WO2018156117A1

WO2018156117A1 - Accelerators for low portland cement compositions

Info

Publication number: WO2018156117A1
Application number: PCT/US2017/018935
Authority: WO
Inventors: Thomas Jason Pisklak; Thomas Singh SODHI; Ronnie Glen Morgan; Sean William RIGGIO; Samuel J. Lewis
Original assignee: Halliburton Energy Services, Inc.
Priority date: 2017-02-22
Filing date: 2017-02-22
Publication date: 2018-08-30

Abstract

Disclosed herein are phosphate accelerators for cement compositions with a reduced Portland cement content. A method of cementing may comprise: providing a low Portland cement composition comprising a pozzolan, a phosphate accelerator, and water, wherein the phosphate accelerator comprises a polyphosphate, wherein the low Portland cement composition is free of Portland cement or comprises Portland cement in an amount of about 50% by weight of cementitious components or less; and allowing the low Portland cement composition to set.

Description

ACCELERATORS FOR LOW PORTLAND CEMENT COMPOSITIONS

BACKGROUND

[0001] In well cementing, such as well construction and remedial cementing, cement compositions are commonly utilized. Cement compositions may be used in a variety of subterranean applications. For example, in subterranean well construction, a pipe string (e.g., casing, liners, expandable tubulars, etc.) may be run into a well bore 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 well bore 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 well bore and may bond the exterior surface of the pipe string to the subterranean formation. Among other things, the cement sheath surrounding the pipe string functions to prevent the migration of fluids in the annulus, as well as protecting the pipe string from corrosion. Cement compositions also may be used in remedial cementing methods, for example, to seal cracks or holes in pipe strings or cement sheaths, to seal highly permeable formation zones or fractures, to place a cement plug, and the like.

[0002] Setting times for cement compositions may be adjusted with accelerators. Accelerators speed up the time required for a cement composition to become hardened in a reaction process that shortens WOC (Wait On Cement) time and provides faster drill out, thus saving rig time. This reaction process may be referred to as cement hydration whereby water induces chemical reactions that ultimately lead to bonding. Accelerators essentially speed the reaction with water, which in turn reduces (a) thickening time and/or increases (b) early compressive strength development after set.

[0003] Cement compositions may typically include Portland cement. While Portland cement provides a number of beneficial mechanical properties, Portland cement generally is a major component of the cost for the cement compositions. Additionally, Portland cement production may contribute about 5% yearly to the global carbon footprint. To address these concerns with Portland cement, low Portland cement compositions have been developed in which the concentration of Portland cement has been reduced by inclusion of supplementary cement materials, such as fly ash, volcanic rock, and/or slag, which can contribute to the mechanical properties of the set cement by cementitious activity. However, while such low Portland cement compositions may reduce cost, their design may be challenging as conventional cement additives may function differently in compositions with reduced Portland cement content. For example, accelerators that may function well in Portland cement may not provide the same effects in low Portland cement compositions. Thus, a continuing issue with low Portland cement compositions may be strength development, especially a low rate of strength development at low temperatures.

BRIEF DESCRIPTION OF THE DRAWINGS

[0004] These drawings illustrate certain aspects of some of the embodiments of the present invention, and should not be used to limit or define the invention.

[0005] FIG. 1 is a schematic illustration of showing introduction of a low Portland cement composition into a wellbore.

[0006] FIG. 2 is a schematic illustration of showing introduction of a low Portland cement composition into a wellbore.

DETAILED DESCRIPTION

[0007] The present disclosure may generally relate to cementing methods and systems. Provided herein are phosphate accelerators for cement compositions with a reduced Portland cement content, also referred to as low Portland cement compositions. In particular, the phosphate accelerators may comprise a polyphosphate. The phosphate accelerators may be used in low Portland cement compositions to induce enhanced compressive strengths. Surprisingly, the use of the phosphate accelerators may provide enhanced compressive strength in low Portland cement compositions even at low bottom hole static temperatures, such as about 140 °F (60 °C) or lower.

[0008] The low Portland cement compositions may comprise a pozzolan and water. A phosphate accelerator comprising a polyphosphate may be included in the low Portland cement composition to enhance compressive strength. In addition, the low Portland cement compositions may be considered "low Portland," in that the low Portland cement compositions comprise Portland cement in an amount of about 50% or less by weight of blend ("bwob") present in the low Portland cement composition. The blend may comprise any number of cementitious components. The low Portland cement compositions may also be designed that are free (or essentially free) of Portland cement. As used herein, the term "cementitious component" refers to materials that possess cementitious properties, such as materials with hydraulic or pozzolanic activity. Optionally, the low Portland cement compositions may comprise hydrated lime and/or one or more additional cement additives.

