AU2016222404B2 - Foaming of set-delayed cement compositions comprising pumice and hydrated lime - Google Patents

Abstract

A variety of methods and compositions are disclosed, including, in one embodiment a method of cementing in a subterranean formation comprising: providing a set-delayed cement composition comprising water, pumice, hydrated lime, and a set retarder; foaming the set delayed cement composition; activating the so set-delayed cement composition; introducing the set-delayed cement composition into a subterranean formation; and allowing the set delayed cement composition to set in the subterranean formation. Additional methods, foamed set-delayed cement composition, and systems for cementing are also provided.

Description

2016222404 31 Aug 2016

ABSTRACT

A variety of methods and compositions are disclosed, including, in one embodiment a method of cementing in a subterranean formation comprising: providing a set-delayed cement composition comprising water, pumice, hydrated lime, and a set retarder; foaming the setdelayed cement composition; activating the so set-delayed cement composition; introducing the set-delayed cement composition into a subterranean formation; and allowing the setdelayed cement composition to set in the subterranean formation. Additional methods, foamed set-delayed cement composition, and systems for cementing are also provided.

FOAMING OF SET-DELAYED CEMENT COMPOSITIONS COMPRISING

PUMICE AND HYDRATED LIME

2016222404 31 Aug 2016

BACKGROUND

The present application is a divisional application from Australian patent application no. 2014317923, filed on 8 September 2014, which claims priority to and the benefit from US 14/032,734 , filed on 20 September 2013, and US 61/875,410, filed on 9 Sepember 2013, the entire contents of which are to be taken as incorporated herein by this reference.

[0001] Cement compositions may be used in a variety of subterranean operations. For example, in subterranean well construction, a pipe string (e.g., casing, liners, expandable tubulars, etc.) may be run into a wellbore and cemented in place. The process of cementing the pipe string in place is commonly referred to as primary cementing. In a typical primary cementing method, a cement composition may be pumped into an annulus between the walls of the wellbore and the exterior surface of the pipe string disposed therein. The cement composition may set in the annular space, thereby forming an annular sheath of hardened, substantially impermeable cement (i.e., a cement sheath) that may support arid position the pipe string in the wellbore and may bond the exterior surface of the pipe string to the subterranean formation. Among other things, the cement sheath surrounding the pipe string functions to prevent the migration of fluids in the annulus, as well as protecting the pipe string from corrosion. Cement compositions also may be used in remedial cementing methods, for example, to seal cracks or holes in pipe strings or cement sheaths, to seal highly permeable formation zones or fractures, to place a cement plug, and the like.

[0002] A broad variety of cement compositions have been used in subterranean cementing operations. In some instances, set-delayed cement compositions have been used. Set-delayed cement compositions are characterized by remaining in a pumpable fluid state for at least about one day (e.g. at least about 7 days, about 2 weeks, about 2 years or more) at room temperature (e.g. about 80° F) in quiescent storage. When desired for use, the setdelayed cement compositions should be capable of being activated whereby reasonable compressive strengths are developed. For example, a cement set accelerator may be added to a set-delayed cement composition whereby the composition sets into a hardened mass. Among other things, the set-delayed cement composition may be suitable for use in wellbore applications, for example, where it is desired to prepare the cement composition in advance. This may allow, for example, the cement composition to be stored prior to its use, In addition.

2016222404 29 May 2018 this may allow, for example, the cement composition to be prepared at a convenient location and then transported to the job site. Accordingly, capital expenditures may be reduced due to a reduction in the need for on-site bulk storage and mixing equipment. This may be particularly useful for offshore cementing operations where space onboard the vessels may be hmited.

[0003] While set-delayed cement compositions have been developed heretofore, challenges exist with their successful use in subterranean cementing operations. For example, set-delayed cement compositions prepared with Portland cement may have undesired gelation issues which can limit their use and effectiveness in cementing operations. Other set-delayed compositions that have been developed, for example, those comprising hydrated lime and quartz, ma he effective in some operations but may have limited use at lower temperatures as they may not develop sufficient compressive strength when used in subterranean formations having lower bottom hole static temperatures.

[0003a] The above discussion of background art is included to explain the context of the present invention. It is not to be taken as an admission that any of the documents or other material referred to was published, known or part of the common general knowledge in Australia at the priority date of any one of the claims of this specification.

SUMMARY OF INVENTION [0003b] According to a first aspect of the present invention there is provided a method of making a foamed set-delayed cement composition, the method comprising: mixing a setdelayed cement composition comprising: water, pumice, a dispersant comprising a polycarboxylated ether; hydrated lime, and a set retarder comprising a phosphonic acid derivative; storing the set-delayed cement composition in a pumpable fluid state for at least about one day; adding a foaming additive to the set-delayed cement composition; forming the foamed set-delayed cement composition after the step of storing, the forming comprising: adding a gas to the set-delayed cement composition.

[0003c] According to a second aspect of the present invention there is provided a method of making a foamed set-delayed cement composition, the method comprising: mixing a set-delayed cement composition comprising: water, pumice, a dispersant comprising a polycarboxylated ether; hydrated lime, Portland cement, and a set retarder wherein the set

2016222404 29 May 2018 retarder comprises a primary retarder and a secondary retarder, wherein at least one of said retarders comprises a phosphonic acid derivative; storing the set-delayed cement composition in a pumpable fluid state for at least about one day; foaming the set-delayed cement composition after the step of storing, the foaming comprising: adding a foaming additive and a gas to the set-delayed cement composition.

[0003d] According to a third aspect of the present invention there is provided a foamed cement composition comprising: water; pumice; hydrated lime, wherein a pumice-tohydrated lime weight ratio is about 3:1 to about 5:1; a polycarboxylated ether dispersant; a phosphonic acid derivative set retarder; calcium chloride, wherein the calcium chloride is present in a range of about 1 % to about 20% by weight of the pumice; a foaming additive; and a gas; wherein the foamed cement composition is foamed to a foam quality between about 18% to about 38%.

2a

2016222404 31 Aug 2016

BRIEF BISCRIWION OF THF DRAWINGS (0001] These drawing ilbsteie certahi aspsow of some of the embodimerns af the pmsem method, and should not be used to hm or define the method, (0002] FIG. I illustrates a system O preparation and delivery of a set-ddhyed SeemeM composition to a wellbore In accordance with certain embodimcms, (0003] FIG. 2A illustrates surface equipment that may be used ip placement of a setdelayed cement oomposdloa In a wellbore m accordance with certain smbodiwtds, ((HMM] FIG. 28 Obstndes meeemem of a sm-debycd cement eompositfen bio a wellbor© annulus b accordance with certain embodiments.

DESCRIPTION OP PREFERRED EMBODIMENTS

2016222404 31 Aug

O CM (0005] The example embodiments relate to subterranean cementing operations and, more particularly, in certain embodiments, to set-delayed cement compositions and methods of «sing set-delayed cement compositions in subterranean formations.

