CA2921230C - Two-part set-delayed cement compositions - Google Patents

Two-part set-delayed cement compositions Download PDF

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CA2921230C
CA2921230C CA2921230A CA2921230A CA2921230C CA 2921230 C CA2921230 C CA 2921230C CA 2921230 A CA2921230 A CA 2921230A CA 2921230 A CA2921230 A CA 2921230A CA 2921230 C CA2921230 C CA 2921230C
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slurry
pozzolan
lime
cement composition
cement
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CA2921230A1 (en
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Thomas Jason Pisklak
Kyriacos Agapiou
Peter James Boul
Pauline Akinyi Otieno
Lance Everett Brothers
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Halliburton Energy Services Inc
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Halliburton Energy Services Inc
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • C04B28/10Lime cements or magnesium oxide cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00Clay-wares
    • C04B33/02Preparing or treating the raw materials individually or as batches
    • C04B33/13Compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/18Compositions 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 mixtures of the silica-lime type
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467Compositions 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
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06Arrangements for treating drilling fluids outside the borehole
    • E21B21/062Arrangements for treating drilling fluids outside the borehole by mixing components
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00Sealing or packing boreholes or wells
    • E21B33/10Sealing or packing boreholes or wells in the borehole
    • E21B33/13Methods or devices for cementing, for plugging holes, crevices, or the like
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/20Retarders
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

A variety of methods and compositions are disclosed, including, in one embodiment a method of cementing comprising: providing a pozzolan slurry comprising a pozzolan and water; providing a lime slurry comprising hydrated lime and water; allowing the pozzolan slurry and the lime slurry to remain separate for about one day or longer; mixing the pozzolan slurry and the lime slurry to form a cement composition: and allowing the cement composition to set.

Description

TWO-PART SET-DELAYED CEMENT COMPOSITIONS
BACKGROUND
[0001] The present embodiments relate to subterranean cementing operations and,in certain embodiments, to set-delayed cement compositions and methods of using set-delayed cement compositions in subterranean formations.
[0002] 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 tu.bulars, 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 and position the pipe string in the wellbore and may bond the exterior surface of the pipe string to the IS subtenlinean fbrmation, Among other thins, the cement sheath surrounding the pipe string prevents the migration of fluids in the annulus and protects the pipe string from corrosion.
Cement compositions may also be used in remedial cementing methods to seal cracks or holes in pipe strings or cement sheaths, to seal highly permeable formation zones or fractures, or to place a cement plug and the like.
100031 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., about 7 days, about .2 weeks, about 2 years or more) at room temperature about 800 17) in quiescent storage. When desired for use, the set-delayed cement compositions should be capable of activation and consequently develop reasonable compressive strengths. For example, a cement set activator may be added to a set-delayed cement composition to induce the composition to set into a hardened mass.
Among other things, set-delayed cement compositions may be suitable for use in wellbore applications such as applications where it is desirable to prepare the cement composition in advance. This may allow the cement composition to be stored prior to use. In addition, this May allow the cement composition to be prepared at a convenient location before transportation 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 he particularly useful fur offshore cementing Operations where space onboard the vessels may be limited.

[00041 While set-delayed cement compositions have been developed heretolbre, 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, may he effective in some. operations hut 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. In addition, it may he problematic to activate some set-delayed cement compositions while maintaining acceptable thickening times and compressive strength development.

BRIEF DESCRIPTION OF THE DRAWINGS
[000111 These drawings illustrate certain aspects of some of the embodiments of the present method, and should not be used to limit or define the method.
[00021 FIG. illustrates a system for preparation and delivety of a set-delayed Seeman composition to a wellbore in accordance with certain embodiments.
[0003] FIG. 2A illustrates surface equipment. that may be used in placement of a set-delayed cement composition in a wellbore in accordance with certain embodiments.
[0004] FIG. 2B illustrates placement of a set-delayed cement composition into a wellbore annulus in accordance with eertain embodiments.