[0009] The low Portland cement compositions may have a density suitable for a particular application. The low Portland cement compositions may have any suitable density, including, but not limited to, a density in the range of about 8 pounds per gallon ("ppg") to about 16 ppg (1 g/cm³ to 1.9 g/cm³). In the foamed examples, the foamed cement compositions of the present invention may have a density in the range of about 8 ppg to about 13 ppg (1 g/cm³ to 1.6 g/cm³) (or even lower). The low Portland cement compositions may be foamed or unfoamed 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. Those of ordinary skill in the art, with the benefit of this disclosure, should recognize the appropriate density for a particular application.

[0010] The water used in the low Portland cement compositions may comprise, for example, freshwater, saltwater (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated saltwater produced from subterranean formations), seawater, or combinations thereof. Generally, the water may be from any source, provided that it does not contain an excess of compounds that may undesirably affect other components in the low Portland cement composition. The water may be included in an amount sufficient to form a pumpable slurry. The water may be included in the low Portland cement compositions in any suitable amount, including, but not limited to, the range of about 40% to about 200% bwob. In some examples, the water may be included in an amount in the range of about 40% to about 150% bwob.

[001 1] The low Portland cement compositions may comprise a pozzolan. The term "pozzolan" refers to siliceous or siliceous and aluminous materials that react with calcium hydroxide in the presence of water to form cementitious compounds. Any pozzolan suitable for use in subterranean cementing applications may be used in the low Portland cement compositions. Examples of suitable pozzolans may comprise fly ash, silica fume, agricultural waste ash, natural pozzolans (e.g., volcanic rock), or combinations thereof. The pozzolan may be present in the low Portland cement compositions in any suitable amount, including, but not limited to, an amount in the range of about 5% to about 100% bwob, from about 50% to about 100% bwob, from about 50% to about 80% bwob, or from 80% about 100% bwob. In some examples the pozzolan may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90% or about 100% bwob. Those of ordinary skill in the art, with the benefit of this disclosure, should be able to select an appropriate type and amount of pozzolan for a particular application.

[0012] An example of a suitable pozzolan may comprise fly ash. The fly ash may be used alone or in combination with one or more additional pozzolans, such as silica fume, agricultural waste ash, or natural pozzolans. 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, 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. 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 may be necessary for a low Portland cement composition comprising Class F fly ash. In some embodiments, lime may be 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 comprise, but are not limited to, POZMIX^® A cement additive, commercially available from Halliburton Energy Services, Inc., Houston, Texas.

[0013] Another example of a suitable pozzolan may comprise silica fume. The silica fume may be used alone or may be used in combination with one or more additional pozzolans, such as fly ash, agricultural waste ash, or natural pozzolans. Silica fume may alternatively be referred to as "microsilica" or "condensed silica fume." Silica fume is generally a byproduct material that may be obtained, for example, by reduction of quartz with coal in the manufacture of certain alloys. Silica fume may be processed after recovery, for example, to control particle size. Silica fume may be extremely fine, for example, with a mean particle size of less than 1 micron and, alternatively, less than 0.2 microns. The mean particle size, as used herein, corresponds to d50 values as measured by particle size analyzers such as those manufactured by Malvern Instruments, Worcestershire, United Kingdom. Silica fume may have a high surface area and is generally available in either a powder form or liquid.