[0006] Embodiments of the set-delayed cement compositions may generally eompP'M, water. j-unnee. hydrated inne Kisui a <<· wmrdw Option-.rii\, she - ct-delaye-d cement compositions may further comprise a dispersant. Embodiments of the set-delayed cement compositions may be foamed. Advantageously, embodiments of the set-delayed cernem eompo.-.iti.ons may be capable fo' remaining in a pumpable tiitid sneo lor an extended 10 period of time. For example, the set-delayed cement compositions may remain in a pumpable fluid state for at least about 1 day, about 2 weeks, about 2 years, or longer. Advantageously, the set-delayed cement compositions may develop reasonable compressive strengths after activation at relatively low temperatures. While the set-delayed cement compositions may be suitable for a number of subterranean ..cementing Operations, they may 15 be particularly suitable for use in subterranean formations having relatively low bottom hole static temperatures, e.g.» temperatures less than about 200°F or ranging from about !00°F to about 200ΊΕ In alternative embodiments, the set-delayed cement compositions may be used in subterranean formations having bottom bole static temperatures up to 45GF or higher.

[0007] The water used in embodiments of the set-delayed cement compositions may 20 be from any source provided that it does not contain an excess of compounds that may unde\»abiy affect other components in the set-delayed cement compositions. For example, a set-delayed cement composition may comprise fresh wakt or salt water. Salt water generally may include one or more dissolved salts - therein and may be saturated or unsaturated os desired for a ptHiudur jppbsaOon Scau.iur ⁽v brines -on be sunubtc u-s .25 use hi embodiments. Further the water may he preset» m an amount suffieieei to fours a pumpable slurry. In certain embodiments, the water may be present in the set-delayed convent composition in an amount in the range of from about 33% to about 200% by weight of the pumice. In certain embodiments, the water may be present in the set delayed tetueni compositions in an amount in the range of from about 33'% to about 'fo·',. by we-cfo ot die pumice. One of ordinary skill in the art with the benefit of this disclosure will recognize the appropriate amount of water for a chosen application.

i 0003 i I mhodimeots of the sci-ddaycd eetneni -.oiupositium. mas compis-e punuee Generally, pumice is a volcanic rock that, can exhibit cementitious properties in that it may sot and harden in the presence of hytir.ued limo and water. The pmniix. may also he ground

Generally, the pumice may have any particle size distribution as desired for a particular

2016222404 31 Aug 2016

1.0 application. In certain embodiments, the pumice may have a mean particle size in a range of front about 1 micron to about 200 microns. The mean particle size corresponds to dSO values as measured by particle size analyzers such as those ntanufactured by Malvern htstnmxnis, Wowi'siersbi:,·. I'niled Kingdom hi specuic ettibvibmetos, the pumice may have a mean particle size in a range of .from about I micron to about 200 microns. front about 5 microns to about 100 microns, or front about 10 microns to about 50 microtis. In one particular cmbodim-cii?. the pumi,c may have a mean painek’ size td ics' than about 15 microns. An example of a suitable pumice is available from Hess Pumice Products, inc·., Maiad Idaho. j\ ΒΎ2~ behtweight aggrtomke hmm; ;t partiek: s_;\ oi 1,' tiaso ab<-tft 15 microns. it should be appreciated that particle sizes too small may have mixability problems while particle sizes too large may not be effectively suspended in the compositions. One of ordinary skill in the art. with the benefit of this disclosure, should be able to select a particle sr-v to; ifre pisoVkC rtdUibk f.i? 3 d?ov-, η ,ippl^:,e,o ·>η.

[00(0] i mbodtrnents of the xs-dJmcd ,\ment · ipowfi, > s may comprise hydrated lime. As used heroin, the term hydroied bme’ w th be utuieirtwd to mean calcium hydroxide. Io s<>roe embodiments, the hyuratod bme .. λ be pro' id.’»! as quicklime ieaicinsn oxide) which hydrates when mixed with water to lours the hydrated lime I'he hydrated lime may be included in embodiments of the set-delayed cement compositions, for example, to form a hydraulic composition, with the pumice. For example, the hydrated lime nw be included in a puraiee-toHiydratedHime weight ratio of about 10:1 to about I: J or3H to about 5rt. Where present she hydmwd limv may be included m the '.ci-delayed ,en?eot compositions m ee rmonni m the mugs of from about ίο^-,, μ- aoou* 100% by weigh? oi the pumtee. lot example hi ,,>>roe erobodimen-s. the hydrated time ma,· he pv.enf u? .m .mimne ranging between any of and/or including any oi about 10%, about 20%, about 40%, about 60%, about. 80%, or about 100% by weight of the pumice, io some embodiments, the vementnk'us comj« ί ιοη?Ί pi, ,<.;>( kt di, set-dchived vimwei coropovbnu o:.o costs-si esstmtoufr of Us, piunke .usd the hydrated lint,-. I'm example, the ,,;s-:emtuous components may primarily comprise the pumice and the hydrated, time without mw additional components (e.g., Portland cement, fly ash, slag cement) that hydrauheaik set in the presence of water. One of ordinary skill in the art. with the benefit oi’fr.- disclosure. will recognize the appropriate amount ot the hydroted lime to include for a chosen applleafion.

[0010) Embodiments of the set-delayed cement compositions may comprise a set retarder. Λ broad vauety of »,*t ictaidcr, may be suitable for use in the set-delaved cement con η··.- ikons. Ira eswuplc. th,' o.^; rctaide, ,omp;!,c pnorohnmi. ewe's, sue. w s-fl··'loni'dvu'.iine ten.umotto,kn, phosphoric a,(41 diethyk t-konmu ·. pen?.’{m, ihrton.

s

2016222404 31 Aug 2016 phospbow <ujd\ vie - hgoosoifonutes, such sodium lignosuifbnate, calcium I ignosnl innate, etc.: salts such as stannous sulfate, lead acetate, monobasic calcium phosphate, organic acids, such as citric acid, tartaric add, etc.: cellulose derivatives such as hydroxyl ethyl cellulose (HEC) and earboxymeth)I hydrovjethyl cellulose (VMllFCj, synthetic co- or ier-pohiuem comprising sulfonate and carboxylic add groups such us sulfonate-functionalized acrylamide-acrylic acid eo-polysoers; borate compound' -och as Jk;di ho; nes, sodium ηκι-.borute, sodum; teoabotatc, ρ·’<α.ΐ.Μ»η· pet-tabor.-!;·., demuu’ --,s thereof, or mixtures thereof. Examples of suitable set retarders include, among others, phospliem sete d-ι h. stives example of a sn-table sd reh-.rdei is Micro M.iHE' com, m ichnder, avmbhie from Halliburton Energy Services, Inc. Generally, the set retarder may he tucscnt m the sc1~<kh;ycd cement compositions in an amount sufficient to delay the setting tot j -t’-sned im.>. In some emboumtemv. hre -et reteojer mu\ be present m the setwieI c-cd coiCTt compositions m an amount in the range of from about 0.01 % to about 10% by weight of the pumice, in specific embodiments, the set retarder may be present in an amount ranging between any of and/or including any of about 0.01%, about 0,1%, about. 1%, about 2%, about 4^a ft, about 0%, about 8%, m- about 10%. by vveight of the pntnice. thtc of ordinary skill in the art, with the benefit of this disclosure, w ill recognize the appropriate amount of the set retarder to include for a chosen application.