DESC Rirn ON OF PREFERRED EMBODIMENTS
[00051 The example embodiments relate to subterranean cementing operations and, more particularly, in certain embodiments, to set-delayed cement compositions and methods of using set-delayed cement compositions in subterranean tbrmations.
-5 [00061 Embodiments of the set-delayed cement compositions may generally comprise %iater, a pozzolanõ and hydrated lime. Optionally, the cement compositions may tbrther comprise a dispersant and/or a cement set retarder. Alternatively, embodiments of the set-delayed cement composition may comprise two-part set-delayed cement composition comprising separate component .Slurries with one component slurry comprising a pozzolan and the other component slurry comprising lime. Embodiments of the two-part set-delayed cement compositions are discussed in detail below. Advantageously, embodiments of the set-delayed cement compositions may be capable of remaining in a pumpable fluid state for an extended period of time. For example, the set-delayed cement compositions may remain in a pumpable fluid state for at least about 1 day 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 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 IOW F to about 200"
F. In alternative embodiments, the set-delayed cement compositions may be used in subterranean formations having bottom hole static temperatures up to 4500 F or higher.
1.00071 The water used in embodiments may be from any source provided that it does not contain an excess of compounds that may undesirably affect other components in the set-delayed cement compositions. For example, a cement composition may comprise fresh water or salt water. Salt water generally may include one or more dissolved salts therein and may be saturated or unsaturated as desired for a particular application. Seawater or brines may be suitable for use in embodiments. Further, the water may be present in an amount sufficient to form a punmable slurry. In certain embodiments, the water may be present in the set-delayed cement compositions in an amount in the range of from about 33%
to about 200% by weight of the pozzolan. In certain embodiments, the water may he present in the set-delayed cement compositions in an amount in the range of from about 35% to about 70% by weight of the pozzolan. With the benefit of this disclosure one of ordinary skill in the art will recognize the appropriate amount of water for a chosen application.
[0008] Embodiments of the set-delayed cement compositions may comprise a p0720iall. Any pozzolan is Suitable tbr use in embodiments. Example embodiments comprising a pozzolan may comprise fly ash, silica fume, metakaolin, a natural pozzolan (e.g., pumice), or combinations Thereof [0009] Embodiments of the pozzolan may comprise fly ash. A variety of fly ashes may be suitable, including fly ash classified as Class C and Class F fly ash according to American Petroleum Institute, AN Specification for Materials and 'Vesting fOr Well Cements, API Specification 10, Falb Ed., July 1, 1990. Class C fly ash comprises both silica and lime, so it may set to .form a hardened mass upon mixing with Water. Class F fly ash generally does not contain a sufficient amount of lime to induce a cementitious reaction, therefore, an additional source of calcium ions is necessary tbr a set-delayed cement composition comprising Class F fly ash. In some embodiments, lime may he mixed with Class F fly ash in an amount in the range of about 0.1% to about 100% by weight of the fly 'ash. In some instances, the lime may be hydrated lime. Suitable examples of fly ash include, but are not limited to, POD/11X A cement additive, commercially available from Hatliburton Energy Services, Inc., Houston, Texas.
[0010] Embodiments of the pozzolan may comprise metakaolin. Generally, metakaolin is a white pozzolan that may be prepared by heating kaolin clay, for example, to temperatures in the range of about 600 C to about 8000C.
[00111 Embodiments of the pozzolan may comprise a natural pozzolan. Natural pozzolans are generally present on the Earth's surface and set and harden in the presence of hydrated lime and water. Embodiments comprising a- natural pozzolan may comprise pumice, diatomaceous earth, volcanic ash, opaline shale, tuff, and combinations thereof The natural pozzolans may be ground or unground. Generally, the natural pozzolans may have any particle size distribution as desired for a particular application. In certain embodiments, the natural pozzolans may have a mean particle size in a range of from about 1 micron to about 200 microns. The mean particle size corresponds to (150 values as measured by particle size analyzers such as those manufactured by MifilVerfl Instruments, Worcestershire, United Kingdom. In specific embodiments, the natural pozzolans may have a mean particle size in a range of from about I micron to about 200 micron, from about 5 microns to about 100 microns, or from about 10 micron to about 50 microns. In one particular embodiment, the natural pozzolans may have a mean particle size of less than about 15 microns.
An example of a suitable commercial natural pozzolan is pumice available from Hess Pumice Products, Malad, Idaho, as 05-325 lightweight aggregate, which has a particle size of less than about 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 and may be less reactive due to their decreased surface area. One of ordinary skill in the art, with the benefit of this disclosure, should be able to select a particle size for the natural pozzolarts suitable for use for a chosen application, 100121 Embodiments of the set-delayed cement compositions may comprise hydrated lime. As used herein, the term "hydrated lime" will be understood to mean calcium hydroxide. in some embodiments, the hydrated time may be provided as quicklime (calcium oxide) which hydrates when mixed with water to form the hydrated lime. The hydrated lime may be included in embodiments, for example, to form a hydraulic composition with the pozzolan. For example, the hydrated lime may be included in a pozzolan-to-hydrated-lime weight ratio of about 10:1 to about 1:1 or a ratio of about 3:1 to about 5:1.
Where present, the hydrated lime may be included in the set-delayed cement compositions in an amount in the range of from about 10% to about 100% by weight of the pozzolan. for example. in some embodiments, the hydrated time may be present in an amount ranging between any of andior including any of about 10%, about 20%, about 40%, about 60%, about 80%, or about 100%
by weight of the pozzolan. In some embodiments, the cememitious components present. in the set-delayed cement composition may consist essentially of the pozzolan and the hydrated lime. For example, the cementitious components may primarily comprise the pozzolan and the hydrated lime without any additional =cementitious components (e.g., Portland cement) that hydraulically set in the presence of water. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of hydrated lime to include for a chosen application.
[0013] Embodiments of the .set-delayed cement compositions may comprise a cement set retarder. A broad variety of cement set retarders may be suitable for use in the set-delayed cement compositions. For example, the cement set retarder may comprise phosphonic acids, such as ethylenedia.mine tetra(rnethylene phosphonic acid), diethylenetriarnine penta(methylene phosphonic acid), etc.; lignosulfonates, such as sodium lignosulfonatc, calcium lignosulfonatc, etc.; salts such as stannous sulfate, lead acetate, monobasic calcium Phosphate, organic acids, such as citric add, tartaric acid, etc.; cellulose derivatives such as hydroxyl ethyl cellulose (HEC) and carboxymethyl hydroxyethyl cellulose (CMHEC.); synthetic co- or ter-polymers comprising sulfonate and carboxylic acid groups such as sulfortate-functionalized acrylamidtktcrylie acid co-polymers;
borate compounds such as alkali borates, sodium metaborate, sodium tetraborate, potassium pentaborate; derivatives thereof or mixtures thereof. Examples of suitable cement set retarders include, among others, =phosphonic acid derivatives. One example of a suitable cement set retarder is Micro Matrix cement retarder, available *OM
flalliburton Energy Services, Inc. Generally, the cement set retarder may be present in the set-delayed cement
6 compositions in an amount sufficient to delay the setting for a desired time.
In some embodiments, the cement set retarder may be present in the Set-delayed cement compositions in an amount in the range of from about 0,01% to about 10% by weight of the pozzolan, In specific embodiments, the cement 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%, about 6%, about 8%,, or about 10% by weight of the pozzolan. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the cement set retarder to include for a chosen application.
[0014] As previously mentioned, embodiments of the set-delayed cement compositions may optionally comprise a dispersant. Examples of suitable dispetsants include, without limitation, sulfonated-formaldehyde-based dispersants (e.g., sulfonated 'acetone formaldehyde condensate), examples of which may include Daxtut 19 dispersant available from Geo Specialty Chemicals, Ambler, Pennsylvania. Other suitable dispersants may be polycarboxylated ether dispersants such as Liquiment- 5581F and Liquitnenel 5141, dispersants available from BASF Corporation Houston, Texas; or Ethacryr 0 dispersant available from Comex, Genay, France. An additional example of a suitable commercially available dispersant is C'llem-3 dispersant, available from 11011)11dpi]
Energy Services, Inc, Houston, Texas. The Liquimene 5141.: dispersant may comprise 36% by weight of the polycarboxylated ether in water. While a variety of dispersants may be used in accordance with embodiments, polycarboxylated ether dispersants May be particularly suitable for use in some embodiments. Without being limited by theory, it is believed that polycarboxylated ether dispersants may synergistically interact with other components of the set-delayed cement composition. For example, it is believed that the polyearhoxylated ether dispersants may react with certain cement set retarders (e.g, phosphonic acid derivatives) resulting in formation of a gel that suspends the pozzolan and hydrated lime in the composition for an extended period of time.
[0015] In some embodiments, the dispersant. may be included in the sot-delayed cement compositions in an amount in the range of from about 0.01% to about 5%
by weight of the pozzolan. In specific embodiments, the dispersant May be present in an amount ranging between any of and/or including any of about 0.01%, about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, or about 5% by weight of the pozzolan. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the dispersant to include for a chosen application.
[0016] Some embodiments of the set-delayed cement compositions may comprise silica sources in addition to the pozzolan; for example, crystalline silica and/or amorphous
7 = CA 02921230 2016-02-11
8 PCT/US2014/054794 silica. Crystalline silica is a powder that may be included in embodiments of the set-delayed cement compositions, for example, to prevent cement compressive strength retrogression.
Amorphous silica is a powder that may be included in embodiments of the set-delayed cement compositions as a. lightweight filler and/or to increase Cement compressive strength.
Amorphous silica is generally a byproduct of a ferrosilicon production process, wherein the amorphous silica may be formed by oxidation and condensation of ga,seous silicon suboxide, SiO, which is formed as an intermediate during the process. An example of a suitable source of amorphous silica is Silicalite cement additive available from Halliburton Energy Services, Inc,, Houston, Texas. Embodiments comprising additional silica sources may utilize the additional silica source as needed to enhance compressive strength or set times.
[0017.1 Other additives suitable for use in subterranean cementing operations also may be included in embodiments of the set-delayed cement compositions.
Examples of such additives include, but are not limited to: weighting agents, lightweight additives, gas-generating additives, mechanical-property-enhancing additives, lost-circulation materials, filtration-control additives, fluid-loss-control additives, defoaming agents, foaming agents, thixotropic additives, and combinations thereof in embodiments, one or more of these additives may be added to the set-delayed cement compositions after storing but prior to the placement of a set-delayed cement composition into a subterranean formation. A
person having ordinary skill in the art, with the benefit of this disclosure, Should readily be able to determine the type and amount of additive useful for a particular application and desired result.
[00181 Those of ordinary skill in the art will appreciate that embodiments of the set-delayed cement compositions generally should have a density suitable for a particular application. By way of example, the cement compositions may have a density in the range of from about 4 pounds per gallon (ib/gar) to about 20 lb/gal. In certain embodiments, the cement compositions may have a density in the range of from about 8 lb/gal to about 17 lb/gal. Embodiments of the set-delayed cement compositions may be foamed or unfoamed or may comprise other means to reduce their densities, such as hollow microspheresõ
low-density elastic beads, or other density-reducing additives known in the art.
In embodiments, the density may be reduced after storage, but prior to placement in a subterranean formation.
In embodiments, weighting additives may be used to increase the density of the set-delayed cement compositions. Examples of suitable weighting .additives may include barite, hematite, hausmannite, calcium carbonate, siderite, ilmenite, or combinations thereof:
In particular embodiments, the weighting additives may have a specific gravity of 3 or greater. Those of ordinary skill in the .art, with the benefit of this disclosure, will recognize the appropriate density for a particular application.
[00191 As previously mentioned, the set-delayed cement compositions may have a delayed set in that they remain in a pumpable fluid state for at least one day (e.g., about 1 day, about 2 weeks, about 2 years or more) at room temperature (e.g, about 800 1') in quiescent storage. For example, the set-delayed cement compositions may remain in a purapable fluid state for a period of time from about 1 day to about 7 days or more in some embodiments, the set-delayed cement .compositions may remain in a pumpable fluid State for at least about 1 day, about 7 days, about 10 days, about 20 days, about 30 days, about 40 days, about 50 days, about 60 days, or longer. A fluid is considered to be in a pumpable fluid state where the fluid has a consistency of less than 70 Bearden units of consistency ("130), as measured on a pressurized consistorneter in accordance with the procedure for determining cement thickening times set forth in API RP Practice 1013-2, Recommended Practicefir Testing Well Cements, First Edition, July 2005.
[00201 When desired for use, embodiments of the set-delayed cement compositions may be activated (e.g., by combination with a cement set activator) to set into a hardened mass. The term 'cement set activator" or "activator", as used herein, refers to an additive that activates a set-delayed or heavily retarded cement composition and may also aecelerate the setting of the set-delayed, heavily retarded, or other cement composition.
By way of example, embodiments of the set-delayed cement compositions may be activated to form a hardened mass in a time period in the range of from about 1 hour to about 12.
hours. For example, embodiments of the set-delayed cement compositions may set to form a hardened mass in a time., period ranting between any of andior including any of about 1 day, about 2 days, about 4 days, about 6 days, about 8 days, about 10 days, or about 12 days.
[00211 in some embodiments, the set-delayed cement compositions may set to have a desirable compressive strength after activation. Compressive strength is generally the capacity of a material or structure to withstand axially directed pushing forces. The compressive strength may be measured at a specified time after the set-delayed cement composition has been activated and the resultant composition is maintained under specified temperature and pressure conditions. Compressive strength can be measured by either destructive or non-destructive methods. The destructive method Physically tests the strength of treatment fluid samples at various points in time by crushing the samples in a compression-testing machine. The compressive strength is calculated from the failure load divided by the cross-sectional area resisting the load and is reported in units of pound-force per square inch (psi). Non-destructive methods may employ a UCATm Ultrasonic Cement
9 Analyzer, available from Farm Instrument Company, Houston, TX, Compressive strength values may be determined in accordance with API RP 1013-2, RecoMmended Practice lbr Testing Well Cements, First Edition, July 2005.
100221 By way of example, the set-delayed cement compositions may develop a 24-hour compressive strength in the range of from about 50 psi to about 5tX)0 psi, alternatively, from about 100 psi to about 4500 psi, or alternatively from about 500 psi to about 40(K) psi.
In some embodiments, the set-delayed cement compositions may develop a compressive strength in 24 hours of at least about 50 psi, at least about 100 psi, at least. about. 500 psi, or more. In some embodiments, the compressive strength values may be determined using destructive or non-destructive methods at a temperature ranging from 100" F to 200 IF, [00231 in some embodiments, the set-delayed cement compositions may have desirable thickening times after activation. Thickening time typically refers to the time a such as a set-delayed cement coniposition, remains in a fluid state capable of being pumped. A number of different laboratory techniques may be used to measure thickening time. A pressurized consistometer, operated in accordance with the procedure set forth in the aforementioned API RP Practice 1013,1, may be used to measure whether a fluid is in a puropable fluid state, The thickening time may be the time for the treatment fluid to reach 70 Be and may be reported as the time to reach 70 Be In some embodiments, the cement compositions may have a thickening time of greater than about 1 hour, alternatively, greater than about 2 hours, alternatively greater than about 5 hours at 3,000 psi and temperatures in a range of from about 500 F to about 400' F. alternatively, in a range of from about 800 F to 'about 250' F. and alternatively at a temperature of about 1400 F.
[00241 Embodiments May include the addition of a cement set activator to the set-delayed cement compositions. Examples of suitable cement set activators include, but are not limited to: zeolites, amities such as triethanolamine, diethanolamine;
silicates such as sodiiim silicate; zinc formate; calcium acetate; Groups IA and HA hydroxides such as sodium hydroxide, magnesium hydroxide, and calcium hydroxide; monovalent salts such as sodium chloride; divalent salts such as calcium chloride; nanosilica (i.e., silica having a particle size of less than or equal to about 100 nanarneters); polyphosphates;
and combinations thereof, In some embodiments, a combination of the polyphosphate and a monovalent salt may be used for activation. The monovalent salt may be any salt that dissociates to form a monovalent cation, such as sodium and potassium salts.
Specific examples of suitable. monovalent salts include potassium sulfite, nod sodium sulfate. A
variety of different polyphosphates :may be used in combination with the monovalent salt for activation of the set-delayed cement compositions, including polymeric metaphosphate salts, phosphate salts, and combinations thereof, Specific examples of polymeric metaphosphate salts that may be used include sodium hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate, sodium heptametaphosphate, sodium oetametaphosphate, and combinations thereof. A specific example of a suitable cement set activator comprises a combination of sodium stiltine and sodium hexametaphosphate. in particular embodiments, the cement set activator may be provided and added to the set-delayed cement composition as a liquid additive, for example, a liquid additive comprising a monovalent salt, a polyphosphate, and optionally a dispersant, [9025] The cement set activator Should be added to embodiments of the set-delayed cement composition in an amount sufficient to induce the set-delayed composition to set into a hardened mass. In certain embodiments, the cement set activator may be added to the cement composition in an amount in the range of about 0.1% to about 20% by weight: of the pozzolan, in specific embodiments, the cement set activator may be present in an amount ranging between any of and/or including any of about 0.1%, about 1%, about 5%, about
10%, about 15%, or about 20% by weight of the porzolan. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the cement set activator to include tbr a chosen application.
[0026] Embodiments of the set-delayed cement compositions may comprise the use of two separate component slurries that are combined to form a two-part set-delayed cement composition. Embodiments of the two-part set-delayed cement may comprise providing a pozzolan slurry and a lime slurry which are kept separate in lieu of adding cement set retarders. The two-part set-delayed cement composition may utilize two individual slurries in a manner such that neither slurry is able to hydrate and therefore set independently.
Therefore, each individual slurry of the two-part set-delayed cement composition should remain in a set-delayed state (i.e. remaining in a pumpable fluid state for at least about one day [e.g., at least about I day, about 2 weeks, about 2 years or morel at room temperature in quiescent storage). Embodiments of the two-part set-delayed cement composition may comprise two component slunies. One component Slurry comprises a pozzolan and water.
The other component slurry comprises lime and water. In embodiments: each Slurry may be stored at a well site or other storage site until needed. When needed, the two component slurries may be mixed together prior to or while pumping downhole. The combined slurry may then thicken and set within a desired period of time.
[0027] Advantageously, the use of a two-part set-delayed cement composition may allow .for quicker setting at lower temperatures (e.g. temperatures less than 140 1.).
Furthermore, because the reactive components of the two-part set-delayed cement
11 composition are kept separate, additional additives or higher concentrations of additives (e.g.
additional silica sources, see above) may be added to the two-part set-delayed cement composition without risk of premature setting or gelation.
[002S1 Embodiments of the two-part set-delayed cement compositions may generally comprise two component slurries, a pozzolan slurry and a lime slurry. Both component slurries comprise water. Optionally, either component slurry may further comprise a dispersant and/or a cement set retarder. Advantageously, embodiments of the two-part set-delayed cement compositions may be capable of remaining in a pumpable fluid state for an extended period of time. For example, the two-part set-delayed cement compositions may remain in a pumpable fluid state for at least about 1 day or longer.
Advantageously, the two-part set-delayed cement compositions may develop reasonable compressive strengths after activating (e.g. by mixing the two component slurries) at relatively low temperatures. While the two-part set-delayed cement compositions may be suitable for a number of subterranean cementing operations, they may 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 100' F to about 200 F. In alternative embodiments, the set-delayed cement compositions may be used in subterranean formations having bottom hole static temperatures up to 450 F
Or higher.
100291 Embodiments of the pozzolan slurry comprise a pozzolan. Any pozzolan is suitable fOr use in embodiments. Example embodiments comprising a pozzolan may comprise fly ash, silica fume, metakaolin, diatomaceous earth, a natural pozzolan (e.g., pumice), or combinations thereof. in a two-part set-delayed cement composition embodiment, the pozzolan may be a non-hydraulic pozzolan, i.e. a pozzolan that will not react when mixed with water in the absence of hydrated lime to form a cementitious material. By way of example, some types of Class C fly ash may not be suitable-for use in a two-parr set-delayed cement composition embodiment, because Class C fly ash may comprise lime and will therefore react when mixed with water to become eertientitious, 100301 Embodiments of the pozzolan slurry may comprise fly ash. A variety of fly ashes may be suitable, inclading, fly ash classified as Class F fly ash according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API
Specification 10, Fifth Ed.. July 1, 1990. Class C fly ash comprises both silica and lime, so it may set to form a hardened mass upon mixing with water and may thus be unsuitable fOr use in the pozzolan slurry as it may undesirably set when mixed with the water.
Class F fly ash generally does not contain a sufficient amount of lime to induce a cementitious reaction, therefore, should remain in a pumpable fluid state when mixed with water, Suitable
12 examples of fly ash include, but are not limited to, POZMIX1. A cement additive, commercially available from Hall ihurain Energy Services, Inc., Houston, Texas.
[00311 Embodiments of the pozzolan slurry may comprise metakablin. Generally, metakaolin is a white pozzolan that may be prepared by heating kaolin clay, for example, to temperatures in the range of about 6000C to about g000 C.
100321 Embodiments of the pozzolan slurry may comprise a natural pozzolan.
Natural pozzolans are genemlly present on the Earth's surface and set and lhattlen in the presence of hydrated lime and water. Embodiments comprising a natural pozzolan may comprise pumice, diatomaceous earth, volcanic ash, opaline shale, tuff, and combinations thereof The :natural pozzolans may be ground or unground. Generally, the natural pozzolans may have any particle size distribution as desired fOr a particular application. In certain embodiments the natural pozzolans may have a mean particle size in a range of from about I
micron to about 200 microns. The Mean particle size corresponds to d50 values as measured by particle size analyzers such as those manufactured by :Malvern Instruments, Worcestershire, United Kingdom, In specific embodiments, the natural pozzolans may have a mean particle size in a range of from about 1 micron to about 200 micron, from about 5 microns to about 100 microns, or from about 10 micron to about 50 microns. In one particular embodiment, the natural pozzolans may have a mean particle size of less than about 15 microns, An example of a suitable commercial natural pozzolan is pumice available from Hess Pumice Products, Inc., Malad, Idaho, as DS-325 lightweight aggregate, which has a particle size of less than about 15 microns, It should be appreciated that particle sizes too small may have mixability problems while particle sizes WO large may not be effectively suspended in the compositions and may be less reactive dud to their decreased surface area.
