers' :(VM.Q)õ poly 21 -bicycle) heptene (polynorborneand), end alkylstyrerte. One example- .of a suitable swellable elastotner comprises :a block'copolymer.of a Stytetie butadiene rubber. 'Examples of suitable elaStoniers that swell when contacted .by oil incl ado., but are not limited to, nitrite rubber (NBR), hydrogpnated nitrile rubber (HN BR, Moro rubbers perfluoro rubbers. (EF.KM), tetrall uorethylenefpropylene (r.FE//4 isobutylene maieie.
anhydride, .0ther swellable elastomers that behave 'in a similar fashion With respect to oil or aqueous fluids also may be suitable- for use in particular embodiments o.r the .present invention, Furthermore, conibinations of :suitable swellable elastOmers :may:also be used in particular embodiments of the pres:ent [00301 Some .specific. examples of 'suitable water-swel table polymers, include. but are not !United, to starch-poi yacrYlate acid graft opolynter and. salts thereof,. polyethylene 'oxide polymer, carboxymethyl cellulose type .polymers, polyamlarnide, poly(a.erylic acid) end .salts thereof, poly(acrylic.zicid-co-.a.crylainide) and salts th.eitof, .g,raft-poly(etbylene oxide) .of poly(aerylie acid) and salts thereof; poly(2-hydroxYethyl methaerylate), poly(2-hydroxypropyl methacrylate), .and combinations thereof. Other water-swellable polymers that behave. :in a similar fashion with respect to aqueous fluids also may be 8uitable fc:sruse in particular embodiments of the present invention. In certain embodiments, the water-swellable :polymers may be crosalinked andior ight1y crosslinked. Those of erdinary.:skill the art, with the benefit of this disclosure,. will be able to select an appropriate sWell.able elastorner and/or water-sWellable pOlyrner Or Use. in partiettlar embodiments of the resin-based sealant compositions of the present invention based on vaiiety of faetors,: including the particular :application in .which the composition µvill be Used and the desired .swelling charaCteristics.
[.0031-1 Generally, the:swellable panicles may be included in the. min-bas.ed sealant eompositions. in an amount sufficient to provide the deSited mechaniedTproperties. Insome embodirnents, the swellable panicles may be present in the resin-based.sealant compositions .20 in an amount up to about 25.% by weight of the hardena.ble'' resin: In sorneemboditnents, the swellable particles may be present in the resin-based sealan compositions in a raw of about .51.'") 'to about 25% by weight of the hardenable resin. In sonte ethbodiments: the sellable particles. may be present in the resin-based sealant compositions in .4. range .of about 15% to about 20% by. weigh t of the hardenable resin, [00321 In addition, the= sellable panicles that may be utilized may have a wide variety of shapes and sizes of individual particles suitable for use in accordance .with embodiments Of the preset invention. B y. way of example, the. swell able -particles may have µvell-delined physical shapeas well as. an irregular .geometry, including. the physical. shape of platelets,. shavings, fibers, flakes, ribbons,..rodS, strips, spheroids,.
heads, pellet*, tablets, or .30 any other physical shape. In some embodiments,. the .swellable particles may ha' e a mean panicle size in the range of about 5 microns to about 1,500 microns. In some embodiments, the slyellable particles may have a mean particle sizo in the rang o :of about .20 microns. :to about .500 micrOrts. However, 'particle sizes outside these defined ranges also may be suitable fryr particular applications., I.
[00331 ht some embodiments of the present invention, additional solid.