[0011s As previously mentioned, embodiments of the set-delayed cement compositions may optionally comprise a dispcisam. ί samples of suitable dispersants include, without limitation, suifbnated-ibnnatdehydc-knod dispersants (e.g., sulfonated acetone formaldehyde condensate), examples of which may include Daxad*¹ 19 available from foe·- xpecmiP Chemicilx. Anrit';·. Pent’··,·l··.mid Otb-.-t sunjbl·? dispcrx.-ms rnav b·.polycarhoxylated etbe; foxpes emts sue;; .>s 1 iqu.i ten¹/ s-gip _ah5) Liqubnen; 'ill· available from BASF Corporation Houston, Icvis; or Utbac-rvl G available from Coatex, Genay, France. .An additional example of a suitable commercially available dispersant is ( i'R ·’ fo ,pc;s,i!si. a·, uikmle bran Ikilfo-mtok 1 nugy Sc. · i ?cs. inc f ί-mMom ieteJs. Of particular importance in regards to the examples that follow, is that the LiquimenC 5141.. dispersant c->mprist:s 36% by ‘xcighl or -be polycarroxylatea si -:r m vmef. While a variety of dispersants moy be m-eu ;n accordance ouh embed intents. pfoyciubo .Mated cihcr dispsmantx uu> be particularly suitable for use in some embodiments. Without being limited ire !hci-n. it E beite'.ed that pifoe,irbt;^v.E;ted ethci rasperem is mm, s^itergisiie^ib, interact with other components -.4 die sci-fi·; hoed νν;ο·..';·ί composition I-···' example. It la believed that the poiycarboxviated ether dispersants may react with certain set retarders fe.g..

2016222404 31 Aug 2016 phosphonic acid derivatives) resulting in tbnnatlon of a gel that suspends the pumice and hydrated lime h; the υηηροχίί-οϋ (bra·: extended period of time.

[0012'| In some embodiments, the dispersant, may be included in the set-delayed cement compositions in an amount in the range of from about 0,01% to about 5% by weight of the pumice, in specific embodiments, the dispersant, may be present in an amount ranging, between any of and/or including any of aboui 0.01%. about 0.1%, 0.5%, about 1%, about abci:: *%, ab,, ;i 4%, m bout ?’ i by rooy >· of th· pnnncc, One oi m-diom skid h, the art, with the benefit of this disclosure, will recognize the· appropriate amount of the dispersant to include tor a chosen application.

[00.13] Embodiments of the set-delayed cement compositions may comprise a mechanical property enhancing additive. Mechanical-property-enhancing additives may be included in eiurtoihnisTt, <?'the ·<-delaycd 'omperomra'·. to, ί- cxampic, cn\uu udvpu,ue compressive strength and long-senn sdnctural miegnty, these properties can be affected by the strains, sires-es, temperature. pressure. and inipuci cs'kxts Item a subieiuincan environment. Examples .of mechanical property enhancing additives include fibers, such as graphitic carbon fibers, glass fibers, steel fibers, mineral fibers, siisc.i fiber:-. polyesiet fibers, polyamide fibers, and polyolefin fibers, among others. Speci fic examples of graphitic carbon fibers include fibers derived from polyacrylonitrile, rayon, and petroleum pitch. Where used, the meelunuctd-propers ·, remrare. :ny adoifu-. may be present n- .nt .«new ! irons about 0.01% to about 5% by weight of the pumice, fn speci fic embodiments, the mechanical-propertyenhancing additives may he present in an amount ranging between any of and/or including any of about 0.01%, about 0,1%, 0.5%, about 1%, about 2%, about 3%, about 4%, or about 5% by weight of the pumice. One of ordinary skill -in the an. with the benefit of this disclosure, will recognize the appropriate, amount of the meehantcal-property-enhancing additives to include for a chosen application.

(0014-1 other udditriu, suitable lor use in subterranean cementing operations also mas t\ .nchuk'd m embodiments, .«fife -ret-deke.ed cement coraposmons, ί <,,ϋυρ:ο.\ ο- ’-κ,η additives include, but are not limited to, weighting agcob. lightweight additives, gasgeneiidmn admu.c., lost·.cremation mraerrafr.. tiltraooo-%onn--n ,reldct^;'vs, fluid-loss-control additives, detbaming agents, foaming agents, thixotropic additive», and combinations thereof. In embodiments, one or more of these additives may be added io the set-delayed cement composition after storing but: prior to placement of the set-delayed cement composition into a subterranean formation. A person having ordinary skill in the art, with the benefit of this disclosure, will readily be able to determine the type and amount of additive useful for a particular application and desired result.

2016222404 31 Aug 2016 [0015] Those of ordinary skill in (he art will appreciate that embodiments of the setdelayed cement compositions generally should have a density «liable lor a partieulat ,<ppiu-ufoo R\ w,r, Ο: ί xumpw to wl-tU.p cd tx.· -sent eoe->.->smon\ m'o ha\ e ,j ri-msiiy in the range of from about 4 pounds per gallon (“ib/gal”) to about 20 lb g;b in certain emlxxllmente, the set-delayed cement compositions may have a. density in the -range of from about 8 Ib/gal to about 17 Ib/grfo Embodiments of the set-delayed cement compositions may be foamed or unlearned or may comprise other means to reduce their densities, such as hollow microspheres, low-density elastic beads, or other density-reducing additives known in the art. Sn embodiments, the density may be reduced after storing the composition, hut

SO prior to placement in a subterranean formation, Those· of ordinary skill in the art, with tlte benefit of tins disclosure, will recognize the appropriate density for a particular application, [()016 [ As discussed above, embodiments of the set-delayed cement compositions may be foamed. Emhodimesus of the set-delayed cement compositions may be foamed to provide a lightweight composition that does not evert excc'Mve -force On formations penetrated by the wellbore. In addition to being lightweight, a foamed composition may also improve the ability of the composition to maintain pressure and prevent the flow of formation fluids into and through the composition during its transition time, Foamed compositions may also be advantageous because they have low fluid loss properties. thus limiting kn.-. of fluid circulation. Additionally, foamed compositions when Set may also have a lower modulus of elasticoy than n-m-foamed compoGrtons. wbwh k otwo desirable it enables the resultant set cement composition to resks rts esses everted on ihc composition in Sltii.

[0017 ] to purtxuuu- «.nUxidimetu, die xi-ikUyeu oment eo-urks-founs n be foe,med ui the well me By ol example, ihe set-delayed eeww ce.mposUhU’i may' be foamed immediately prior to use. binbodun-etus may be foamed with a foaming additive and by entraining gas into the set-delayed cement compositions. In particular embodiments, foe foaming additive and gas may be introduced after combination of foe composition with an activator, The set-delayed cement compositions may be foamed, for example, to provide a set-deiaved cement composition with a reduced density.

((10.18] The gas used tor foaming the composition may be· any suitable gas for foaming, including, but not limited to: air, nitrogen, and combinations thetvof, Generally, the gas should be In an amount suflkient to fon> the desired loam. Foaming additives may be included in t-mkufouivutp to. icr exxrtoe. facdii.ue fouiinny anO,-r s'eibik/c tb,; lesniunu foam formed therewith,.