[0014] Another example of a natural pozzolan may comprise an agricultural waste ash. The agricultural waste ash may be used alone or may be used in combination with one or more additional pozzolans, such as fly ash, silica fume, or natural pozzolans. Examples of agricultural waste ash that may be used in the low Portland cement composition comprise, for example, wood (e.g., sawdust, bark, twigs, branches, other waste wood) ash, tree leave ash, corn cob ash, rice hull ash, cane (e.g., sugar cane) ash, bagasse ash, grain (e.g., amaranth, barley, corn flaxseed, millet, oat, quinoa, rye, rice, wheat etc.) and related by-product(s) (e.g., husks, hulls, etc.) ash, orchard ash, vine trimming ash, grass (e.g., Korai, Tifton, native shiba, etc.) ash, straw ash, ground nut shell ash, legume (e.g., soybean) ash, and combinations thereof. Combinations of pozzolans may also be used, such as a combination of two or more different pozzolans. A cement composition may comprise a first pozzolan (e.g., volcanic rock or other suitable pozzolan) in an amount of about 30% to about 50% bwob, a second pozzolan (e.g., fly ash or other suitable pozzolan) in an amount of about 30% to about 50% bwob, and Portland cement in an amount of about 0% to about 40% bwob and, alternatively, the first pozzolan in an amount of about 40% to about 45% bwob, the second pozzolan in an amount of about 40% to about 45% bwob, and the Portland cement in an amount of about 10% to about 20% bwob.

[0015] Another example of a suitable pozzolan may comprise natural pozzolans. Natural pozzolans are generally present on the Earth's surface and may exhibit pozzolanic activity. Suitable natural pozzolans may comprise volcanic rock, diatomaceous earth, volcanic ash (e.g., tuff), metakaolin, zeolite, calcined clays, shale (e.g., calcined shale, opaline shale, etc.), and combinations thereof. The natural pozzolans may be ground or unground. Natural pozzolans may comprise materials, such as calcined clays, metakaolin, and calcined shale, which has been heat treated, for example, in a kiln to enhance their pozzolanic activity. Generally, the natural pozzolans may have any particle size distribution as desired for a particular application. The natural pozzolans may have any suitable particular size, including, but not limited to, a mean particle size in a range of from about 0.1 microns to about 200 microns, or even smaller. In specific examples, 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. One of ordinary skill in the art, with the benefit of this disclosure, should be able to select a natural pozzolan and particle size suitable for use for a chosen application.

[0016] As previously described, the low Portland cement compositions may optionally comprise hydrated lime. As used herein, the term "hydrated lime" will be understood to mean calcium hydroxide. The hydrated lime may be provided as quicklime (calcium oxide) which hydrates when mixed with water to form the hydrated lime. For example, quicklime may be used in preparing the cement composition, which will hydrate to form the hydrated lime. The hydrated lime may be included in the low Portland cement composition, for example, to provide a pozzolanic reaction with the pozzolan in the low Portland cement composition. 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 examples, the hydrated lime may be present 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. One of ordinary skill in the art, with the benefit of this disclosure, should recognize the appropriate amount of hydrated lime to include for a chosen application.

[0017] The low Portland cement compositions may comprise Portland cement. Portland is generally a hydraulic cement that sets and hardens by reaction with water. Portland cements that are suited for use in the present disclosure may be classified as Classes A, C, G, and H cements according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Ed., July 1 , 1990. In addition, in some examples, Portland cements suitable for use may be classified as ASTM Type I, II, or III. The low Portland cement compositions disclosed herein may be considered "low Portland," as they may comprise the Portland cement in an amount of about 50% bwob or less, about 40%> bwob or less, about 30%> bwob or less, or about 20%> bwob or less. One of ordinary skill in the art, with the benefit of this disclosure, should recognize the appropriate amount of Portland cement to include for a chosen application.

[0018] In addition to Portland cement, the low Portland cement compositions may further comprise one or more additional cementitious component with cementitious activity, such as cement kiln dust, slag cement, high alumina content cement, and gypsum cement, among others. Other additives suitable for use in cementing operations also may be included the low Portland cement compositions. Examples of such additives include, but are not limited to: weighting agents, retarders, accelerators, activators, gas control additives, lightweight additives, gas-generating additives, mechanical-property-enhancing additives, lost-circulation materials, filtration-control additives, fluid-loss-control additives, defoaming agents, foaming agents, transition time modifiers, dispersants, thixotropic additives, suspending agents, and combinations thereof. One of ordinary skill in the art, with the benefit of this disclosure, should be able to select an appropriate additive for a particular application. [0019] As previously described, a phosphate accelerator comprising a polyphosphate may be used to enhance compressive strength of the low Portland cement compositions. The phosphate accelerator may be dry blended with the pozzolan, hydraulic cement, and/or lime prior to combination with the water. A variety of different polyphosphates may be used for acceleration of the low Portland cement compositions, including polymeric metaphosphate salts, phosphate salts, and combinations thereof, for example. Specific examples of polymeric metaphosphate salts that may be used include, but are not limited to, sodium hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate, and combinations thereof. Interestingly, sodium hexametaphosphate is also known in the art to be a strong retarder of Portland cements, but has been shown herein to be an accelerator for low Portland cement compositions comprising a pozzolan.