materials May also be included in the Mitt...based Sealant composition to enhance the strength, hardness,. and/or toughness of the resuiting well-bore seal, The solid materials may include both natural .and man-ntade .materials, and may have: any shape, including, but not limited. to, beaded, cubic, bar-shaped, cylindrical, or mixtures thereof, and may be in any form. including, but not limited to flake or fiber thrm. Suitable materials may include, but are not limited' to, cellulose :Om, carbon fibers; glass fibers, minemi fibers!, plastic fibers (e4, .polypropylene and polyacrylic nitrile .fibers).,. metallic fibers, metal shavings, .Kcvlar fibers,. basalt fibers, wollastonite, micas (e.g., phlogopiteS and .muscoVites), and mixtures thereo1 ln soine embodiments, nanopartieles andior nanolibers may also be ineluded in the resin-based sealant composition, wherein the nanoparticles and/or nanofibers have at least one dimension less than .1 micron and, alternatively, less than about 1.00 nanometers, 110034j Carbon fibers. suitable for use in particular embodiments of the present invention include high tensile modulus carbon fibers which. have. a high tensile. strength. In some embodiments, the tensile modulus of the carbon libers may exceed 1.80 GPaõ and the tensile strength of the carbon fibers May exceed 3000 NIPa.. Generally. the fibers-may baVe mean length of about 1. Mill or. less. In some embodiments, the mean length :of the carbon fibers is from about 50 to about 500 microns. .111 jriarticulat embodiment, the carbon fibers have .a mean length in the range of fm.in about 100 to about 200 microns. in particular .20 einbodiments, the carbon fibers May be milled carbon .fibers. Suitable, commercially available earbon fibers include, but are not limited. to, ".AGIVI-94" a.nd.
"A1ìM-99". carbon fibers both available from Asbury Graphite :Mills, Inc,õ of Asbury, N.J.
[00351 .M.etallit fibers suitable. fbr .use irt particular embodiments of the present invention may include non-amorphous (Leõõ .crystalline) metallic fibers. in particular embodiments, the ion-amorphous metallic fibers may be obtained by cold drawing steel wires (Le., .steel. wool). Suitable metallic fibers include, but are not limited to, steel fibers,.
Gotteridly, the length and kliameter of the metallic fibers .may be adjusted such that the fibers are flexible and easily dispersible in the resin-based sealant composition, and the resin-based .sealatit cotnpOsition is easily .pumpable.
1(0361. These: additionai solid materials may be present in the resin-based sealant composition fthe present invention individually or in combination_ Additionally, the solid materials of the present invention may be present in the resin-based sealant compOSition in a variety of lengths. andlor aspect ratioS. A .persou having ordinary skill in.
the art, with the benefit .of this .diselosure,. will recognize the mixtures. of type, length,.
andfor aspect. ratio to 1.4 use AO achieve the desired properties of a resin-based sealant composition fur a. particular application.
[0037] In particular embodiments of the present .invention, the liquid hardenable :resin component, optional liquid hardening. agent component, and. CtiD, as well as any of the additional optional additives te.,g., weighting nteraI seIJahle particles,.
additional solid materials) inay he either batch-mixed o.r mixed on-the-fly. As used. herein, the term "on-the-fly"
tiwi herein to .inean that a flowing Stream IS continuously introduced. into another flowing stream so that the streams are combined and mixed while continuing to.
now as .a single'Strearn as part of the on-going treatment. Such miXing may 'also be described as 1 time" miking. On-the-fly mixing,..asopposed to batch or partial batch mixing, may reduce waste and :simplify subterranean treatments:: This is due,. in part,. to the fact that, in particular embodiments, if .the components are Mixed and then circumstances dictate that the subterranean treatment 'be. stopped or postponed, the mixed components May b.e.eorne.
unusable. By having the ability to rapidly Shut down the mixing .of stream.s:
(m-the-fly ìn :such embodiments, mmecessary waste may be avoided, resulting in, inter alia, increased efficiency and etist. savings.. However, other embodiments of the present invention .may uiIuv fur batch mixing of the resin-based sealant composition. In these embodiments, the resin-based. .sealant composition may he sufficiently stable to allow the composition to be prepared in advance of its introduction .into the well bore without the composition becoming unusable if not promptly introduced. into the well bore.