One of ordinary skill in the art, with the benefit of this disclosure, should be able to select a particle size for the natural pozzolans suitable for use for a chosen application, [0033] Embodiments of the pozzolan slurry comprise water. The water used in embodiments of the pozzolan slurry may be from any source provided that it does not contain an excess of compounds that may undesirably affect other components in the pozzolan slurry. For example, the pozzolan slurry may comprise fresh water or salt water.
Salt water generally may include one or more dissolved salts therein and may be saturated or unsaturated as desired. for a particular application. Seawater or brines may he suitable for use in embodiments, Further, the water may be present in an amount sufficient to form a pumpable slurry. In certain embodiments, the water may be individually present in the pozzolan slurry in an amount in the range of .1Tom about 33% to about 200% by weight of the pozzolan. In certain embodiments, the water may be present in the pozzolan slurry in an
13 amount in the range of from about 35% to about 85% by weight of the pozzolan.
With the benefit of this disclosure One of ordinary skill in the art will recognize the appropriate amount of water fir a chosen application. Embodiments of the pozzolan slurry may comprise additives suitable for use in subterranean cementing operations. Any additive, including additional silica sources, may be added to the pozzolan slurry. Examples of additives include, but are not limited to: weighting additives, lightweight additives, gas-generating additives. Mechanical-property-enhancing additives, lost-circulation materials, filtration-control additives, fluid-loss-control additives, defoaming agents, foaming events, thixotropic additives, dispersants, cement set activatotslaccelerators, cement set retarders, and combinations thereof. In embodiments of the pozzolan slurry, one or more of these additives may be added to the pozzolan slurry before or after storing. Additionally one or more of these additives may be added to the pozzolan slurry before or after mixing the pozzolan slurry with the lime slurry. A person having ordinary skill in the art, with the benefit ofthis disclosure, should readily be able to determine the type and amount of additive useful fbr a particular application and desired result.
[0034] Embodiments of the lime slurry comprise hydrated lime. As used herein, the term "hydrated lime" will be understood to mean calcium hydroxide. In some embodiments, the hydrated lime may be provided as quicklime (calcium oxide) Which hydrates when mixed with water to form the. hydrated Hine. The hydrated lime may be included in embodiments of the lime slurry to form a hydraulic composition with the pozzolan. For example, the hydrated lime may be included in a poz.zolan-to-hydrated-lime weight ratio of about 10:1 to about 1:1 or a ratio of about 3:1 to about 5:1, based on the combined mix of both component slurries.
Where present, the lime slurry may comprise an amount of hydrated lime between about 10% to about 100% by weight of the pozzolan present in the pozzolan slurry. In some embodiments, the hydrated lime may be present in the lime slurry in an amount ranging between any of and/or including any of about 10%, about 20%, about 40%, about 60%, about 80%, or about 100% by weight of the pozzolan in the pozzolan shirty. In some embodiments, the cementitions components present in the two-part set-delayed cement composition may consist essentially of the pozzolan and the hydrated lime. For example, the cementitious components may primarily comprise the pozzolan (e.g., pumice) and the hydrated lime without any additional cementitions components (e.g., Portland cement) that hydraulically set in the presence of water. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of hydrated lime to include for a chosen application.
14 100351 Embodiments of the lime slurry comprise water. The water used in embodiments of the lime slurry may be from any source provided that it does not contain an excess of compounds that may undesirably affect other components in the lime shirty. For example, the lime slurry may comprise fresh water or salt water. Salt water generally may include one or more dissolved salts therein and may be saturated or unsaturated as desired for a particular application. Seawater or brines may he suitable for use in embodiments.
Further, the water May be present in an amount sufficient to form a pumpable slurry. In certain embodiments, the water may be individually present in the lime slurry in an amount in the range of from about 33% to about 200% by weight of the lime. In certain embodiments, the water may be present in the lime slurry in an amount = in the range of from about 35% to about 70% by weight of the lime. With the benefit of this disclosure one of ordinary skill in the art will recognize the appropriate amount of water .for a chosen application, [00361 Embodiments of the lime slurry may comprise additives suitable for use in subterranean cementing operations. Any additive, including additional silica sources, may be added to the lime slurry. Examples of such additives include, but are not limited to:
weighting additives, lightweight additives, gas-generating additives, mechanical-property-enhancing additives, lost-circulation materials, filtration-control additives, fluid-loss-control additives, defbaming agents, foaming agents, thixotropic additives, dispersants, cement set activators/accelerators, cement set retarders, and combinations thereof. In embodiments of the lime slurry, one or more of these additives may be added to the lime slurry before or after storing. Additionally one or more of these additives may be added to the lime slurry before or after mixing the lime slurry with the pozzolan slurry. A person having ordinary Skill in the art, with the benefit of this disclosure, should readily be able to determine the type and amount of additive useful for a particular application and desired result, [0037] Embodiments of the two-part set-delayed cement compositions may comprise a cement set retarder as described above. Any cement set retarder described in embodiments of the set-delayed cement compositions above may also be suitable for embodiments of the two-part set-delayed cement compositions. Cement set retarders may be added to one or both component slurries or may be added to the combined slurry. Amongst .other reasons, cement set retarders may be added to increase thickening time.
In some embodiments, the cement set retarder may be present in the component slurries (either individually or in both) or in the combined slurry of the two-part set-delayed cement compositions in an amount in the range of from about 0.01% to about 10% by weight of the pozzolan. In specific embodiments, the cement 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%, about 6%, about 8%, or about 10% by weight of the pozzolan -for the pozzolan slurry or by weight of the lime for the lime slurry. One of ordinary skill M the art, with the benefit of this disclosure, will recognize the appropriate amount of the cement set retarder to include for a chosen application.
[0038] As previously mentioned, embodiments of the two-part set-delayed cement compositions may optionally comprise a dispersant as described above. Any dispersant described in embodiments of the set-delayed cement compositions may also be suitable for embodiments of the two-part set-delayed cement compositions. In some embodiments, the dispersant may be included in one or both of the component slurries or in the combined slurry of the two-part set-delayed cement compositions in an amount in the range of from 'about 0.01% to about 5% by weight of the pozzolan or the hydrated lime. In specific embodiments, the dispersant may be present in an amount ranging between any of and/or including any of about 0.01%, about 0A%, about 0.5%, about 1%, about 2%, about 3%, about 4%, or about 5% by weight of the pozzolan or the hydrated lime. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the dispersant to include for a chosen application.
[0039] Embodiments may include the addition of a cement set activator to the two-part set-delayed cement compositions as described above. The cement set activator may be included to accelerate setting times, amongst other reasons. Any cement set activator described in embodiments of' the set-delayed cement compositions may also be suitable for embodiments of the two-part set-delayed cement compositions. Any cement set activator may be added to either one or both of the component slurries as well as to the combined slurry in an amount sufficient to accelerate the setting of the combined two-part. set-delayed composition if added to only a component slurry, the acceleration of the set time should happen when the component slurries are mixed). In embodiments, the cement set activator may be added to the component slurries (either individually or both) or to the combined slurry of the two-part set-delayed cement composition in an amount in the range of about 0.1% to about 20% by weight of the pozzolan. In specific embodiments, the cement set activator may be present in the component slurries (either individually or in both) or in the combined slurry of the two-part set-delayed cement composition in an amount ranging between any of and/or including any of about 0.1%, about 1%, about 5%, about 10%, about
15%, or about 20% by weight of the pozzolan. One of' ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the cement set activator to include for a chosen applicatiOn.
16 = CA 02921230 2016-02-11 10040] Those of ordinary skill in the art will appreciate that embodiments of the two-pan set-delayed cement compositions generally Should have a density suitable for a particular application. By way of example, the combined two-part set-delayed cement compositions may have a density in the range of from about 4 pounds per gallon (Ibigar) to about 20 lb/gal. In certain embodiments, the combined two-patt set-delayed cement compositions may have a density in the range of from about 8 lb/gal to About
17 lb/gal.
Embodiments of the two-part set-delayed cement compositions may be foamed or unlbamed 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.
In embodiments, the density may be reduced after storage, but prior to placement in a subterranean fbrmation.
In embodiments, weighting additives may be used to increase the density of the two-part set-delayed cement compositions. Examples of suitable weighting additives may include barite, hematite, hausmannite, calcium carbonate, siderite, iimenite, or combinations thereof, In particular embodiments, the weighting additives may have a specific gravity of 3 or greater.
Those of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate density for a particular application.
[0041] As previously mentioned, the component slurries of the two-part set-delayed cement compositions may have a delayed set in that they remain in a pumpable fluid State for at least one day (e.g.. about I day, about 2 weeks, about 2 years or more) at room temperature (e4., about 80" F) in quiescent storage. For example, the component slurries of the two-part set-delayed cement compositions may remain in a pumpable fluid state for a period of time from about 1 day to about 7 days or more. In some embodiments, the component: slurries of the two-part set-delayed cement compositions may remain in a pumpable fluid state for at 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, or longer. A fluid is considered to be in a pumpable fluid state where the fluid has a consistency of less than 70 Bearden units of consistency ("Bc"), as measured on a pressurized consistometer in accordance with the procedure for determining cement thickening times set fbrth in API RP
Practice 10B-2, Recommended Pmealeelbr Testing Well Cemenn, First Edition, July 2005.
[0042] When desired for use, embodiments of the two-part set-delayed cement compositions may be activated (e.g., by combining the pozzolan and lime slurries) to set into a hardened mass. By way of example, embodiments of the two-part set-delayed cement compositions may be activated to form a hardened mass in a time period in the range of from about 1 hour to about 12 hours. For example, embodiments of the two-part set-delayed cement compositions may set to form a hardened mass in a time period ranging between any of andior including any of about I day, about 2 days, about 4 days, about 6 days, about 8 days, about 10 days, Or about 12 days.
[00431 In some embodiments, the two-part set-delayed cement compositions may set to have a desirable compressive strength after activation. Compressive strength is generally the capacity of a material or structure to withstand axially directed pushing forces. "The compressive strength may be measured at a specified time after the two-part set-delayed cement composition has been activated and the resultant composition is maintained under specified temperature and pressure conditions. Compressive strength can be measured by either destructive or non-destructive methods. The destructive method physically tests the strength of treatment fluid samples at various points in time by crushing the samples in a compression-testing machine. The compressive strength is calculated from the failure load divided by the (1-ms-sectional area resisting the load and is reported in units of pound-three per square inch (psi). Non-destructive methods may employ a UCATs` Ultrasonic Cement Analyzer, available from Faim Instrument Company, Houston, TX. Compressive strength values May be determined in accordance with API RP 10B-2, Recommended Practice fir &sling Well Cemons, First Edition, July 2005.
[0044] By way of example, the two-pan set-delayed cement compositions may develop a 24-hour compressive strength in the range of from about 50 psi to about 5000 psi, alternatively, from. about 100 psi to about 4500 psi, or alternatively from about 500 psi to about 4000 psi. In some embodiments, the two-part set-delayed cement compositions may develop a compressive strength in 24 hours of at least about 50 psi, at least about 100 psi, at least about 500 pSi, or more. In some embodiments, the compressive Strength values may be determined using destructive or non-destructive methods at a temperature ranging from 100"
F to 200 F.
[00451 In some embodiments, the two-part set-delayed cement compositions may have desirable thickening times after activation, Thickening time typically refers to the time fluid, such as a set-delayed i:ttnent composition, remains in a fluid state capable of being pumped. A number of different laboratory techniques may be used to measure thickening time. A pressurized consistometer, operated in accordance with the procedure set forth in the athrementioned API RP Practice 1013-2, may be used to measure whether a fluid is in a pumpable fluid state. The thickening time may be the time for the treatment fluid to reach 70 Be and may be reported as the time to reach 70 Bc, In some embodiments, the two-part set-delayed cement compositions may have a thickening time of greater than about 1 hour, alternatively, greater than about 2 hours, alternatively greater than about 5 hours at between about 1,000 psi to about 20,000 psi and temperatures in a range of from about 50Q F to about
18 400'F, alternatively, in a range of from about 80' F to about 2500 F, and alternatively at a temperature Of about 1400 F.
[0046] Embodiments of the two-part set-delayed cement. composition may be used to displace a prior placed fluid (i.e. embodiments of the two-part set-delayed cement composition may be used as a spacer fluid). The pozzolan slurry of the two-part set-delayed cement composition, comprising a pozzolan and water, may be similar in composition to conventional spacer fluids. Because of this similarity, the pozzolan slurry may be used as a spacer fluid in embodiments, The pozzolan slurry may be used to displace a drilling mud, separate cement from a drilling mud, displace another treatment fluid, separate the drilling mud from a treatment fluid, and/or separate cement from a treatment fluid, Advantageously, the use of the pozzolan slurry as a spacer fluid may condition the subterranean formation with part of the same composition that ultimately May be used as the annular Sealant.
Therefore, the risk of incompatibilities 'between sealant and Spacer fluid may be reduced.
[0047] In embodiments wherein the poz2Aan component slurry of the two-part set-delayed cement composition may be used as a spacer fluid, the density of the pozzolan slurry may be adjusted by the addition of water and/or a viscosifier. The water and viscosifiers may he added in any amount to achieve the appropriate density to provide a suitable theological hierarchy for a given application. An example of a suitable viscosifier is SA-l015 suspending agent available from Halliburton Energy Services, Houston, TX.
Additionally, weighting agents may be added to adjust the density as may be appropriate to maintain a suitable theological hierarchy. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate density and method Of density adjustment necessary for a chosen application.
[0048] Moreover, in embodiments wherein the pozzolan Slurry may be used as a spacer fluid, the spacer fluid may be foamed with a foaming additive and/or a gas. The spacer fluid may be foamed, for example, to provide a spacer fluid with a reduced density.
The as used for fiaarning the composition may be any suitable gas flar foaming, including, but not limited to: air, nitrogen, or combinations thereof. Generally, the gas should be present in an amount sufficient to form the desired amount or quality of foam.
Foaming additives may be included in embodiments to, for example, facilitate foaming and/or stabilize the resultant foam formed therewith. Examples- of suitable foaming additives include, but are not limited to: mixtures of an ammonium salt of an alkyl ether sulfate, a cocoamidopropyl betaine surfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodium chloride, and water, mixtures of an ammonium salt of an alkyl ether sulfate surfactant, a cocoamidopropyl hydrox,ysultaine surfactant, a cocoamidopropyl.
19 dimethylamine oxide surfactant, sodium chloride, and water; hydrolyzed keratin; mixtures of an etboxylated alcohol ether sulfate surfactant, an alkyl or alkene amidopropyl betaine surfactant, and an alkyl or alkene dimethylamine oxide surfactant; aqueous solutions of an alpha-oleftnic sulfonate surfactant and a betaine surfactant; and combinations thereof. An example Of a suitable foaming additive is ZONESEALANTrm 2000 agent, available from Halliburton Energy Services, Houston, TX.
[0049] ft is to be understood, that any additive, component, or embodiment disclosed herein may additionally be used or combined with embodiments of the two-part set-delayed cement composition. For example, previously described additives such as weighting agents, lightweight additives, gas-generating additives, mechan ica 1-property-enhancina additives, lost-circulation materials, filtration-control additives, fluid-loss-control additives, defoaming 'agents, foaming agents, thixotropic additives, dispersants, cement set retarders, cement set activators/accelerators, additional silica sources, and the like, and combinations thereof may all be used with embodiments of the pozzolan slurry, lime slurry, and the combined slurry of the two-part set-delayed cement compositions in the same manner as previously described.
The two-part set-delayed cement composition embodiment is therefore inclusive of every additive, component, or other embodiment that may be used in combination;
including the use of cement set activators and cement set. retarders. For example, the two-part set-delayed cement composition may comprise a cement set activator to accelerate setting time and enhance early strength, additionally or alternatively, the two-part set-delayed cement composition may comprise a cement set retarder to delay thickening time. Any additive, component: or embodiment disclosed herein may be added to one or both of the component slurries or to the combined slurry of the two-part set-delayed cement compositions.
Moreover, any additive, component, or embodiment disclosed herein that is used with the pozzolan slurry, the lime slurry, or the combined slurry may also be used with embodiments of the two-part set-delayed cement composition that comprise a spacer fluid.
[0050] As will be appreciated by those of ordinary skill in the art embodiments of the set-delayed cement compositions including the two-part set-delayed cement compositions may be used in a variety of subterranean operations, including primary and remedial cementing. In some embodiments, a set-delayed cement composition (in.
the two-part set-delayed cement composition embodiments, this may he a combined two-part set-delayed cement composition) may be provided that. comprises water, a pozzolan, hydrated lime, a cement set retarder, and optionally a dispersant. The set-delayed cement Composition may be introduced into a subterranean formation and allowed to set therein. As used herein, introducing the set-delayed cement composition into a subterranean formation includes introduction into any portion of the subterranean formation, including, without limitation, into a wellbore drilled into the subterranean formation, into a near wellbOre region surrounding the wellbore, or into both. Embodiments may further include activation of the set-delayed cement composition. The activation of the set-delayed cement composition may comprise, for example, addition of a cement set accelerator to the set-delayed cement composition or the mixing of the two component slurries of the two-part set-delayed cement composition.
100511 In some embodiments, a set-delayed cement composition may be provided that comprises water, a pozzoltin, hydrated lime, a cement set retarder, and optionally a dispersant. The set-delayed cement composition may be stored, for example, in a vessel or other suitable container. In alternative embodiments a two-part set-delayed cement composition may be provided that comprises a lint part comprising a pozzolan and water component slurry and a second part comprising a hydrated lime and water component slurry.
The first and second parts may individually stored and combined prior to or while pumping downhole. The set-delayed cement compositions may be permitted to remain in storage for a desired time period. For example, the set-delayed cement compositions may remain in storage for a time period of about I day, about 2 weeks, about 2 years, or longer. For example, the set-delayed cement compositions May remain in storage for a time period 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 60 days, or up to about 2 years.
In some embodiments, the set-delayed cement composition may remain in storage for a time period in a range of from about I day to about 2 years or longer, Thereafter, the set-delayed. cement composition may he activated, for example, by mixing the two-component slurries together, introduced into a subterranean formation, and Allowed to set therein.
100521 In primary cementing embodiments,. for example, embodiments of the set-delayed cement composition may be introduced into an annular space between a conduit located in a wellbore and the walls of a wellbore (and/or a larger conduit in the wellbore), 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 4 barrier that prevents the migration of fluids in the wellbore. The set-delayed cement composition may also, for example, support the conduit in the wellbore.
f00531 In remedial cementing embodiments, a set-delayed cement composition may be used, for example, in squeeze-cementing operations or in the placement of cement plugs, By way of example, the set-delayed composition may be placed in a wellbore to plug art opening (e.g., a void or crack) in 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 microarmulus).
100541 An embodiment comprises a method of cementing comprising: providing a pozzolan slurry comprising a pozzolan and water; providing a time slurry comprising hydrated lime and water; allowing the pozzolan slurry and the time slurry to remain separate 'for about one day or longer; mixing the pozzolan slurry and the lime slurry to limn a cement composition; and allowing the cement composition to set.
[0055] An embodiment comprises a method of displacing a fluid in a subterranean formation comprising: providing a pozzolan slurry comprising a pozzolan and water;
providing a lime slurry comprising hydrated lime and water; introducing at least a portion of the pozzolan slurry into a wellbore that penetrates a subterranean formation such that the pozzolan slurry displaces at least one fluid from the Webore; activating the set-delayed cement composition by mixing at least a portion of the pozzolan slurry and at least a portion of the lime slurry to form a cement, composition; introducing the cement composition into a subterranean formation; and allowing the cement composition to set in the subterranean formation.
[0056] An embodiment comprises a system for cementing comprising: a pozzolan slurry comprising a pozzolan and water; a lime slurry for combination with the pozzolan slurry to form a cement composition comprising hydrated lime and water.
[0057] Referring now to FIG. I, preparation of a set-delayed cement composition in accordance with example embodiments will now be described. FIG. 1 illustrates a system 2 for preparation of a set-delayed cement composition and delivery to a wellbore in accordance with certain embodiments. As shown, the set-delayed cement composition may be mixed in mixing equipment 4, such as a jet mixer, re-circulating mixer, or a batch mixer, for example, and then pumped via pumping equipment 6 to the wellbore. In some embodiments, the mixing equipment 4 and the pumping equipment 6 may be disposed on one or more cement trucks as will be apparent to those of ordinary skill in the art. In some embodiments, a jet mixer may be used, for example, to continuously mix the limesettable material with the water as it is being pumped to the wellbore. In two-part set-delayed embodiments, mixing equipment (e.g., a jet mixer, re-circulating mixer, and/or a batch mixer) may be used to mix the combined two-part set-delayed cement composition slurry.
[0058] An example technique lOr placing a set-delayed cement composition into a subterranean formation will now be described with reference to FIGS. 2A and 213. FIG, 2A
illustrates surface equipment 10 that may be used in placement of a set-delayed cement composition in accordance with certain embodiments. It should be noted that while FIG. 2A