2016222404 31 Aug 2016 [0019} 'in particular embodiments. (he foaming additive may include a surfactant or combination of surfactants that reduce il\ rfufrec icnsion of the water. By way of example, the foaming agent may comprise an anionre nonionic, amphoteric rineiudmg /witte-riumv surfactants), cationic surfactant, or mixtures thereof. Examples of soitabie foaming additives include, hut arc not limited to: betaines: anionic surfactants such as hydrolyzed keratin: amine oxides such as a alkyl or alkene dimethyl amine oxides; eocoamidopropyl dimethylamine oxtde: methyl ester sulfonates; alkyl or alkene amtdbbeiaines such as eocoamidopropyl betaine; alpha-olefin sulfonates; quaternary surfactants such as trimethyltailowammonium chloride and trfraetbylcocoamiHoniutn chloride; C8 to C22 alkyiethoxylate sulfates; and combinations thereof. Specific examples of suitable teaming agents include mixtures of an ammonium salt of an alkyl ether sulfate, a eocoamidopropyl betaine surfactant, a eocoamidopropyl dimethylamine oxide surfactant sodium chloride, and water: mixtures of an ammonium salt of an alkyl ether sulfate surfactant, a eocoamidopropyl hydroxy .uitame >uj factum, a eocoamidopropyl dhnethybimine «.-ride sunacicnt. sodium

IS chloride, and water; mixtures of an ethoxylated alcohol ether sulfete surfactant, an alkyl or alkene amidopropyl betaine s'urfitctam, and an alkyl or alkene dimethylamine oxale surfactant: aqueous solutions of an alpha-olefinic sulfonate surfactant and a betaine .surfactant; and combination?» thereof Examples of suitable foaming additives are /OM SEAl AM * 200(5 agent and Foamer K)2k'‘, both available from Halliburton 1 nergy >L->ceshK HousU'ii, R\e\ I >nhodm'.,n’s may re: foamed ' nhin :·, fo su'quality range 1 between about 5% to about E0% and, more particularly, from about 18% to about 38%, As nred herem, the term foam qts-sbr/' refrn. m ten: wfomw ofMmfoncd gas md k dci ned b\ the following formula; Foam Quality ^;;; (Total Foam Volume·- Liquid Volume) / Total Foasn Vol time.

[0020] As previously mentioned, the cement compositions may have a delayed set in that they remain in a pumpable fluid state for at least one day (e.g., at least about I day, ab-m· 2 we Aw ahsu.t > y-?;:u. or longer! at room temperature in quiescent storage. For example, the set-delayed cement compositions max temain in a pumpable fluid state for a period of time from about 1 day, abom 2 weris, about 2 years, or longer. In some embodiments, (he set-delayed cement compositions may remain in a pumpable fluid state for af least about I day, about 7 days, about 10 days, about 20 days, about 30 days, about 40 days, about 50 days, about 60 days, about 2 years, or longer. A fluid is considered to be in a pumpable fluid slate where the fluid has a consistency of less than 70 Bearden units of ^.onstsUtecy rlteA a·, measured on a high-tempesaiure high-presstrre consistomeicr at room temp-.-: at me teg. about K>r'lrf in accordance with the procedure for determining cement

2016222404 31 Aug 2016 thickening fnnes «.u forth in API RF Practice 1 OB-2, /Wee /or Testing

Rtii < I U 4 Flhii-.m July 2ϊί 5.

[0021] When desired for use, embodiments of the set-delayed cement 'compositions may be activated (e.g., by combination with an aunaier} to tbe^-by set into a hardened mass. By way of example, embodiments of the set-delayed cement compositions may be activated to set to form a hardened mass in a time period in the range of from about 1 hour to about 12 imuts. For example, embodiments of the set-delayed cement compositirsns may set to fonn a hardened mass in a time period ranging between any of and/or including any of about 1 day, about 2. days, about 4 days. about o days, about S days obout todays, or about (2 days, | (A) 22 j in some embodiments. the set-delayed cement compositions may set to have a desirable eompresv’.'. -tovngth aftet an non. ί omprc»sEv '-trengtb c- generally the nmaeny ol a m.uer-.d or -troetnre to- ntthf'S. i.d axtady directed pushing to’Ces Ί :k compress?ve strength rosy be measured at a specified time after the set-delayed edrhent composition has been activated and the resultant composition is maintained under specific ernpemtyre uitd ntessuu controls Compse: ,Ae strength nm be measured by either a desityetbe method or non-desunctive method, 'Ihc dcsttikine method physically tots the Strength of treatment fluid samples et various points in. time by crushing the samples in a eoinprcssion-icsting machine. '1 he compressive strength is calculated from the failure load

2.0 divided by the cross-sectional area tossting the load and is reported in units of pound-force per square inch tpsi). Non-destructive methods typically may employ an Ultrasonic Cement Analyzer i“UCA), available from Farm Instrument Company, Houston. TX. Compressive strengths may he determined in accordance with API IIP 10B-2, Rec/unmemkd Practice for Testing Well Cements Emm bunion. July 2<O5.

2.5 j .0(123] By way of example, the set-delayed content eomnosition. may develop a 24hour compressive strength in the range of from about 50 psi to about 5000 psi, alternatively, from about 100 psi to about 4500 psi, or aiternatively from about 500 psi to about 4000 psi, in some embodiments, she set-delaved eerottd eompo-,iss.»n may develop a compressive strength in 24 hour» of at least about. 50 psi, at ions! about 100 psi, ai teast about 500 psi. or more. In some embodiments, the compressive strength values may be determined using destructive or non-dcsiruetive methods at a temperature ranging from 100-F η» 200Ί⁷.

[^AO24‘· I mlwdnn ’.A may uxtode the addition ui’u cement x-t activator to the setdelayed eenunE comp·».mom,. I xnopk-:,. ; cm.mk < c: ru; set aciivatot'- include, but are not limned to; amines stub a-, tnethaimhimhie, diethanolamine, \dnat> such us sodium silicate; zinc formate; calcium acetate; Groups 1A and HA hydroxides such as sodium

2016222404 31 Aug 2016 hydroxide, magnesium hydroxide, and calcium hydroxide; monovalent sails such as sodium chloride; divalent salts such as calcium chloride; nanosilica (i.e., silica having a particle size of k-,, ibai's or ,-·4^!ί<·ϊ to uhovt I Oh nanometers!; p-ilsphosphau-s: and eomhrn.mmis therooi In MRU embodiments. a -.omhunm-m of die polyphospb.ne and a monfoni-mt ^ah be used tor activation. The monovalent salt, may be any salt that dissociates to form a monovalent eanon, such x sodium and potassium salts Specific example.’ of suitable monovalent salts include p nissinn·. sulfate, ami sodium suHate, Λ -..irrois oi -hlleren! poiyphcsphjes sn.iy be used in combination * iih the monovalent salt for activation of the set-delayed cement compoHbons ix luimg pobm.ju, metaphosphate salts, phosphate salts, and combinations thereof Sxxi u exam »ies of polymeric metaphosphate salts that may be used include sol e ix\. PvU,! ,ν'ι,'ς s κ m ti-mbi-iphosplnm' vUmm umarncfjjiiiosphaic, sodium p,. tUu nt ip'-i'^h it> soduun huptamclaphosphate, sodium oetametaphosphate, and combinations thereof, A specific example of a suitable cement set activator comprises a -.ombina-u-n ofwxiiuui sulhro and sodium hevuiiiciitphosphak’ In pasficular embodiments, the activator may be provided and added to the set-dchiycd cement composition as u liquid additive, for example, a liquid additive comprising a monovalent salt, a polyphosphate, and optionally a dispersant.