[0038] Generally, embodi Men ts of the resin-based sealant eornpositions of the .present invention .inay be used for any of a. variety different purposes in .which the resin-baSed .:Sealant: eompoSition may be prepared and al loWtd to harden, lit 'Sprite embodiments, the resin-based sealant composition rma.y be introduced into a subterranean form.ation and .allowed to harden. As used herein, introducing the resin-based sealant composition into a subterranean formation includes: introduction intaany portiOn of the:
subterranean formation, including, 'without limitation, into a well bore drilled into the subterranean formation,. into a near well 'bore region surrounding the well bore, .or into both. The resin-based sealant composition may be allowed to harden in the subterranean formation for a number of purpOses including, without limitation: to isolate the subterranean tbrmation from a portion of the well. bore; to support a conduit in the well bore;. tO plug a void:in the conduit; plug a void in a cement .sheath disposed in an annulus of the .well bore; to plug a perforation; to plug void micro-annulus): betWeen the cement sheath and .the conduit; to pre-vent the loss of aqueous or nonaqueous drilling fluids into loss .circulation zones such as a void, .vtigular zone,. or frieture; to plug a well for abindonment purposes; to 'form a temporary plug to. divert Ueatment flttids;.a8.a chemical packer to be Used as a fluid in front.of cement slurry in cementing operations; or to seai an annulus betWeen the :well bore and a.n ekpandable pipe or pipe stritta. For instance, the :resin-based sealant composition fltay withstand substantial amounts Of .pressure, .e.g.õ the hydrostatic- pressure of a drilling -fluid or cement slurry, without being dislodged or extruded. The resin-based sealant composition may set into a.
flexible, resilient and tough .material, which may prevent further fluid losses when circulation 1.S.reSumed, The resitt-baSed Sealant compoition mart-II-so form a non-flowing, intact tnass inside the loss-circulation .zone, This .mass plugs the Zone and inhibits loss of subsetlitently pumped drilling fluid, which alloWs few liirt her (hitting, [0039] In primary-cementing etnbodiments, .for example, embodiments :of the resin-based .sealant composition may be introduced into: a well-bore annulus .such :as a space betw.een a wail of a well bore and 4 conduit (Op, pipe strings, liners) located in the well bore or between the: conduit and a larger conduit in the well bore. The resin-based sealant composition may be allowed to harden to form an annular sheath of the hardened composition in the well-bore annulus. Among other things,. the hardened compoSition fOrrned by the res.in,7based sealant composition may ibrin a barrier, preventing the Migration of fluids in the well bore. The hardened composition also may, .for .example, support the conduit in the well bore andfor form a bond 'between the :Nvell-bore.wall and the conduit.
[0040] In some em.bodiments, the conduit rnay also be cemented into a well-bore .20 annulus by utilizing what is blown as a reverse-cementing method. The reversecementing method comprises: displacing the. resin-based sealant composition into the annulus between the conduit and the annulus between an iSting string, or an open hole :section a the wellbore, As the resin-based .sealant composition is ptmipeddoWn the annular spare, drilling fluids ahead of the resin-based ..sealant composition are displaced .around the lower ends of the conduit and up the inner diameter of the conduit and out at the !..a.trface. The fluids ahead of the resin-based sealant composition may also be displaced upwardly through a workstring that has -been run into the inner diameter of the conduit and sealed MT at its lower end..
:Because the work stringhas:a smaller inner diameter, fluid velocities ìii.
the work string will be higher and will Mire .effiCiently transfer the cuttings washed out of the .annulus during placement of the resin-based sealant. coinposition.. In an embodiment, a small amount of resin-based sealant co.mposition will be pumped into the conduit and the work string. .As soon .as a desired a:mount o.f resin-baõsed sealant composition has been pumped into the .annulus, the work string may be pulled out of its Seal receptacle and excess resin-lased sealant composition that has entered the work string can be reverse-circulated out the lower end of the work .string to .the surface, 1.6 I00411 nremedial-cernenting embodiments, a resin-based.sealant composition may be Used, for example, in scpiecze-eementing operations or in the .piacetnent dement plugs.
By way of example, the resin-based 'sealant compositio.ri may be placed in .a.well bore to .plug voids, such as holes or cracks. in the Pipe stringS; holes, cracks, spaces, or channels in the sheath; and very .small spaces (com.monly tafetted to as "Micro-annuli") between the sheath and the exterior surface of the pipe or well-bore wal [0042] It should be understood that the compositions and methods..are described in terms of "comprising," containing," or "including" various COMpOrteritS Or steps, the tonipositiOnS and methods can= alSo "cobsist essentiallY or 1--ny "consist Or the 'various compone.nts and steps. Moreover, the indefinite artieles'4`a" :or "an," .as used in the claims, are defined herein to mean oneor more than one of the element that it intro.duces.
[00431 For the = sake of brevity, only certain ranges are. explicitly :diSclosed herein.