generally depicts a land-based operation, those skilled in the art will readily recognize that the principles described herein are equally applicable to subsea operations that employ floating or sea-based platforms and rigs, without departing from the scope of the disclosure.
As illustrated by MG. 2A, the surface equipment 10 may include a cementing unit 12, which may include one or more cement trucks. The cementing unit 12 may include mixing equipment 4 and pumping equipment 6 (e.g.õ FIG. I) 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..
[00591 Turning now to FIG. 213, the set-delayed cement composition 14 may be placed into a subterranean formation 20 in accordance with example embodiments. As illustrated, a wellbore 22 may be drilled into the subterranean formation 20.
While welltwe 22 is shown extending generally vertically into the subterranean formation 20, the principles described herein are also applicable to wellborns that extend at an angle through the subterranean formation 20, such as horizontal and slanted wellbores. As illustrated, the wellbore 22 comprises walls 24. In the illustrated embodiment, a surface casing 26 has been inserted into the wellbore 22. The surface casing 26 may be cemented to the walls 24 of the wellbore 22 by cement sheath 28.. In the illustrated embodiment, One or more additional conduits (e.g, intermediate casing, production casing, liners, etc), shown here as casing 30 may also be disposed in the wellborn 22. As illustrated, there is a wellbore annulus 32 formed between the casing 30 and the walls 24 of the wellbore 22 and/or the surface easing 26. One or more centralizers 34 may be attached to the casing 30. for example, to centralize the easing 30 in the wellborn 22 prior to and during the cementing operation.
1006011 With continued reference to FIG. 28, the set-delayed cement composition 14 may be pumped down the interior of the casing 30. 'fhe set-delayed cement composition 14 may be allowed to flow down the interior of the casing :10 through the easing shoe 42 at the bottom of the easing 30 and up around the casing 30 into the wellborn annulus 32. The set-delayed cement composition 14 may be allowed to set in the wellbore annulus 32, for example, to form a cement sheath that supports and positions the easing 30 in the wellbore 22. While not illustrated, Other techniques may also be utilized for introduction of the set-delayed cement composition 14. By way of example, reverse circulation techniques may be used that. include introducing the set-delayed cement composition 14 into the subterranean formation 20 by way of the wellbore annulus 32 instead of through the casing 30.
[0061,1 As it is introduced, the set-delayed cement composition 14 may displace other fluids 36, such as drilling fluids andior spacer fluids that may be present in the interior of the casing 30 and/or the wellbore annulus 32. At least a portion of the displaced fluids 36 may exit the wet-11)6re annulus 32 via a flow line 38 and be deposited, for example, in one or more retention pits 40 (e.g., a mud pit), as shown on Fla 2A. Referring again to FIG. 213, a bottom plug 44 may be introduced into the wellbore 22 ahead of the set-delayed cement composition 14, for example, to septirate the set-delayed cement composition 14 from the fluids 36 that may be inside the casing 30 prior to cementing. Alter the bottom plug 44 readies the landing collar 46, a diaphragm or other suitable device should rupture to allow the set-delayed cement composition 14 through the bottom plug 44. In FIG. 213, the bottom plug 44 is shown on the landing collar 46. In the illustrated embodiment, a top plug 48 may he introduced into the .wellbore 22 behind the set-delayed cement composition 14. The top plug 48 may separate the set-delayed cement composition 14 from a displacement sfluid 50 and also push the set-delayed cement composition 14 through the bottom plug 44.
[00621 The exemplary set-delayed cement compositions disclosed herein may directly or indirectly affect one or more components or pieces of equipment associated with the preparation, delivery, recapture, recycling, reuse, and/or disposal of the disclosed set-delayed cement compositions. For example, the disclosed set-delayed cement compositions may directly or indirectly affect one or more mixers, related mixing equipment, mud pits, storage facilities or units, composition separators, heat exchangers, sensors, gauges, pumps, compressors, and the like used generate, .store., monitor, regulate, and/or recondition the exemplary set-delayed cement compositions. The disclosed set-delayed cement compositions may also directly or indirectly affect any transport or delivery equipment used to convey the set-delayed cement compositions to a well site or downhole such as, for example, any transport vessels, conduits, pipelines, trucks, tubulars, and/or pipes used to compositionally move the set-delayed cement compositions from one location to another, any pumps, compressors, or motors (e.g., topside or downhole) used to drive the set-delayed cement compositions into motion, any valves or related joints used to regulate the pressure or flow rate of the set-delayed cement compositions, and any sensors (i.e., pressure and 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 that may come into contact with the set-delayed cement compositions such as, but not limited to, wellbore casing, welthore liner, completion string, insert strings, drill string, coiled tubing, slickline, wirehne, drill pipe, drill collars, mud motors, downhole motors and/or pumps, cement pumps, surface-mounted Motors and/or pumps, centralizers, turbolizers, scratchers, floats (c.gõ shoes, collars, valves, etc.), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromeclumical devices, etc.). sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g.,.
inflow control devices, autonomous inflow control devices, outflow control devites, etc.), couplings (es., electro-hydraulic wet connect, dry connect, inductive coupler, etc:), control lines (e.g., electrical, fiber optic, hydraulic, etc.), surveillance lines, drill bits and reamers, sensors or distributed sensors, downhole heat exchangers, valves and corresponding actuation devices, tool seals, packers, cement plugs, bridge plugs, and other wellbore isolation devices, or components, and the like.
EXAMPLES
[0063] To tacilitate a better understanding of the present embodiments, the following examples of certain aspects of some embodiments are given. In no way Should the following examples be read to limit, or define, the entire scope of the embocliments.
Example 1 [0064] A two part set-delayed cement composition was prepared which comprised the following component slurries:
Table I
Slurry A Compositional Makeup Slurry 13 Compositional Makeup Component Weight. (g) Component Weight (g) Water 175.0 Water 350.0 'Pumice 500.0 ' Hydrated Lime 350.0 Silica Additive 100.0 Weighting Agent 70.0 ¨Weighting Agent 30.0 Dispersant 2,0 -----\
rDispersant :3.5 [00651 Slurry A was prepared in a Waring' blender by first adding water to the :
blender followed by a dispersant, Liquiment t? - 5581F dispersant. The dispersant was allowed to fully disperse, then the pumice, silica (Silicalite cement additive), and a weight additive (MicroMaxr FP weight additive) were added. After all of the components were added, Slurry A was blended at a speed of 6000 rpm for 40 seconds to fully homogenize the sample.
Slurry B was prepared in the same manner as Slurry A. The calculated density of Slurry A
was 13.33 pounds per gallon (ppg) and Slurry B was 12.75 ppg [00661 Immediately after preparation (designated Day 0) and periodically thereafter, the theological properties of the samples were determined using a Model 35A
Fann Viscometer and a No. 2 spring with a Farm Yield Stress Adapter (FYSA), in accordance with . , the procedure set forth in API RP- Practice 1013-2., Recommended Prodiee fin.
Testing Well Cements. Dispersant. was added as needed to .maintain adequate viscosity values. % bwoP
refers to "percent by weight of the pumice," and .% bwont. refers to "percent by weight. of hydrated lime."
Table 2.
Slurry A itheofogical Profile FY.SA Readings Additional ' Dispersant 1 3 6 100 200 300 31) 6D
(% bwoP) t Day 0 48 49 71 87.5 103 48 47 ¨
¨ ¨
Da!?' 3 15 27.5 42 58.5 73 21 23 0.01 !
Day 7 25.5 26.5 47.5 67.5 89 17 14 --!
... _________________________________________________________________________ Day 40 4_5 8 56 99 143 1 1 0.10 ' Table 3 Slurry IA kheological Profile I
MA Readings Additional Dispersant .
3 6 100. 200 300 3D 61) M.bwolt0 , :
Day 0 25 /7 41 57 78 10 10 ....
, . , Day 3.. 215 23 80,5 145 214 12 12 -- , ' .
Day-7 22 26 80,5 149.5 .220 12 .12 _ . ___________________________________ .
Day 40 3 3,5 16 .:.,. -?,-.
.1 30.5 1 1 0.02 ............. ,.
[00671 To form the set:table combined slurry, 129.4 grams Of Slurry B was -added to 500.0 grams of-Slurry A. This was performed by adding Slurry A to a Waring' blender set to 4000 rpm and slowly pouring in Slurry El to term Slurry A13 with a final slurry composition of:

Table 4 Slurry AB Compositional Makeup . .
Component % buOP
Water 95.0 Pumice 100.0 Silica Additive 20.0 'Hydrated Lime 20.0 ¨ Weight Additive ¨ 10.0 Dispersant 0.80 [0068] The calculated density of Slurry AB was 13,23 ppg. A portion of Slurry AB
was accelerated with 10% bwoP CaC.12 by mixing 200.0 grams of Slurry A.B with 21.92 grams of 43% CaC12 solution. This Sample is shown in table -5 as accelerated.
Immediately after preparation, the theology of the sample was measured using a Model 35A
Fann Viscometer and a No. 2 spring with a Fan Yield Stress Adapter (FYSA), in accordance with the procedure set forth in API RP Practice 1013-2, Recommended Practice fOr Testing Well Cements.

Table 5 Slurry AB Rheological Profile FYSA Readings Unaccelerated 2 2 15 36 59 1 1 Accelerated 1 2 12 I 28 50 1 [00691 .After mixing the two component slurries to activate the set-delayed cement composition, the combined slurry was cured in a 2" by 4" plastic cylinder that was placed in a water bath at between about 90 F to about 150c F to form set cylinders. Then the destructive compressive strength (C.S.) was measured using a mechanical press in accordance with API RP Practice 1013-2, Recommended Practice )(Or Testing Well Cements.
The results of this test are set tbrth in Table 6 below. The reported compressive strengths are an average for two cylinders of each sample_ Compressive strength measurements were taken at 24 hours, 100701 For comparison, a non-two part set-delayed slurry was prepared by combining 350 grams water, 500 grams pumice, 100 grams hydrated lime, 20 grams Micromax4 weight additive, 6,25 grams Micro Matrix cement retarder, and 3.5 grams Liquimene 5581F dispersant, This slurry (-NCI) was aged 35 days prior- to use, activated with 10% bwoP CaCl2sOlution. and cured in the water baths at the same time as-Slurry AB.
Table 6 (ompressive Strength Tests Slurry Temp.-( Fl Time .(firs) C.S. (psi) AB (accelerated) 90,0 24 .105 NCI 90.0 24 Fluid*
AB 100.0 24 98 _ AB (accelerated) 100.0 24 165 _ NCI 100.0 24 .Fluid*
AB 120.0 24 1718 NCI 120.0 24 Gel**
AB 140.0 24 2240 NCI 140.0 431 AB 150.0 24 2479 NC1 150.0 802 Slurry remained unset and tlowable " Slurry was gelled and not I.-towable [00711 As Example I shows, slurry AB is more active at lower temperatures than NCI. Without being limited by theory, this effect may be due to the tack of cement retarders in 81.urry AB and/or the inclusion of a Silica additive.
Example 2 00721 In the previous examples the porzolan and lime slurries were mixed to give a hydrated lime content of 20.0% bwoP. The next example illustrates how it may he advantageous to mix the two parts in different ratios to produce slurries with varying lime content. In this example, 258.8 grams of Slurry 13 was mixed with 500,0 exams of Slurry A to give a lime 15content of 40% bwoP:
Table .7 Slurry AB Compositional Makeup Component bwor Water- 1 15,0 Pumice I 00.0 Silica Additive 20.0 = =
=
Hydrated Lime 40,0 Weighting Agent 14,0 'Dispersant 0.93' [00731 After mixing, this sample was cured in a water bath at 90 V for 24 hours then crushed to obtain a compressive strength of 150 psi. The Strength of this sample was about 33% greater than the sample with only 20% lime content (105 psi).
Example 3 00741 A two part set-delayed cement composition was prepared which comprised the following component slurries:
Table 8 Slurry C Compositional Makeup Slurry D Compositional Makeup Component Weight (g) Component Weight (g) Water 325.0 Water 350.0 Pumice 500.0 Hydrated Lime 350,0 Weighting Agent 30.0 Weighting Agent 70.0 Dispersant 3.5 Dispersant2.0 [00751 Slurry C was prepared in a Warine blender by first adding water to the blender followed by a dispersant, Liquimentv 5581F dispersant. The dispersant was allowed to hilly disperse, then the pumice and a weight additive (MicroMax''''' PI
weight additive) w-ere added, After all of the components were added, Slurry C was blended at a speed of 6000 rpm for 40 seconds to fully homogenize the sample. Slurry was prepared in the same manner as Slurry C. The calculated density of Slurry C was 13.24 pounds per gallon (ppg) and Slurry 13 was 12.75 ppg.
100761 immediately after preparation (designated Day 0) and periodically thereafter, the theological properties of the samples were determined using a Model 35A
Fann Viscometer and a No. 2 spring with a Farm Yield Stress Adapter (FYSA), in accordance with the procedure set forth in API RP Practice 10B-2, Recommended Practice fitt.
Testing Well Cements. Dispersant was added as needed to maintain adequate viscosity values.
Table 9 Slurry C ftheological Profile . .

