# Patent

## Title
Settable compositions comprising a natural pozzolan and associated methods

## Abstract

An embodiment of a method of cementing comprises: introducing a cement composition into a subterranean formation, wherein the cement composition comprises cement kiln dust, a natural pozzolan, and water; and allowing the cement composition to set. Another embodiment of a method comprises: introducing a cement composition into a subterranean formation, wherein the cement composition comprises a cement, a natural pozzolan, and water, wherein the cement comprises Portland cement interground with burned shale; and allowing the cement composition to set. Another embodiment includes a cement composition comprising at least one additive selected from the group consisting of cement, cement kiln dust, Portland cement interground with burned shale, and a combination thereof; a natural pozzolan; and water.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation in part of U.S. application Ser. No. 12/349,676, entitled “Extended Settable Compositions Comprising Cement Kiln Dust and Associated Methods,” filed on Jan. 7, 2009, which is a divisional of U.S. application Ser. No. 12/034,886 entitled “Extended Settable Compositions Comprising Cement Kiln Dust and Associated Methods, filed on Feb. 21, 2008, which is a continuation in part of U.S. application Ser. No. 11/223,669 entitled “Settable Compositions Comprising Cement Kiln Dust and Additive(s),” filed Sep. 9, 2005, the entire disclosures of which are incorporated herein by reference.