(06.'fo 1 hv tefnent so! -hon'd Iv .nklcd -, mhodime-nts ->f ihe sci delayed cement compo-nOon tn an amount sufficient to actixute the set-delayed ceracht composuion t· - - k vto .1 13 rdened ip ι-s In txrfnn e-n-boihrnenn>, ;^;v cement xi ret·-.,nor may be added to the set-delayed cement composition in an amount m the range of about 1% to about 20% by vt min ofibe pumux. In specUk embodnocnis. the eemcri vi a· ‘Amo·· m,o be prv.r·! in an amount ranging between any of and or including any of about i%, about 5%, about 10%, about 15%, or about 20% by weight ol the pumice. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the cement set activator to inehide for a chosen application, [0026( As vdl iv appro-, cued by those of onhn sry skid in the art, embodiment of the set-delayed cement compositions may be used in a variety of subterranean operations, ins'lu-hng pfommy and remedial cementing In some ,roh-'»bnronr· a -rot-del e.ed cement composition may be provided that comprises wafer, pumice, hydrated lime, a set retarder, and optionally a dispersant. The set-delayed cement composition may he introduced into a subterranean formation and allowed to set therein, As used herein, introducing the setdelay cd eemem composition iii<o _t> ,ubterranean fonnaoo'i mebidet mmndueiJiv· mto au\ poi'uon of the sufoerr.'iiViin Ιοπη,ί··mu, iriue-nim, -mh·-!! fomt.moo, im,·- n -lehbore folded into the siikie.-roneju formation m\s u :X u well 1-.1:-,- tcyion ¹ nrooundhw hie webboic. or mt-1

2016222404 31 Aug 2016 both. Embodiments may further include activation of the set-delayed cement composition. The activation of foe wt-delayed remem' emnposifotu posy eompr-sc. for example, the addition of & cement set activator to the set-delayed cement composition.

[0027] in some embodiments, a set· delayed cement composition may be provided mat eompne-w wtsU'w purmee, J:\drated hms.. a 5e· retarder. and opnot’idb a disper-int 1 Ue set-delayed cement composition may be stored, for example, in a vessel or other suitable container. The sef-delaved cement composition may be permitted to remain in storage tor a desired time period. For example, the set-delayed cement composition may remain in storage for a time period of about 1 day, about 2 weeks, about 2 years, or longer. For oampk, he m-,d.!>ed ^.meut κ,ηηροοοοη senna i shetor a tan·. p,. nod of about I day, about 2 days, about 5 days, about 7 days, about 10 days, about 20 days, about 30 days, about 40 days, about 50 days, about 00 days, about 2 years, or longer, in some embodiments, the set-delayed cement compoMrion may remain in storage tor ,t time pc nod in ά range of fora about 1 day to about 2 years or longer. Thereafter, the set-delayed cement composition may be activated, for example, by addition of a cement set activator, introduced iuui ; subt -r. mean to’-muiton, mfo allowed to set therein. topu-utob, »he ,>. -dehned cement >;crapn\toco may he fbame-J prior re m-mducram into the Ofoterraocm formation.

(002bi in primary cementing emhe-diments, tor example, embodiments of the setdelayed cement composition may be introduced Into an annular space between a conduit located in a o· There .uni the w.-JB of a w-Jiborc food os a large: >.onduii <n P'c wdmwe). wherein the wellbore penetrates the subterranean formation. The set-delayed cement composition may be allowed to set in the annular space to form an annular sheath of hardened cement. The set-delayed cement composition may form a barrier that prevents the migration of thuds in the wellbore. The set-delayed cement composition may also, tor example, support the conduit in the wellbore.

|thh'··»| to rm cdial ementbig einbedimeuw. a .set-delayed cemera compose ι·>;ϊ niiiv bo used, for cxmnple. in queevc-s < meutinc onenmoos e-j m dw placement of .wment plugs. By way of example, the set-delayed composition may be placed in a wellbore to plug an opening such as a void or crack that is m the formation, in a gravel pack, in the conduit, in the cement sheath, and/or between the cement sheath and the conduit (e.g.. a microannulus), (00301 An example embefonten! ^unpa-es a method, uf cememme. in a subterranean formation etm.onse.g. p-oufom- a set-fo 1 o-ed cen'v -3 composition comprising water, pumice, hydrated '-uh, and a set mt m e: foam ag foe »e: delayed cement composition; stuwnmg me ^-ranted sto-delays t‘ , mud soinpouram. u bodnemg the foamed set-dek-eed to

2016222404 31 Aug 2016 cement composition into a subterranean formation: and allowing the foamed set-delayed eompmerimi m \c: m the sunk ranean torma-to·!.

[0031] An example embodiment comprises a foamed set-delayed eemem composition comprising: water, pumice·» hydrated lime, a foaming additive, entrained gas., .5 and a set retarder.

(00321 ,-\o exampie embodiment otapivs a system for cementing comprising: a set-delayed cement composition, comprising water. pumice, hydrated lime, a set retarder, a foaming additive for foaming the «-delayed cement composition; a gas for foaming the set» dehowi cemcni comp»».=:bon; end .< cement set aeto-uto!· to? uuhation oi fee set-Uelayed cement composition.

[0033, Roiernm,; i.ow to Th I. prepamtion e-fa set-dday-.-d cetoeto <. οηρη m- o in ;!(-,ord,»Kc viih evsmpi? euihiuJi-'it-fUs viii now to- Awr-G.-d FIG, 1 d imtruk, i soitir 2 for preparation of a set-delayed cement composition and delivery to & wclihue o ._Svcvn.,mee with certain embodiments. As shown, the set-delayed cement composition may be mixed in mixing equipment 4, such as a jel mixer, re-awmating nu^r. ot a b:»uh nnxvt, fot example, arsd then pumped via pumping equipment 6 to the wellbore. in some embodiments, the mixing equipment 4 and the pumping equipment 6 may bo disposed on one or more cement trucks w -U be apparent to those of onhe-ai c skill ο_; the art it’· votrs embodiments, a mixer may be used, for example, to continuously mix the lime/sehable material with the water as it is being pumped to the wellbore, l00?4i Ac example tedmique for placing a set-dc laved cement composition info a subterranean formation will -now be described with reference to FIGS, 2-A and 2B. FIG, 2A illustrates surface equipment 10 that may he used in placement of a set-delayed cement compuiit'.i'n in ,ttx i.dancc v :;i ecru, r 'mbodsok· lx it ,.i>>uid be ο- -'ed mat wink FIG 2-’’ generally de-pjeo; a land-L-jsed ops-ontou, diose fehkb h- the <m will readily swogns/e that foe principles described beum are equally applicable to subsea operations that employ floating or sea-based platforms and rigs, without departing from the scope· of the disclosure. As illustrated by FIG. 2A, the surface equipment 10 may include a cementing unit 12,'which may include one or mere cement trucks. The cementing unit 12 may include mixing equipment 4 and pumping equipment 6 (e.g.. FIG. 1) as will be apparent to those of ordinary skill in the art. The cementing unit 12 may pump a set-delayed cement composition 14 through a feed pipe 16 and to a cementing head 18 which conveys the set-delayed cement composition .14 downhole.

hhitoj iurnub: n-m to Fb·. 2B. th·· kU-dG'c.ed cement ompos.tonn 14 may be placed into a subterranean formation 20 in accordance with example embodiments. As

2016222404 31 Aug 2016 illustrated, a wellbore ?? may be drilled into the subterranean formation 20. While wellbore 22 o -how i idntg centmlh variedly into the subterranean formation 20, the principles dtwibed herein at·⁴ also applicable tr» wellbores that extend at an angle through the suhu. ¹ neat v um 20. ,-.ueh as hori/mttai and slanted wellbores. As illustrated, the '\vbHit ,«rnp« ' rsib 2+. in the dlussuued embodiment, -a surfacecasing 26 has been Inserted into the Wellbore 22. TSie surface casing 26 may be cemented to the walls 24 of the wellbore 22 by cement sheath 28, In the illustrated embodiment, one or mote additional conduits (e.g., intermediate easing, production casing, liners, etc.), shown here as casing 30 may also be drisso>e, t iv Ilbon. ?.?. As fore reme-j. -here n. a v-'ilboic imnulus 32

W formed between t v kSmuj; Ό and the walls 24 of the wellbore 22 and/or the surface casing 26 ^f *ne or na’.e .urn. hvs- '+ v be .m rebec ?> c.w 36 k- tuple. t>-ecu·. d?A *he vasjfig 70 ;!·<, v/hoi, ptn> ό and da , g the .s .w» am, v men.