FY$A R.eadings .
Additional , Dispersant 3 6 100 200 300 3.1) 61) (% bwom =
Day 0 3 4 , -83.5 167 251 0.5 0,5 --I
, Day 3 14.5 16.5 1 46 75 104 7 8 . , Day 7 5 8 I 81 154.5 274 1 2 0,01 i. 1 :
Day 40 1 4 6.5 56.5 106 154 1.5 1.5 0.02 .
:
Table 10 Slurry D Itheologieal Profile FYSA Readings.
Additional Dispersant , 3 6 100 200 300 3D 61) e/i) bwollt.)-, __________________________________________________________________________ Day 0 75 /7 41 57 78 10 10 ¨
_________________ ______I _____ Day 3 2L5 23 80.5 145 214 12 12 --Day 7 11 26 80.5 149.5 220 12 17 --Day 40 3 3.5 16 13 30.5 7 7 0.02 [0077] To form the settable combined slurry, .129.4 grams of Slurry D was added to 500,0 grams of Slurry C. This was perfbrmed by adding Slurry C to a Waring blender set to 4000 rpm and slowly pouring in Slurry D to -form Slurry CD with- a final slurry composition of:
Table 11 Slurry CD Compositional Makeup Component 14i bwoP
___________________________________________ , Water 85.0 Pumice 100.0 Hydrated Lime 20.0 Weighting Agent 10.0 Dispersant 0.80 100781 The calculated density of Slurry CD was 13.13 ppg. A pottion of Slum, CD
was accelerated with tO% bwoP CaCl2 by mixing 2000 grams of Slurry CD with 21_51 grams of 43% CaC12 solution. This sample is shown in table 11 as accelerated.
Immediately after Preparation, the theology of the sample was measured using a Model 35A
Farm Viscometer and a No. 2 spring with a Fann Yield Stress Adapter (FYSA), in accordance with the procedure Set forth in API RP Practice 10B-2, Recommended Pro ice fir MO*
Well Cements, Table 12 Slurry CD ltheological Profile FYSA Readings Unaccelerated Slurry was pourable hut very thick AcceleMted 7.5 8 ii L 14 41.5 3 3 [00791 After mixing the two component slurries to activate the set-delayed cement eoMposition, the coMbined slurry was cured in a 2" by 4" plastic cylinder that was placed in a water bath at 190 F to form set cylinders. Then the destructive compressive strength (C.S.) was measured using 4 mechanical press in accordance with API RP Practice 1013-2, Recommended practice for Testing Well Cements, The results of this test are set Ruth in Table 12 below. The reported compressive strengths are an average for two cylinders of each sample. The samples and controls were cured at 1. atmosphere, between about 90' I' to about J50' F; compressive strength measurements were taken at 24 or 48 hours.
[00801 For comparison, a non-two part set-delayed shirty was prepared by combining 350 grams water, 500 grams pumice, 100 grams hydrated lime, 20 grams Micromait weight additive, 6,25 grams Micro Matrix, cement retarder, and 3,5 grams Uquimentr 5581F dispersant.. This slurry (NCI) was aged 35 days prior to use, activated with 10% hwoP C1C12 solution, and cured in the water baths at the same time as Slurry AB.