[0020] The phosphate accelerator may be used in an amount sufficient to provide a desirable level of acceleration. The phosphate accelerator may be used in any suitable amount, including, but not limited to, an amount of about 1% to about 10% bwob, about 2% to about 8% bwob, or about 3% to about 6% bwob. One of ordinary skill in the art, with the benefit of this disclosure, should recognize the appropriate amount of the accelerator to include for a chosen application.

[0021] The low Portland cement composition with the phosphate accelerator may set to have a desirable compressive strength. 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 low Portland cement composition has been prepared and the resultant composition is maintained under specified temperature and pressure conditions. Compressive strength can be measured by either destructive or nondestructive methods. The destructive method physically tests the strength of set cement 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). Nondestructive methods may employ a UCA^™ ultrasonic cement analyzer, available from Fann^® Instrument Company, Houston, TX. Compressive strength values may be determined in accordance with API RP 10B-2, Recommended Practice for Testing Well Cements, First Edition, July 2005. [0022] The low Portland cement compositions may develop a suitable 24-hour compressive strength, including, but not limited to, in the range of from about 100 psi (7 kg/cm²) to about 5000 psi (352 kg/cm²), alternatively, from about 200 psi (14 kg/cm²) to about 4500 psi (316 kg/cm²), or alternatively from about 500 psi (35 kg/cm²) to about 4000 psi (281 kg/cm²). The compressive strength values may be determined, for example, using destructive or non-destructive methods at a temperature of approximately 100 °F (38 °C). By inclusion of the phosphate accelerator, the compressive strength may be increased by about 10%, about 50%, about 100% or more over the same composition without the phosphate accelerator.

[0023] The low Portland cement composition with the phosphate accelerator may also have desirable thickening times. Thickening time typically refers to the time a fluid, such as a cement 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 aforementioned API RP Practice 10B-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 Be. The low Portland cement compositions may have any suitable thickening time, including, but not limited to, greater than about 1 hour, alternatively, greater than about 2 hours, alternatively greater than about 5 hours at 3,000 psi (21 1 kg/cm²) and temperatures of about 140 °F (60 °C).

[0024] Suitable low Portland cement compositions may be prepared in accordance with any suitable technique. The desired quantity of water may be introduced into a mixer (e.g., a cement blender) followed by the dry blend. The dry blend may comprise the pozzolan and any additional solid additives, such as the Portland cement or additional cementitious components. The phosphate accelerator may be dry blended with the solid additives or the water, as desired for a particular application. Additional liquid additives, if any, may be added to the water as desired prior to, or after, combination with the dry blend. This mixture may be agitated for a sufficient period of time to form a pumpable slurry. By way of example, pumps may be used for delivery of the low Portland cement composition into the wellbore. As will be appreciated, the low Portland cement composition and/or the dry blend may be prepared at the well site or prepared offsite and then transported to the well site. If prepared offsite, the dry blend and/or low Portland cement composition and may be transported to the well site using any suitable mode of transportation, including, but not limited to, a truck, railcar, barge, or the like. Alternatively, the low Portland cement composition and and/or dry blend may be formulated at the well site, for example, where the components of the low Portland cement composition and and/or dry blend may be delivered from a transport (e.g., a vehicle or pipeline) and then mixed prior to placement downhole. As will be appreciated by those of ordinary skill in the art, with the benefit of this disclosure, other suitable techniques for preparing the low Portland cement compositions and may be used in accordance with this disclosure.

[0025] As will be appreciated by those of ordinary skill in the art, the low Portland cement composition may be used in a variety of subterranean operations, including primary and remedial cementing. A low Portland cement composition may be provided that comprises a pozzolan and water. A phosphate accelerator may be included in the low Portland cement composition to enhance compressive strength. Optionally, the low Portland cement composition may further comprise Portland cement and/or the additional additives disclosed herein. The low Portland cement composition may be introduced into a subterranean formation and allowed to set therein. As used herein, introducing the low Portland cement composition into a subterranean formation includes introduction into any portion of the subterranean formation, including, but not limited to, into a wellbore drilled into the subterranean formation, into a near wellbore region surrounding the wellbore, or into both.