[0036] With eomfoued rfouenee tt? I G .'υ A , Λ <>ys.d <v £ c^mpt-shfon 14 may be pungvd do·.’n the in-cr-of ol th tts-om Ό lh Λ'4'λ ¹ emcm eomposhrem 14 may be allowed io flow down the interior of the casing 30 through the mfo-ig shoe 4.2 at the bottom of the casing 30 and up around fbe casing 30 into the wellbore anntsk»:- 32. The setdelayed cement composition 14 may he allowed to set in the wellbore annulus 32, for evuople, u- funs a (.>':ncnt riw.ub tha? opports and p< «dt s'-·- the cam-g '0 In too reedl-m: 32. While not fomoas-m, f-dv?· techniques m.re also be utilized Ins lntro-.hv.non of the set20 echoed ^.emeui emnp, re-mn '3 ίΐ\ w;j, , feKa.no·.' re\e w e'reutatJon revhrm-iK·- nsa\ be used du-f include mtroduem-: the >.-ei-4ektycd cement v-iupositu·]! 14 inn? ttre sub-errencan formation 20 by-· way of the wellbore annulus 32 Instead of through the casing 30, [0037] As it is introduced, the set-delayed cement composition .14 may displace other fluids 36, such as drilling fluids and or spacer fluids that may be present in the interior of the casing 30 and/or the w'ellbore annulus 32. At least a portion of the displaced fluids 36 may exit the wellbore annulus 32 via a flow line 38 and be deposited, for example, in one or more retention pits 40 (e.g.. « mud pit), as showr- on F 1(4 2 ^A. Referring again to PIG. 2B, a bottom plug 44 may be introduced info the wellbore 22 ahead of the set-delayed cement composition 14, for example, to separate the set-delayed cement composition 14 from the fluids 36 that may be inside the casing 30 prior to cementing. After the bottom plug 44 reaches the landing collar 46, a diaphragm or other suitable device shock! rupture to allow the set-delayed cement composition 14 through the bottom plug 44, In PIG, 2B. the bottom phm 44 i? >t;,mu on the landing collar 46 In the iiiustmu-d embodiment. a u-p plug 48 may foo-Oikaed ink- die ufofoore ”2 behind the svi-dektsed vement comp-suhm ί -I the rep

2016222404 31 Aug 2016 pku. ·Ε· m;n '.vpar.ue -he sto-deGy-⁴ cement omposPion 14 jrijin a dispiov.-mcm (hod 50 and also push the set-delayed cement composition 14 through the bottom plug 44.

lOOoifl :;:e esempbis set'-S-.hted ic-aOl w-nipt>$ha-its. disclosed herein may directly or indirectly affect one or more components or pick's oi equipment associated with the preparation, ckhveiy. rexur-tutv, r..\',ehng, ooise, arm or dispel eiibe di.xlowd xcidefiycd cornua v-'inpoMi-.-no bm -uample, ih·’ dfech-wd sei-i!el.i>ed ceiiKut -.ompo-r.lr-ns may directly or indirectly affect one or more misers, rcku-.-J ndsism -.quipmetfl. mod pits, storage facilities or unite, composition separators, heal exchangers, sensors, gauges, pumps, compressors, and the like used generate. store, monitor, regulate, and nr recondition the

I0 exemplary set-delayed cement cornposhirms. The disclosed set-delayed ceme-ni compositions may also directly or indirectly affect any transport oi delivery equipment used to convey the set-delayed cement compositions to a well site or downhole such as. for example, any transport vee?U$, conduite. pipelines, trucks, mbulan», and or pip*,'- twed to composhit-nally move the set-delayed cement compositions from one location to another, any pumps.

1.5 compressors, or motors (e.g,, topside or downhole) used to drive the set-delayed cement compositions into motion, any valves or related joint» used to regulate (he pressure or flow rats ol Ή,- xct-rtekncd cement comp·· uions, and -m\ wiv.-ir the., pm-, mm <mc temperature!, gauges, and or combinations thereof, and the .like. The disclosed set-delayed cement compositions may also directly or indirectly affect the various downhole equipment and tools tha=i may come into contact with the set-delayed cement compositions such as, hut not limited to, wellbore casing, wellbore liner, completion string, insert strings, drill string, coiled tubing, slickline, wireline, drill pipe, drill collars, mud motors, downhole memm and/or pumps, cement pumps, suriace-mounted motors and/or pumps, centralizers, turboliw’·'·. serai-· hets, flu-_:o ie.g . shoes, etohuv. i.dves, -,-tori. togwog fool- arid rehitou telemetry equipment, actuators (e.g,, electromechanical devices, hydromechanical devices, ,-se.i sliding sleew . produv’.t.tn vi\w· ph’to -.teem· ilk·' flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, etc.), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive coupler, etc,), control lines (e.g., electrical, fiber optic, hydraulic, etc.), surveillance lines, drill bits and reamers, xn-ors or dh-trlbuted seowns. dov-nhof heat w.ehangvi... ·4\« and cosiv.a wip-ng actuation devices, tool seals, packers·, cement plugs, bridge plugs, and other wellbore •\ol:'.th'n -,h> or eoinpouente md die hfe

2016222404 31 Aug 2016

EXAMPLES [0039] To facilitate a better understanding of the present embodiments, the following exainpies of certain aspects of some embodiments are given, hi no way should the following examples be read to limit, or define, the scope of die embodiments.

Example I [0040] A sample set 'delayed cement composition was prepared with the following components: pumice (DS-325 lightweight aggregate), hydrated lime, dispersant (Liquiment'*'' 558 iP), primary retarder <. Micro Munfr cement retarde?·? weighting additive (MicmMax* Weight Additive, available from Halliburton Energy Services, Inc.. Houston, Texas), secondary rviardc? DIR'-' ..ement u-tvder, available from Halliburton Energy Services, lne._s Houston, Texas), Class H Portland cement, and water. Each component, with the exception of the primary retarder (Micro Matrix⁴' cement retarder), is presented as a percentage of the weight of pumice (hwoP). The primary retarder is measured in units of gallons per 46 pound sack of pumice (gal/sk). The compositional makeup is listed in S able i below.

Table 1

Sample SeMMayed Cement Compositional Makeup

Material	.Amount	Units	.......................................... Γ Weight (g)	% bw in total ;
Pumice	106	% bwoP	58682.7	55,56
Hydrated lime	20	% bwoE	11736.5	............. 1 11.11 ]
Dispersant	0.5	% IwoP	291.;	0.28
Primary Retarder	0.06	plAk	734.6	0.70
Weighting Additive	2	% bwoP	1173,7	1.11
Secondary Retarder	0.5	% bwoP	293,4	0,28
Portland Cement	2	% bwoP	1173.7	UH
Water	53.7	% bwoP	31534,5.	29.86
Total	-	..	105620.2	100 ............. .......