However, ranges front any lower limit ittay .be Combined with any upper limit to. recite a range not explicitly -recite& as. well as, ranges from any lower limit .may be combined with.
any other lower limn to recite a range not explicit1y. recited, in the same way, ranges from any upper limit may.'he combined with any other upper limit to recite a range not explicitly reeitett Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, .any number and tiny included range. -falling within the range are specifically disclosed. In particular, every range of values (of the form, "from about a..
to:about b," or, equivalently, "from approximately a to b," ór. eiiva1rnt1 from approximately a-h") disclosed he-rein is to 'be understood to setforth every number and range encompassed Nvithin the broader range of values even if not explicitly recited. Th.U.Sõ eveq point or individual value may serve as its.oWn lower of upper limit combined with any other point or individual value or any other lower or upper limit,. to recite a range not.explicitlyrecited.
[0044] Therefore, 'the present .invention is well adapted to attain .the endsrnd advantages mentioned ass wallas those that are inherent therein.. The particular embodiments disclosed.aboye ore illustrative only, as the present. invention may be modified and pradticed in different but equivalent manners 'apparent .to those:skilled in the art having the benefit of the .teachings. herein. Although individual onibodiments are discusw4, the invention co*ers all combinations =i-)..f all thoseembodiments. Furthermore, no limitations are intended to the details. .of COnStrtMi011 or.design herein .sbown, other than as described in tbe claims below;
MS , the terms in the claims hava their plain, ordinary meaning unless-othenise explicitly and ejeady defined by. the patentee.. It is therefore vvident that the particular illustrative embodithents .disclosed above may be altered' :or modified and all such variatiOns are .35. :considered .within the scope and spirit of the -present iriVentiOri, if there is any conflict in the =USageS= of a word or term in this speeificatiot and one or more patent(s) Or other documenti that may be ineortxyrated herein by teferetWe, the definitions that are cOnsisient with thi.
specification should be adopted,
Claims (19)
1. A resin-based sealant composition comprising:
a liquid hardenable resin component; and kiln dust.
a liquid hardenable resin component; and kiln dust.
2. A composition according to claim 1 wherein the liquid hardenable resin:
component comprises a hardenable resin selected from the group consisting a an epoxy-based resin, a novolak resin, a polyepoxide resin, a phenol-aldehyde resin, a urea-aldehyde resin, a urethane resins, a phenolic resin, a furan resin, a furan/furfuryl alcohol resin, a phenolic/latex resin, a phenol formaldehyde resin, a bisphenol A diglycidyl ether resin, a butoxymethyl butyl glycidyl ether resin, a bisphenol A-epichlorohydrin resin, a bisphenol F
resin, a glycidyl ether resin, a polyester resin: and hybrids and copolymers thereof, a polyurethane resin and hybrids and copolymers thereof, an acrylate resins, and any combination thereof.
component comprises a hardenable resin selected from the group consisting a an epoxy-based resin, a novolak resin, a polyepoxide resin, a phenol-aldehyde resin, a urea-aldehyde resin, a urethane resins, a phenolic resin, a furan resin, a furan/furfuryl alcohol resin, a phenolic/latex resin, a phenol formaldehyde resin, a bisphenol A diglycidyl ether resin, a butoxymethyl butyl glycidyl ether resin, a bisphenol A-epichlorohydrin resin, a bisphenol F
resin, a glycidyl ether resin, a polyester resin: and hybrids and copolymers thereof, a polyurethane resin and hybrids and copolymers thereof, an acrylate resins, and any combination thereof.
3. A composition according to claim 1 or 2 wherein the resin-based sealant composition further comprises a liquid hardenable resin component, the liquid hardenable resin component comprising a hardening agent selected from the group consisting of an, aliphatic amine, an aliphatic tertiary amine, an aromatic amine, a cycloaliphatic amine, a heterocyclic amine, an amido amine, a polyamide, a polyethyl amine, a polyether amine, a polyoxyalkylene amine, a carboxylic anhydride, a triethylenetetraamine, an ethylene diamine, a N-cocoalkyltrimethylene, an isophorone diamine, a N-aminophenyl piperazine, imidazoline, a 1,2-diaminocyclohexane, a polyetheramine, a diethyltoluenediamine, a 4,4'-diaminodiphenyl methane, a methyltetrahydrophthalic anhydride, a hexahydrophthatic anhydride, a maleic anhydride, a polyazelaic polyanhydride, a phthalic anhydride, and any combination thereof.