[0026] In primary cementing, for example, the low Portland 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 low Portland cement composition may be allowed to set in the annular space to form an annular sheath of hardened cement. The low Portland cement composition may form a barrier that prevents the migration of fluids in the wellbore. The low Portland cement composition may also, for example, support the conduit in the wellbore.

[0027] In remedial cementing, a low Portland cement composition may be used, for example, in squeeze-cementing operations or in the placement of cement plugs. By way of example, the low Portland composition may be placed in a wellbore to plug an 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 microannulus). [0028] Accordingly, this disclosure describes systems, compositions, and methods relating to low Portland cement design process. Without limitation, the systems, compositions and methods may further be characterized by one or more of the following statements:

[0029] Statement 1. A method of cementing comprising: providing a low Portland cement composition comprising a pozzolan, a phosphate accelerator, and water, wherein the phosphate accelerator comprises a polyphosphate, wherein the low Portland cement composition is free of Portland cement or comprises Portland cement in an amount of about 50% by weight of cementitious components or less; and allowing the low Portland cement composition to set.

[0030] Statement 2. The method of statement 1 further comprising introducing the low Portland cement composition into a wellbore.

[0031] Statement 3. The method of statement 2 wherein the low Portland cement composition is introduced into the wellbore using one or more pumps.

[0032] Statement 4. The method of any previous statement wherein the low Portland cement composition is used in primary cementing to form a set cement sheath in a wellbore annulus.

[0033] Statement 5. The method of any previous statement, further comprising mixing the components of the low Portland cement composition using mixing equipment, the components comprising the pozzolan, the phosphate accelerator, and the water.

[0034] Statement 6. The method of any previous statement wherein the pozzolan comprises at least one material selected from the group consisting of fly ash, silica fume, agricultural waste ash, and a natural pozzolan.

[0035] Statement 7. The method of any previous statement wherein the pozzolan comprises a first pozzolan in an amount of about 30% to about 50% by weight and a second pozzolan in an amount of about 30% to about 50% by weight.

[0036] Statement 8. The method of statement 7 wherein the first pozzolan comprises volcanic rock, wherein the second pozzolan comprises fly ash, and wherein the Portland cement is present in an amount of about 10% to about 20% by weight of the cementitious components.

[0037] Statement 9. The method of any previous statement further comprising dry blending the phosphate accelerator with the pozzolan and the Portland cement prior to combination with the water. [0038] Statement 10. The method of any previous statement wherein the polyphosphate comprises sodium hexametaphosphate.

[0039] Statement 1 1. The method of any previous statement wherein the phosphate accelerator increases compressive strength of the low Portland cement composition by an amount of at least about 25% to about 50% as compared to use of no phosphate accelerator in the low Portland cement composition, wherein the compressive strength is a twenty-four hour compressive strength.

[0040] Statement 12. The method of any previous statement wherein the low Portland cement composition further comprises at least one material selected from the group consisting of hydrated lime, cement kiln dust, slag cement, high alumina content cement, and gypsum cement.

[0041 ] Statement 13. The method of statement 1 wherein pozzolan comprises volcanic rock in an amount of about 30% to about 50% by weight and fly ash in an amount of about 30% to about 50% by weight, wherein the Portland cement is present in an amount of about 10%) to about 20%> by weight of the cementitious components, wherein the polyphosphate comprises sodium hexametaphosphate.

[0042] Statement 14. A cement composition comprising: a pozzolan; a phosphate accelerator, wherein the phosphate accelerator comprises a polyphosphate; and water, wherein the cement composition is free of Portland cement or comprises Portland cement in an amount of about 50% by weight of cementitious components or less.

[0043] Statement 15. The composition of claim 14 wherein the pozzolan comprises at least one material selected from the group consisting of fly ash, silica fume, agricultural waste ash, and a natural pozzolan.

[0044] Statement 16. The composition of statement 14 or statement 15 wherein the pozzolan comprises a first pozzolan in an amount of about 30%> to about 50% by weight and a second pozzolan in an amount of about 30% to about 50% by weight.

[0045] Statement 17. The composition of statement 16 wherein the first pozzolan comprises volcanic rock, wherein the second pozzolan comprises fly ash, and wherein the Portland cement is present in an amount of about 10% to about 20% by weight of the cementitious components.