2016222404 31 Aug 2016 [0041 { The sample fo Example I remained thud, msxable, pumpabk, find stable with no solids settling or gelation for greater than 40 days, The sample had a measured density of 13.5 pounds per gallon. Minimal doses of dispersant were added during the storage period to maintain the slurry’s optimal rheology, This exemplary sample serves as the base slurry for the remaining examples provided below.

Example 2 [0042] The rheological properties of the sample set-delayed cement composition of Example 1 meiwused auct Mormg t w «.ample» n r»««r. a-i operators and pressure fora period of 41 days. After preparation, the rheological properties of the samples were determined using a Model 35A l-'ann Viscometer and a No. 2 spring with a Pann Yield Stress Adapter» in accordance with the procedure set forth in API IIP Practice 1 OB-2,

Pwtiee for Testing fob// Cewte. The results of this test are set forth in

Table 2 below.

Table 2

Viscashy Test?»

Age ui Sympic (days)	FYSA Readmits ..................................................................................................................................
RPM :	3	1 6	( 100	200	: 300	i	AD
41	A VO.:	13	113	t 35	i 56	: 75.5	5 j	4

Example 3 [0043] Three -sample set-delayed cement compositions, samples I -3, and two controls» controls 1 and 2, were prepared from the base slurry described in Example 1. boomer 1026™, a foaming additive, was added to each of the three .samples in varying amounts after a time period of'41 days. Additionally, a cement set activator, CaCb, was added to sample 2 and control 2, The amount of the cement set activator added to each sample was sufficient to deliver a 5¾ by weight of pumice activator amount to the setdelayed cement composition. The base and foamed densities were measured. Additfonsliy. the destructive compressive strength was measured using a mechanical press in accordance with API RF Practice 1 OB-2, Rec<>irtmentiea‘ Practice for Jesting fob// Ce/neMs, Adtfofonally, -be dest.-uctive i.-ompressivc strength w&> measured by allowing the samples to cure in a 2 by 4” plastic cylinder that was placed in a water bath at 19iPF t«.> form set cylinders Immediately after removal from the waier bad':, destructive : stwegth were determined using a mechanical press in accordance with API RF 10B 2, rv»v?/u«t/e.ri

1?

2016222404 31 Aug 2016

Priieik-t for Testing Wetf CcsisunE. The rosohs of this test are set forth below. The reported compressive strengths are an average for two cylinders of each sample. The samples and controls were cared at I atmosphere, I9O^QF; compressive strength measurements were taken at 72 hours.

Table 3

Compositional Makeup and Cbarneterisdes

··.·.·—- —........>	SampC ;	Samplc'2	Sample 3	Control 1	Control 2
Sample Weight (g)	1363.2	1363.2	1363.2	817,5	817.3
j 1 onming Additive (g)	3.14	— ............ 12.21	14
1 Activator (g)		37.87 >	-	r	25,8
Baw, 'Density (pre;	13.5	13,5	13,5	13,5	13.3* 7
Foamed Density tppg)	H	9.1	9,2.	·	7
Foam Quality	%%	33%	32%		-
t empress! ve Strength (psi)	P 10. A’	.............................. 534,45	135.(8	i 1222.46	i 1360.14

^Density of Control 2 with the Activator, [0044] in addition to the characteristics, of Table X the foam stability of samples 1-3 was measured m both the slurry state and the set stats. This data is set forth io Table 4 below.

2016222404 31 Aug 2016

Tssbk 4

Fumn Stability Mejssurero«sis.

Foam Stability	Sample 1	Sample 2	Sample.)
	, Slurry	Set	Starry	Set	Slurry	Set
Mow than a trace of hoc fluid?	U	N		N	N	N :
Hubbles [>n sun'ace of bubble coalescing (breaking, enlargement, merging}?	:N	N	N •	N	N	N
1 seesslve colunin-hvigh; reduction?	N		N	N	N	i H )
Signs of (.Unsay xcutogation (so'eahnw w dark coionuioo from. top to bottom}?	I N	N	N	: N	f N : ..........	: N

[0045] The Archimedes Method was used to measure the slurry density of Samples D3 in top, middle, and bottom portions. Densities that were close in weight from top to bottom indicate stable foam while considerable variation in densities indicates unstable foam. AH units are in pounds per gallon. This data is set forth in Table 5 below.

Table 6 .Density Uniformity

Archimedes hktiiod	bs ample 1	Example 2	1” sample 3
Top (ppgl	10,5«	s.os	9.26
Middle (ppg)	10.5?	S.99	930
Bottom t ppg)	10,46	.............T.........	9,25

[()046] Lastly, the rheology of foamed Samples 1-3 was measured «slog the same 10 technique as used in Example 2 to measure the rheology of the base slurry. The base slurry &

designated as Control 1 in Table 6 below. The rheology data is set forth in Table 6 below.

2016222404 31 Aug 2016

Table ij Viscosity Tests

		FYSA 'Readings
Density ippg’S	RPM :	i 3 :i	i 6 1	-- - . 100	200 i	300	3D	6D
'()!fflroi j	13.5	Ava	13	i 13	i /A I	56	: 75,5 :	5	4
Sample 1	II	AVG.	? 10	- 105	i 33,5 :	50,25	65,5	; 3,5	] 2:5 :
Sample 2	9,1	AVG.	2.25	) 3 ]	1 .17.5 ·.;	] 29.5	40	1.5	1 ;
Sample 3 | 9,2	AVG.	: 17	17.5	40.5	36.5	70.5	12 '	9

μ,·04?| Ha-opiv * thus, indier-.kv shat me hnwd sicuR-. exh-bh «ood compressive strength while maintaining suitable rheologies and uniform densities.

[0048] Two sample set-delayed cement compositions, samples 4 and 5, were prepared from the base slurry described in Example L A ten-ent ses -.yrtivanu. VaCl·.. ww added to the samples in an amount sufficient to deliver a 5% by weight of pumice activator

K) amount io the set-delayed cement composition. Sample S further included graphitic carbon fibers in an amount of about 0.18% by weight of the pumice. 'she ymphltiv <,4}br« fibers were PAN carbon fibers derived irons polyacrylonitrile, Foamer 1026^, a foaming additive, was added to each of the samples in an amount of 0,18% by weight of the pumice. Additionally, the destructive compressive strength was measured by allowing the samples to

IS cure in a 2” by 4^<! plastic cylinder that was placed in a water bath at 190%' to form set cylinders. Immediately after removal from the water bath, destructive compressive strengths were determined using a mechanical press in accordance with API RP 10B-2, jteeommvtided Precito/or Tasting 029/ The results of this test are set forth below. The reported compressive strengths are an average for three cylinders of each sample. The samples and controls were cured at 1 atmosphere, I9(TF; compressive strength measurements were taken at 72 hours.