4. A composition according to any preceding claim the method of claim 1 wherein the kiln dust comprises cement kiln dust.
A composition according to any preceding claim wherein the kiln dust comprises lime kiln dust.
6. A composition according to any preceding claim wherein the kiln dust is present in an amount in a range of from about 1% to about 60% by volume of the resin-based sealant composition.
7. A composition according to any one of claims 1 to 5 wherein the kiln dust comprises cement kiln dust and is present in an amount in a range of from about 20% to about 40% by volume of the resin-based sealant composition, wherein the liquid hardenable resin composition is present in an amount in a range of from about 50% to about 75% by volume of the resin-based sealant composition and further comprises a solvent, and wherein the resin-based sealant composition further comprises a liquid hardenable resin component in an amount in a range of from about 5% to about 25% by volume of the resin-based sealant composition.
8. A composition according to any preceding claim wherein the resin-based sealant composition further comprises a weighting material selected from the group consisting of hollow microspheres, silica, ilmenite, hematite, barite, Portland cement, manganese tetraoxide, and any combination thereof.
9. A composition according to any preceding claim wherein the resin-based sealant composition further comprises a swellable particle.
10. A composition according to any preceding claim wherein the resin-based sealant composition further comprises a component selected from the group consisting of cellulose fibers, carbon fibers, glass fibers, mineral fibers, plastic fibers, polypropylene.
fibers, polyacrylic nitrile fibers, metallic fibers, metal shavings, Kevlar fibers, basalt fibers, wollastonite, micas, phlogopites, muscovites, nanoparticles, nanofibers, and any combination thereof.
fibers, polyacrylic nitrile fibers, metallic fibers, metal shavings, Kevlar fibers, basalt fibers, wollastonite, micas, phlogopites, muscovites, nanoparticles, nanofibers, and any combination thereof.
11.A method comprising:
providing a resin-based sealant composition according to any preceding claim; and allowing the resin-based sealant composition to harden.
providing a resin-based sealant composition according to any preceding claim; and allowing the resin-based sealant composition to harden.
12. A method of forming a seal in a subterranean formation comprising:
introducing a resin-based sealant composition according to any one of claims 1 to 10 into a subterranean formation; and allowing the resin-based sealant composition to harden in the subterranean formation
introducing a resin-based sealant composition according to any one of claims 1 to 10 into a subterranean formation; and allowing the resin-based sealant composition to harden in the subterranean formation
13. A method according to claim 11 or claim 12 wherein the resin-based sealant composition is non-aqueous such that the kiln dust does not hydrate during the step of allowing the resin-based sealant composition to harden,
14. A method according to any one of claims 11 to 13 further comprising allowing the kiln dust to hydrate when contacted by one or more aqueous fluids atter the step of allowing the resin-based sealant composition to harden.
15. A method according to any one of claims 11 to 14 wherein the resin-based sealant composition is used in a primary-cementing method.
16. A method according to any one of claims 11 to 14 wherein the resin-based sealant composition is used in a remedial-cementing method.
17. A method according to any one of claims 11 to 16 wherein the resin-based sealant composition is used in a reverse-cementing method.
18. A method according to any one of claims 11 to 17 wherein the resin-based sealant composition is allowed to harden and form a resin sheath in a well-bore annulus between a conduit in the subterranean formation and a well-bore wall or between the conduit and a larger conduit in the subterranean formation.
19. A method according to any one of claims 11 to 17 wherein the resin-based sealant composition is allowed to harden to seal a void in a sheath located, in a. well-bore annulus or conduit in the subterranean formation, to seal a void in the subterranean formation, to seal a space between an interior surface of the sheath and the conduit, and/or to seal a space between an exterior surface of the sheath and the subterranean formation or a larger conduit in the subterranean formation.