[0046] Statement 18. The composition of any one of statements 14 to 17 wherein the polyphosphate comprises sodium hexametaphosphate.

] ] [0047] Statement 19. The composition of any one of statements 14 to 17 wherein the polyphosphate comprises a polymeric metaphosphate salt.

[0048] Statement 20. The composition of any one of statements 14 to 19 wherein the phosphate accelerator is present in an amount sufficient to increase compressive strength by an amount of at least about 50% as compared to use of no phosphate accelerator in the cement composition, wherein the compressive strength is a twenty-four hour compressive strength.

[0049] Statement 21. A system comprising: a low Portland cement composition comprising a pozzolan, a phosphate accelerator, and water, wherein the phosphate accelerator comprises a polyphosphate, wherein the low Portland cement composition is free of Portland cement or comprises Portland cement in an amount of about 50% by weight of cementitious components or less; and a pump fluid fluidly coupled to a tubular in fluid communication with a wellbore, wherein the tubular is configured to convey the low Portland cement composition to the wellbore.

[0050] Statement 22. The system of statement 21 further comprising a vessel disposed upstream of the pump, wherein the low Portland cement composition is disposed in the vessel.

[0051] Statement 23. The system of statement 21 or statement 22 wherein the polyphosphate comprises sodium hexametaphosphate.

[0052] Methods of using the low Portland cement compositions described herein in well cementing will now be described in more detail with reference to FIGS. 1 -2. FIG. 1 illustrates an example system 100 that may be used for preparation and delivery of a low Portland cement composition downhole. It should be noted that while FIG. 1 generally depicts a land-based operation, those skilled in the art should 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 on FIG. 1 , the system 100 may include a vessel 105 and a pump 1 10. The pump 1 10 may be positioned downstream of the vessel 105 and may be fluidly coupled to a tubular 1 15 that is in fluid communication with the wellbore 120. The tubular 1 15 may be configured to circulate or otherwise deliver the low Portland cement composition to the wellbore 120. The tubular 1 15 may be comprised, for example, of one or more different pipes that extend into the wellbore 120. The pump 1 10 may be, for example, one or more high pressure or low pressure pumps, which may be depend on, the viscosity and density of the low Portland cement composition. The pump 1 10 may draw the low Portland cement composition from the vessel 105, elevate the low Portland cement composition to an appropriate pressure, and then introduce the low Portland cement composition to the tubular 1 15 for delivery downhole. The vessel 105 and pump 1 10 may be disposed on one or more cement trucks, for example. While not illustrated, system 100 may further include a recirculating mixer, a batch mixer and/or a jet mixer, which may be used for example, in preparation and/or storage of the low Portland cement composition. Non-limiting additional components that may be present include, but are not limited to, supply hoppers, valves, condensers, adapters, joints, gauges, sensors, compressors, pressure controllers, pressure sensors, flow rate controllers, flow rate sensors, temperature sensors, and the like.

[0053] Turning now to FIG. 2, the low Portland cement composition 200 may be placed into a subterranean formation 205. As illustrated, wellbore 120 may be drilled into the subterranean formation 205. While wellbore 120 is shown extending generally vertically into the subterranean formation 205, the principles described herein are also applicable to wellbores that extend at an angle through the subterranean formation 205, such as horizontal and slanted wellbores. As illustrated, the wellbore 120 comprises walls 210. A surface casing 215 may be cemented to the walls 210 of the wellbore 120 by cement sheath 220. One or more additional pipe strings (e.g., intermediate casing, production casing, liners, etc.), shown here as casing 225 may also be disposed in the wellbore 120. As illustrated, there is a wellbore annulus 230 formed between the casing 225 and the walls 210 of the wellbore 120 (and/or a larger conduit such as the surface casing 215). One or more centralizers 240 may be attached to the casing 225, for example, to centralize the casing 225 in the wellbore 120 prior to and during the cementing operation.

[0054] With continued reference to FIG. 2, the low Portland cement composition 200 may be pumped down the interior of the casing 225. The low Portland cement composition 200 may be allowed to flow down the interior of the casing 225 through the casing shoe 235 at the bottom of the casing 225 and up around the casing 225 into the wellbore annulus 230. The low Portland cement composition 200 may be allowed to set in the wellbore annulus 230, for example, to form a cement sheath that supports and positions the casing 225 in the wellbore 120. While not illustrated, other techniques may also be utilized for introduction of the low Portland cement composition 200. By way of example, reverse circulation techniques may be used that include introducing the low Portland cement composition 200 into the subterranean formation 205 by way of the wellbore annulus 230 instead of through the casing 225.