Table 13 Compressive Strength Tests Slurry Temp, ( F) Time (hrs) C.S. (psi) CD 90.0 48 98 CD (activated) 90.0- 48 128 'NCI 90.0 48 Fluid*
CD 100,0 48 105 CD (activated) 100.0 48 216 NCI 100.0 48 120.0 24 78 .NCI 120.0 24 Gel"
CD 140.0 24 566 NC--r 24 431 CD 150.0 24 710 NCI 150.0 24 802 * Slurry remained unset and flowable ** Slurry was gelled and not flowable Example 4 [0081] A two part set-delayed cement composition was prepared which comprised the following component slurries:
Table 14 Slurry .E Compositional Makeup Slurry P Compositional Makeup Component Weight (g) =ME Weight (g) 111=11111Mall 11111011.11113111 Pumice 600.0 111=13111111.1 Dispersant 4.5 Dispersant 0.7 [0082] Slurry E was prepared in a Warine blender by first adding water to the blender .followed by a dispersant, Liquitnee 5581F dispersant. The dispersant was allowed to fully disperse, then the pumice was-addiA Alter all of the components were added, Slurry E was blended at a speed of 6000 rpm for 40 seconds to fully homogenize the sample. Slurry F was prepared in the same manner as Slurry E. 'the calculated density of Slurry E was 13,4 pounds per gallon (ppg) and Slurry F was 12.4 ppg. Slurry E and -Slurry F were then stored for 48 hours. After 48 hours neither slurry contained free water. However, Slurry F was slightly gelled. and required mixing to make it flowable.
[00831 At 48 hours, 778.7 grams of Slurry E was added to 175.4 grains of Slurry F.
TIth was performed by adding Slurry E to a Waring!. blender set to 4000- rpm and slowly pouring in Slurry F to form Slurry EP, When they were mixed a gel formed and LO gram of dispersant (Liquimere 5581F dispersant) was added to make the mixture flowable.
Table 15 Compositional Mix of Slurry FE
Mix Amount Wt. (g) Vol. (ml.,) Density (ppg) Slurry F. 778.7 484.2 13.4 Slurry F 175,4 118.1 12.4 [00841 The calculated density of the final slurry was 13.2 ppe. 15.0 grams Of powder (2.5% bwoN4-11.,) was added to the final slurry before placing it in a consistometa.
The thickening time was measured as 5:38 hours at 140'F and 3000 psi. The thickening time was measured using a high-temperature high-pressure consistometer in .accordance with the procedure for determining cement thickening times set forth in API RI' Practice I 013-2, Recommended Pracfice /Or Testing Well Cements, First Edition, 'July 2005.
100851 It should be understood that the compositions and methods are described in terms of "comprising," "containing," or "including" various components or steps, the compositions and methods can also "consist essentially or or "consist of' the various components and steps. Moreover, the indefinite articles "a" or "an," us used in the claims, are defined herein to mean one or more than one of the element that it introduces.
[00861 For the sake of brevity, only certain ranges are explicitly disclosed herein.
However, ranges from any lower limit may be combined with any upper limit to mite 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 any upper limit may be combined With any other upper limit to mite 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 !idling 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," or, equivalently, "from approximately a-b") disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values oven if not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
[0087] Therefore, the present embodiments are well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. 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 herein. Although individual embodiments are discussed, the disclosure covers all combinations of all of the embodiments. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of those embodiments. 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 referred to herein, the definitions that are consistent with this specification should be adopted.