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| US13/598,052 US20120328377A1 (en) | 2005-09-09 | 2012-08-29 | Resin-Based Sealant Compositions Comprising Cement Kiln Dust and Methods of Use |
| PCT/US2013/057213 WO2014036218A1 (en) | 2012-08-29 | 2013-08-29 | Resin-based sealant compositions comprising cement kiln dust and methods of use |
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| CA2910489A1 (en) | 2013-05-15 | 2014-11-20 | Sangamo Biosciences, Inc. | Methods and compositions for treatment of a genetic condition |
| CN108300435B (en) * | 2018-02-08 | 2021-09-07 | 陕西海睿能源技术服务有限公司 | Embedded high-pressure-bearing plugging agent |
| US11168243B2 (en) | 2018-08-30 | 2021-11-09 | Saudi Arabian Oil Company | Cement compositions including epoxy resin systems for preventing fluid migration |
| US11352541B2 (en) | 2018-08-30 | 2022-06-07 | Saudi Arabian Oil Company | Sealing compositions and methods of sealing an annulus of a wellbore |
| US10696888B2 (en) * | 2018-08-30 | 2020-06-30 | Saudi Arabian Oil Company | Lost circulation material compositions and methods of isolating a lost circulation zone of a wellbore |
| CN110003853A (en) * | 2019-04-28 | 2019-07-12 | 祝亚琴 | Efficient sealing agent |
| US11332656B2 (en) | 2019-12-18 | 2022-05-17 | Saudi Arabian Oil Company | LCM composition with controlled viscosity and cure time and methods of treating a lost circulation zone of a wellbore |
| US11370956B2 (en) | 2019-12-18 | 2022-06-28 | Saudi Arabian Oil Company | Epoxy-based LCM compositions with controlled viscosity and methods of treating a lost circulation zone of a wellbore |
| US11193052B2 (en) * | 2020-02-25 | 2021-12-07 | Saudi Arabian Oil Company | Sealing compositions and methods of plugging and abandoning of a wellbore |
| US11236263B2 (en) | 2020-02-26 | 2022-02-01 | Saudi Arabian Oil Company | Method of sand consolidation in petroleum reservoirs |
| US11827841B2 (en) | 2021-12-23 | 2023-11-28 | Saudi Arabian Oil Company | Methods of treating lost circulation zones |
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| US5098612A (en) * | 1988-12-10 | 1992-03-24 | Rowsell Farrell D | Method of preparing solidified and stabilized hazardous or radioactive liquids |
| US7607483B2 (en) * | 2004-04-19 | 2009-10-27 | Halliburton Energy Services, Inc. | Sealant compositions comprising colloidally stabilized latex and methods of using the same |
| US7488705B2 (en) * | 2004-12-08 | 2009-02-10 | Halliburton Energy Services, Inc. | Oilwell sealant compositions comprising alkali swellable latex |
| US7743828B2 (en) * | 2005-09-09 | 2010-06-29 | Halliburton Energy Services, Inc. | Methods of cementing in subterranean formations using cement kiln cement kiln dust in compositions having reduced Portland cement content |
| US7789150B2 (en) * | 2005-09-09 | 2010-09-07 | Halliburton Energy Services Inc. | Latex compositions comprising pozzolan and/or cement kiln dust and methods of use |
| US20120328377A1 (en) * | 2005-09-09 | 2012-12-27 | Halliburton Energy Services, Inc. | Resin-Based Sealant Compositions Comprising Cement Kiln Dust and Methods of Use |
| US7762329B1 (en) * | 2009-01-27 | 2010-07-27 | Halliburton Energy Services, Inc. | Methods for servicing well bores with hardenable resin compositions |
| WO2011012922A1 (en) * | 2009-07-29 | 2011-02-03 | SERVICES PETROLIERS SCHLUMBERGER, dénommée SLB | Compositions and methods for servicing subterranean wells |
| US8143198B2 (en) * | 2009-08-25 | 2012-03-27 | Hallilburton Energy Services Inc. | Radiation-induced triggering for set-on-command compositions |
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| MX2015002335A (en) | 2015-09-23 |
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| EP2890756A1 (en) | 2015-07-08 |
| EP2890756A4 (en) | 2016-04-13 |
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| AU2013308769A1 (en) | 2015-02-26 |
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Effective date: 20150223 |
|
| MKLA | Lapsed |
Effective date: 20220301 |
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| MKLA | Lapsed |
Effective date: 20200831 |