[0055] As it is introduced, the low Portland cement composition 200 may displace other fluids 245, such as drilling fluids and/or spacer fluids that may be present in the interior of the casing 225 and/or the wellbore annulus 230. At least a portion of the displaced fluids 245 may exit the wellbore annulus 230 via a flow line 125 and be deposited, for example, in one or more retention pits 130 (e.g., a mud pit), as shown on FIG. 1. Referring again to FIG. 2, a bottom plug 250 may be introduced into the wellbore 120 ahead of the low Portland cement composition 200, for example, to separate the low Portland cement composition 200 from the other fluids 245 that may be inside the casing 225 prior to cementing. After the bottom plug 250 reaches the landing collar 255, a diaphragm or other suitable device should rupture to allow the low Portland cement composition 200 through the bottom plug 250. In FIG. 2, the bottom plug 250 is shown on the landing collar 255. As illustrated, a top plug 260 may be introduced into the wellbore 120 behind the low Portland cement composition 200. The top plug 260 may separate the low Portland cement composition 200 from a displacement fluid 265 and also push the low Portland cement composition 200 through the bottom plug 250.

[0056] The exemplary low Portland 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 cement compositions. For example, the disclosed low Portland 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 low Portland cement compositions. The disclosed low Portland cement compositions may also directly or indirectly affect any transport or delivery equipment used to convey the low Portland 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 low Portland cement compositions from one location to another, any pumps, compressors, or motors (e.g., topside or downhole) used to drive the low Portland cement compositions into motion, any valves or related joints used to regulate the pressure or flow rate of the low Portland cement compositions, and any sensors (i.e., pressure and temperature), gauges, and/or combinations thereof, and the like. The disclosed low Portland cement compositions may also directly or indirectly affect the various downhole equipment and tools that may come into contact with the low Portland cement compositions such as, but not limited to, wellbore casing, wellbore liner, completion string, insert strings, drill string, coiled tubing, slickline, wireline, drill pipe, drill collars, mud motors, downhole motors and/or pumps, cement pumps, surface-mounted motors and/or pumps, centralizers, turbolizers, scratchers, floats (e.g., shoes, collars, valves, etc.), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromechanical devices, etc.), sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, etc.), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive coupler, etc.), control lines (e.g., electrical, fiber optic, hydraulic, etc.), surveillance 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

[0057] To facilitate a better understanding of the present disclosure, the following examples of certain aspects of the present disclosure are given. In no way should the following examples be read to limit, or define, the entire scope of the disclosure.

Example 1

[0058] In this example, the effectiveness of various accelerators in a low Portland cement composition was evaluated. This example was performed using the formulation shown below in Table 1 , wherein the type of accelerator was varied.

Table 1

[0059] Each sample was dry blended with the various accelerators except for the control which had no accelerator and then mixed according to API procedures. After preparation, the samples were each poured into 2 inch (5 cm) x 4 inch (10 cm) cylinders and cured in a water bath for 24 hours at 100 °F (38 °C) and ambient pressure, after which samples were crushed (using a Tinius Olsen load frame) to obtain compressive strengths in "unconfined loading" conditions. The results of this example for each accelerator are in Table 2.

Table 2

Sodium Sulfate 449 psi 62

(32 kg/cm²)

Sodium Chloride 549 psi 98

(39 kg/cm²)

[0060] Surprisingly, the two most common accelerators, sodium hydroxide and calcium chloride performed very poorly and did not function as accelerators in the lower Portland cement composition. As can be seen in Table 2, sodium hydroxide had a 5% decrease in compressive strength as compared to Control with no accelerator and calcium chloride showed no change. However, sodium sulfate and sodium chloride did function as accelerators. Accordingly, it can be observed that conventional cement accelerators may not function as expected in low Portland cement compositions.

Example 2

[0061] To identify accelerators for use in low Portland cement compositions, additional compositions were evaluated using the formulation of Table 1. The test conditions and accelerator concentrations were the same as used in Example 1.

Table 3

Sodium Aluminate 308 psi 12

(22 kg/cm²)

[0062] Surprisingly, while other compounds accelerated the low Portland cement composition to some degree, sodium hexametaphosphate increased the compressive strength by 105% as compared to the Control with no accelerator.