Claims (25)

What is claimed is:
1. A method of cementing in a subterranean formation comprising:
providing a pozzolan slurry comprising a pozzolan and water, wherein the water is present in the pozzolan slurry in an amount of about 33%
to about 200%
by weight of the pozzolan;
providing a lime slurry comprising hydrated lime and water, wherein the lime is present in the lime slurry in an amount of about 10% to about 100%
by weight of the amount of pozzolan present in the pozzolan slurry, wherein the water is present in the lime slurry in an amount of about 33% to about 200% by weight of the lime;
allowing the pozzolan slurry and the lime slurry to remain separate for about one day or longer;
mixing the pozzolan slurry and the lime slurry to form a cement composition on a surface not within the subterranean formation or mixing the pozzolan slurry and the lime slurry to form a cement composition within the subterranean formation;
placing the cement composition into the subterranean formation; and allowing the cement composition to set in the subterranean formation in which the cement composition was placed.
2. A method according to claim 1 wherein the pozzolan is selected from the group consisting of fly ash, silica fume, metakaolin, pumice, and any combination thereof.
3. A method according to claim 1 or 2 wherein at least one of the pozzolan slurry, the lime slurry, or the cement composition further comprises a dispersant.
4. A method according to claim 3 wherein the dispersant comprises at least one dispersant selected from the group consisting of a sulfonated-formaldehyde-based dispersant, a polycarboxylated ether dispersant, and any combination thereof.
5. A method according to any one of claims 1 to 4 wherein at least one of the pozzolan slurry, the lime slurry, or the cement composition further comprises a cement set retarder.
6. A method according to claim 5 wherein the cement set retarder is selected from the group consisting of a phosphonic acid, a phosphonic acid derivative, a lignosulfonate, a salt, an organic acid, a carboxymethylated hydroxyethylated cellulose, a synthetic co- or ter-polymer comprising sulfonate and carboxylic acid groups, a borate compound, and any combination thereof.
7. A method according to any one of claims 1 to 6 wherein at least one of the pozzolan slurry, the lime slurry, or the cement composition further comprises a cement set activator; wherein the cement set activator comprises at least one cement set 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.
8. A method according to any one of claims 1 to 7 further comprising storing at least one of the pozzolan slurry or the lime slurry for a time period of about 7 days or longer prior to the step of mixing.
9. A method according to any one of claims 1 to 8 further comprising pumping the cement composition through a feed pipe and into a wellbore annulus that is penetrating the subterranean formation.
10. A method according to claim 1 wherein the pozzolan slurry and the lime slurry are mixed on the surface to form the cement composition.
11. A method of displacing a fluid in a subterranean formation comprising:
providing a pozzolan slurry comprising a pozzolan and water, wherein the water is present in the pozzolan slurry in an amount of about 33%
to about 200%
by weight of the pozzolan;
providing a lime slurry comprising hydrated lime and water, wherein the lime is present in the lime slurry in an amount of about 10% to about 100%
by weight of the amount of pozzolan present in the pozzolan slurry, wherein the water is present in the lime slurry in an amount of about 33% to about 200% by weight of the lime;
introducing a first portion of the pozzolan slurry into a wellbore that penetrates the subterranean formation such that the first portion of the pozzolan slurry displaces at least one fluid from the wellbore;
mixing a second portion of the pozzolan slurry and at least a portion of the lime slurry to form a cement composition, wherein the second portion of the pozzolan slurry and the portion of the lime slurry are mixed on a surface not within the subterranean formation or mixing the second portion of the pozzolan slurry and the portion of the lime slurry to form a cement composition within the subterranean formation;
placing the cement composition into the subterranean formation; and allowing the cement composition to set in the subterranean formation in which the cement composition was placed.
12. A method according to claim 11 wherein the pozzolan is selected from the group consisting of fly ash, silica fume, metakaolin, pumice, and any combination thereof.
13. A method according to claim 11 or 12 wherein the first portion of the pozzolan slurry that displaces at least one fluid from the wellbore is foamed prior to displacing at least one fluid from the wellbore.
14. A method according to any one of claims 11 to 13 wherein at least one of the pozzolan slurry, the lime slurry, or the cement composition further comprises a dispersant.
15. A method according to any one of claims 11 to 14 wherein at least one of the pozzolan slurry, the lime slurry, or the cement composition further comprises a cement set retarder.
16. A method according to any one of claims 11 to 15 wherein at least one of the pozzolan slurry, the lime slurry, or the cement composition comprises a cement set activator.
17. A method according to any one of claims 11 to 16 further comprising storing at least one of the pozzolan slurry or the lime slurry for a time period of about 7 days or longer prior to the step of mixing.
18. A method according to any one of claims 11 to 17 further comprising pumping the cement composition through a feed pipe and into a wellbore annulus that is penetrating the subterranean formation.
19. A method according to claim 11 wherein the second portion of the pozzolan slurry and the portion of the lime slurry are mixed on the surface to form the cement composition.
20. A system for cementing in a subterranean formation comprising:
a pozzolan slurry comprising a pozzolan and water, wherein the water is present in the pozzolan slurry in an amount of about 33% to about 200% by weight of the pozzolan;
a lime slurry for combination with the pozzolan slurry to form a cement composition, wherein the lime slurry comprises hydrated lime and water, wherein the lime is present in the lime slurry in an amount of about 10% to about 100% by weight of the amount of pozzolan present in the pozzolan slurry, wherein the water is present in the lime slurry in an amount of about 33% to about 200% by weight of the lime; and mixing equipment capable of mixing the pozzolan slurry and the lime slurry.
21. The system of claim 20 wherein the mixing equipment comprises a jet mixer capable of continuously mixing the pozzolan slurry and the lime slurry to form a cement composition as the pozzolan slurry and the lime slurry are pumped into the subterranean formation or a batch mixer capable of mixing the pozzolan slurry and the lime slurry to form a cement composition on a surface not within the subterranean formation, and wherein the system further comprises pumping equipment for delivering the cement composition into a wellbore.
22. A method of cementing in a subterranean formation comprising:
providing a pozzolan slurry comprising a pozzolan and water;
providing a lime slurry comprising hydrated lime and water;
allowing the pozzolan slurry and the lime slurry to remain separate for about one day or longer;
mixing the pozzolan slurry and the lime slurry to form a cement composition on a surface not within a subterranean formation or mixing the pozzolan slurry and the lime slurry to form a cement composition within a subterranean formation, wherein the cement composition comprises a cement set retarder comprising a phosphonic acid derivative, and wherein the cement composition further comprises a dispersant comprising a polycarboxylated ether dispersant;
placing the cement composition into a subterranean formation; and allowing the cement composition to set in the subterranean formation in which the cement composition was placed.
23. The method of claim 22 wherein the pozzolan is selected from the group consisting of fly ash, silica fume, metakaolin, pumice, and any combination thereof.
24. The method of claim 22 wherein at least one of the pozzolan slurry, the lime slurry, or the cement composition further comprises a cement set activator, wherein the cement set activator comprises at least one cement set activator selected from the group consisting of an amine, a silicate, zinc formate, calcium acetate, a Group IA
hydroxide; a Group 11A hydroxide, a monovalent salt, a divalent salt, nanosilica, a polyphosphate, and any combination thereof.
25. The method of claim 22 further comprising storing at least one or the pozzolan slurry or the lime slurry for a time period of about 7 days or longer prior to the step of mixing.
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