2016222404 31 Aug 2016

Table 7

CumposHluntiil Makeup and Charseiemrics

.. ...... ..............................„Ά	Sample 4	Sample 5
Base Slurry (g)	1000	1000
Carbon Fiber I'g)	-,.	s 10
Activator (gj	ί 27,8	7 2T8 7
Foaming Additive tg)	TO	: 10
B;tsc Density (ppgs	13,5	; 13.5
Foamed Density (ppg)	8.33	7 8.33
t 'mnpret-.sivv Strength (psi)	: 62	143 „„„

[0049] It should be understood that the compossbons and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the competitions and methods can also “coumm essentially of’ or “consist of’ the various components and steps. Moreover, the indefinite articles “a” or “an” as.used in the claims, are defined herein ;e mean nne or nnsre than one of the element that h mtrodu<.'.re, (0050’J For the sake of brevity, only certain ranges are explicitly disclosed herein,

I lowevsr. ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from shy upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range arc specifically disclosed. In particular, every r.ntge of values (of the form, “from about a to about bor, equivalently, “from approximately a to b,” or. equivalently, “frost approximately a-b¹’} disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values even if not explicitly melted. Thus, every point or individual value may serve ns h\ own lower --r upper hnvt combined with any other punt or individual vi-hic or auy other sower or upp^;?f hmh. to recite ; range tun e.\p!icilly recited.

(0051] Therefore, the present embodiments are well adapted to attain the ends and advantages mentioned as welldui nsv mberenr thereto. The particular embodiments disclosed above are illustrative only, and may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings

2016222404 31 Aug 2016 herein. Although individual embodiments are discussed, the invention covers all combinations of all those embodiments. Furthermore-, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee, it is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and ail such variations are considered within the scope and spirit of the invention. If there is any conflict in the usages of a word or term in this specification and one or more patent(s) or other documents that may be incorporated herein by reference, the definitions that are consistent with this specification should be adopted.

[0052] Where the terms ’’comprise, comprises, ’'comprised or comprising are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more other features, integers, steps or components, or group thereof.

2016222404 29 May 2018

Claims (20)

1. The claims defining the invention are as follows:

   1. A method of making a foamed set-delayed cement composition, the method comprising:

   mixing a set-delayed cement composition comprising: water, pumice, a dispersant comprising a polycarboxylated ether; hydrated lime, and a set retarder comprising a phosphonic acid derivative; storing the set-delayed cement composition in a pumpable fluid state for at least about one day;

   adding a foaming additive to the set-delayed cement composition;

   forming the foamed set-delayed cement composition after the step of storing, the forming comprising:

   adding a gas to the set-delayed cement composition.
2. 2. The method according to claim 1, wherein the foaming additive is selected from the group consisting of: a betaine; hydrolyzed keratin; an amine oxides; an alkyl or alkene dimethyl amine oxide; a cocoamidopropyl dimethyl amine oxide; a methyl ester sulfonate; an alkyl or alkene dimethyl amidobetaine; cocoamidopropyl betaine; an alphaolefin sulfonate; a quaternary surfactant; trimethyltallowammonium chloride; trimethylcocoammonium chloride; a Ck to C22 alkylethoxylate sulfate; and any combination thereof.
3. 3. The method according to claim 1 or 2, wherein the foamed set-delayed cement composition has a foam quality between about 5% to about 80%.
4. 4. The method according to any one of claims 1 to 3, wherein the foamed setdelayed cement composition has a density between about 9 pounds per gallon to about 11 pounds per gallon.
5. 5. The method according to any one of claims 1 to 4 wherein the set retarder further comprises at least one retarder selected from the group consisting of a phosphonic acid derivative, a lignosulfonate, a salt, an organic acid, a cellulose derivate, a synthetic co23

   2016222404 29 May 2018 or ter-polymer comprising sulfonate and carboxylic acid groups, a borate compound, and any combination thereof.
6. 6. The method according to any one of claims 1 to 5, wherein the dispersant further comprises a sulfonated-formaldehyde-based dispersant.
7. 7. The method according to any one of claims 1 to 6, wherein the foamed setdelayed cement composition further comprises a cement set activator, and wherein the cement set activator comprises at least one activator selected from the group consisting of an amine, a silicate, zinc formate, calcium acetate, a Group IA hydroxide, a Group IIA hydroxide, a monovalent salt, a divalent salt, a nanosilica, a polyphosphate, and any combination thereof.
8. 8. The method according to any one of claims 1 to 7, wherein the foamed setdelayed cement composition remains in a pumpable state for at least about one day to about one week.
9. 9. The method according to any one of claims 1 to 8, wherein the pumice has a particle size of about 1 micron to about 200 microns.
10. 10. The method according to any one of claims 1 to 9, wherein the hydrated lime is present in an amount of about 10% to about 100% by weight of the pumice.
11. 11. The method according to any one of claims 1 to 10, wherein the set retarder is present in an amount of about 0.01% to about 10% by weight of the pumice.
12. 12. The method according to any one of claims 1 to 10, wherein the dispersant is present in an amount of about 0.01% to about 5% by weight of the pumice.
13. 13. The method according to any one of claims 7 to 12, wherein the cement set activator is present in an amount of about 1% to about 20% by weight of the pumice.
14. 14. The method according to any one of claims 1 to 13, wherein the set-delayed cement composition further comprises at least one mechanical property enhancing additive selected from the group consisting of graphitic carbon fibers, glass fibers, steel fibers, mineral fibers, silica fibers, polyester fibers, polyamide fibers, and polyolefin fibers, and any combinations thereof.

    2016222404 29 May 2018
15. 15. The method of claim 14 wherein the mechanical property enhancing additive is present in an amount from about 0.01% to about 5% by weight of the pumice.
16. 16. The method according to any one of claims 1 to 15, wherein the set-delayed cement composition develops a 24-hour compressive strength of about 500 psi to about 2400 psi.
17. 17. A method of making a foamed set-delayed cement composition, the method comprising:

    mixing a set-delayed cement composition comprising:

    water, pumice, a dispersant comprising a polycarboxylated ether;

    hydrated lime,

    Portland cement, and a set retarder wherein the set retarder comprises a primary retarder and a secondary retarder, wherein at least one of said retarders comprises a phosphonic acid derivative;

    storing the set-delayed cement composition in a pumpable fluid state for at least about one day;

    foaming the set-delayed cement composition after the step of storing, the foaming comprising:

    adding a foaming additive and a gas to the set-delayed cement composition.
18. 18. The method according to claim 17, wherein the set retarder further comprises at least one retarder selected from the group consisting of a phosphonic acid, a lignosulfonate, a salt, an organic acid, a cellulose derivate, a synthetic co- or ter-polymer comprising sulfonate and carboxylic acid groups, a borate compound, and any combination thereof.

    2016222404 29 May 2018
19. 19. The method according to any one of claims 17 to 19, wherein the foamed setdelayed cement composition further comprises a cement set activator, and wherein the cement set activator comprises at least one activator selected from the group consisting of an amine, a silicate, zinc formate, calcium acetate, a Group IA hydroxide, a Group IIA hydroxide, a monovalent salt, a divalent salt, nanosilica, a polyphosphate, and any combination thereof.
20. 20. A foamed cement composition comprising:

    water;

    pumice;

    hydrated lime, wherein a pumice-to-hydrated lime weight ratio is about 3:1 to about 5:1;

    a polycarboxylated ether dispersant;

    a phosphonic acid derivative set retarder;

    calcium chloride, wherein the calcium chloride is present in a range of about 1 % to about 20% by weight of the pumice;

    a foaming additive; and a gas;

    wherein the foamed cement composition is foamed to a foam quality between about

    18% to about 38%.

    WO 2015/035280

    PCT/US2014/054496

    2016222404 31 Aug 2016 i/2

    WO 2015/035280

    PCT/US2014/054496

    2016222404 31 Aug 2016

    2/2.