[0063] 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 of or "consist of the various components and steps. Moreover, the indefinite articles "a" or "an," as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

[0064] 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 recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range 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 even 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.

[0065] Therefore, the present disclosure is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular examples disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Although individual examples are discussed, the invention covers all combinations of all those examples. 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 examples disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. If there is any conflict in the usages of a word or term in this specification and one or more patent(s) or other documents that may be incorporated herein by reference, the definitions that are consistent with this specification should be adopted.

Claims

CLAIMS What is claimed is:

1. A method of cementing comprising:

providing a low Portland cement composition comprising a pozzolan, a phosphate accelerator, and water, wherein the phosphate accelerator comprises a polyphosphate, wherein the low Portland cement composition is free of Portland cement or comprises Portland cement in an amount of about 50% by weight of cementitious components or less; and

allowing the low Portland cement composition to set.

2. The method of claim 1 further comprising introducing the low Portland cement composition into a wellbore.

3. The method of claim 2 wherein the low Portland cement composition is introduced into the wellbore using one or more pumps.

4. The method of claim 2 wherein the low Portland cement composition is used in primary cementing to form a set cement sheath in a wellbore annulus.

5. The method of claim 1, further comprising mixing components of the low Portland cement composition using mixing equipment, the components comprising the pozzolan, the phosphate accelerator, and the water.

6. The method of claim 1 wherein the pozzolan comprises at least one material selected from the group consisting of fly ash, silica fume, agricultural waste ash, and a natural pozzolan.

7. The method of claim 1 wherein the pozzolan comprises a first pozzolan in an amount of about 30% to about 50% by weight and a second pozzolan in an amount of about 30% to about 50% by weight.

8. The method of claim 7 wherein the first pozzolan comprises volcanic rock, wherein the second pozzolan comprises fly ash, and wherein the Portland cement is present in an amount of about 10% to about 20% by weight of cementitious components present in the low Portland cement composition.

9. The method of claim 1 further comprising dry blending the phosphate accelerator with the pozzolan and the Portland cement prior to combination with the water.

10. The method of claim 1 wherein the polyphosphate comprises sodium hexametaphosphate.

1 1. The method of claim 1 wherein the phosphate accelerator increases compressive strength of the low Portland cement composition by an amount of at least about 25% to about 50% as compared to use of no phosphate accelerator in the low Portland cement composition, wherein the compressive strength is a twenty-four hour compressive strength.

12. The method of claim 1 wherein the low Portland cement composition further comprises at least one material selected from the group consisting of hydrated lime, cement kiln dust, slag cement, high alumina content cement, and gypsum cement.

13. The method of claim 1 wherein pozzolan comprises volcanic rock in an amount of about 30% to about 50% by weight and fly ash in an amount of about 30% to about 50% by weight, wherein the Portland cement is present in an amount of about 10% to about 20% by weight of the cementitious components present in the low Portland cement composition, wherein the polyphosphate comprises sodium hexametaphosphate.

14. A cement composition comprising:

a pozzolan;

a phosphate accelerator, wherein the phosphate accelerator comprises a polyphosphate; and

water,

wherein the cement composition is free of Portland cement or comprises Portland cement in an amount of about 50% by weight of cementitious components or less.

15. The composition of claim 14 wherein the pozzolan comprises at least one material selected from the group consisting of fly ash, silica fume, agricultural waste ash, and a natural pozzolan.

16. The composition of claim 14 wherein the pozzolan comprises a first pozzolan in an amount of about 30% to about 50% and a second pozzolan in an amount of about 30% to about 50%.

17. The composition of claim 16 wherein the first pozzolan comprises volcanic rock, wherein the second pozzolan comprises fly ash, and wherein the Portland cement is present in an amount of about 10% to about 20% by weight of cementitious components present in the cement composition.

18. The composition of claim 14 wherein the polyphosphate comprises sodium hexametaphosphate .

19. The composition of claim 14 wherein the polyphosphate comprises a polymeric metaphosphate salt.

20. The composition of claim 14 wherein the phosphate accelerator is present in an amount sufficient to increase compressive strength by an amount of at least about 50% as compared to use of no phosphate accelerator in the cement composition, wherein the compressive strength is a twenty-four hour compressive strength.