BACKGROUND
The present invention relates to cementing operations and, more particularly, in certain embodiments, to settable compositions comprising water, a natural pozzolan, and at least one of cement, Portland cement interground with burned shale, or cement kiln dust.
Settable compositions may be used in primary cementing operations whereby pipe strings, such as casing and liners, are cemented in well bores. In performing primary cementing, a settable composition may be pumped into an annular space between the walls of a well bore and the pipe string disposed therein. The settable composition sets in the annular space, thereby forming an annular sheath of hardened cement (e.g., a cement sheath) that supports and positions the pipe string in the well bore and bonds the exterior surface of the pipe string to the walls of the well bore.
Settable compositions also may be used in remedial cementing operations, such as sealing voids in a pipe string or a cement sheath. As used herein the term “void” refers to any type of space, including fractures, holes, cracks, channels, spaces, and the like. Such voids may include: holes or cracks in the pipe strings; holes, cracks, spaces, or channels in the cement sheath; and very small spaces (commonly referred to as “microannuli”) between the cement sheath and the exterior surface of the well casing or formation. Sealing such voids may prevent the undesired flow of fluids (e.g., oil, gas, water, etc.) and/or fine solids into, or from, the well bore. The sealing of such voids, whether or not made deliberately, has been attempted by introducing a substance into the void and permitting it to remain therein to seal the void. If the substance does not fit into the void, a bridge, patch, or sheath may be formed over the void to possibly produce a termination of the undesired fluid flow. Substances used heretofore in methods to terminate the undesired passage of fluids through such voids include settable compositions comprising water and hydraulic cement, wherein the methods employ hydraulic pressure to force the settable composition into the void. Once placed into the void, the settable composition may be permitted to harden.
Remedial cementing operations also may be used to seal portions of subterranean formations or portions of gravel packs. The portions of the subterranean formation may include permeable portions of a formation and fractures (natural or otherwise) in the formation and other portions of the formation that may allow the undesired flow of fluid into, or from, the well bore. The portions of the gravel pack include those portions of the gravel pack, wherein it is desired to prevent the undesired flow of fluids into, or from, the well bore. A “gravel pack” is a term commonly used to refer to a volume of particulate materials (such as sand) placed into a well bore to at least partially reduce the migration of unconsolidated formation particulates into the well bore. While screenless gravel packing operations are becoming more common, gravel packing operations commonly involve placing a gravel pack screen in the well bore neighboring a desired portion of the subterranean formation, and packing the surrounding annulus between the screen and the well bore with particulate materials that are sized to prevent and inhibit the passage of formation solids through the gravel pack with produced fluids. Among other things, this method may allow sealing of the portion of the gravel pack to prevent the undesired flow of fluids without requiring the gravel pack's removal.
Settable compositions also may be used during the drilling of the well bore in a subterranean formation. For example, in the drilling of a well bore, it may be desirable, in some instances, to change the direction of the well bore. In some instances, settable compositions may be used to facilitate this change of direction, for example, by drilling a pilot hole in a hardened mass of cement, commonly referred to as a “kickoff plug,” placed in the well bore. Certain formations may cause the drill bit to drill in a particular direction. For example, in a vertical well, this may result in an undesirable well bore deviation from vertical. In a directional well (which is drilled at an angle from vertical), after drilling an initial portion of the well bore vertically, the direction induced by the formation may make following the desired path difficult. In those and other instances, special directional drilling tools may be used, such as a whipstock, a bent sub-downhole motorized drill combination, and the like. Generally, the directional drilling tool or tools used may be orientated so that a pilot hole is produced at the desired angle to the previous well bore in a desired direction. When the pilot hole has been drilled for a short distance, the special tool or tools are removed, if required, and drilling along the new path may be resumed. To help ensure that the subsequent drilling follows the pilot hole, it may be necessary to drill the pilot hole in a kickoff plug, placed in the well bore. In those instances, prior to drilling the pilot hole, a settable composition may be introduced into the well bore and allowed to set to form a kickoff plug therein. The pilot hole then may be drilled in the kickoff plug, and the high strength of the kickoff plug helps ensure that the subsequent drilling proceeds in the direction of the pilot hole.
In certain applications, extended settable compositions have been used heretofore. As used herein, the term “extended settable composition” refers to a settable composition capable of remaining in a pumpable fluid state for an extended period of time (e.g., at least about 1 day). A fluid is considered to be in a pumpable fluid state where the fluid has a viscosity of less than 70 Bc, as measured using an FANN Atmospheric Consistometer Model 165AT (available from FANN Instrument Company, Houston, Tex.) at room temperature (for example, 78° F.). In general, the extended settable compositions comprise cement, water, and a set retarder and remain in a pumpable fluid state for an extended period of time. When desired for use, the extended settable composition should be capable of being activated whereby reasonable compressive strengths are developed. For example, a cement set accelerator may be added to the extended settable composition whereby the composition sets into a hardened mass. Among other things, the extended settable compositions of the present invention may be suitable for use in well bore applications, for example, where it is desired to prepare the settable composition in advance. This may allow, for example, the settable composition to be stored prior to its use. In addition, this may allow, for example, the settable composition to be prepared at a convenient location and then transported to the job site for use. Accordingly, capital expenditures associated with the cementing operations may be reduced due to a reduction in the need for on-site bulk storage and mixing equipment.
Settable compositions (and extended settable compositions) used heretofore commonly comprise Portland cement. Portland cement generally is a major component of the cost for the settable compositions. To reduce the cost of such settable compositions, other components may be included in the settable composition in addition to, or in place of, the Portland cement. Such components may include fly ash, slag cement, shale, metakaolin, micro-fine cement, and the like. “Fly ash,” as that term is used herein, refers to the residue from the combustion of powdered or ground coal, wherein the fly ash carried by the flue gases may be recovered, for example, by electrostatic precipitation. “Slag,” as that term is used herein, refers to a granulated, blast furnace by-product formed in the production of cast iron and generally comprises the oxidized impurities found in iron ore. Slag cement generally comprises slag and a base, for example, such as sodium hydroxide, sodium bicarbonate, sodium carbonate, or lime, to produce a settable composition that, when combined with water, may set to form a hardened mass.
During the manufacture of cement, a waste material commonly referred to as “CKD” is generated. “CKD,” as that term is used herein, refers to a partially calcined kiln feed which is removed from the gas stream and collected, for example, in a dust collector during the manufacture of cement. Usually, large quantities of CKD are collected in the production of cement that are commonly disposed of as waste. Disposal of the waste CKD can add undesirable costs to the manufacture of the cement, as well as the environmental concerns associated with its disposal. The chemical analysis of CKD from various cement manufactures varies depending on a number of factors, including the particular kiln feed, the efficiencies of the cement production operation, and the associated dust collection systems. CKD generally may comprise a variety of oxides, such as SiO2, Al2O3, Fe2O3, CaO, MgO, SO3, Na2O, and K2O.
SUMMARY
The present invention relates to cementing operations and, more particularly, in certain embodiments, to settable compositions comprising water, a natural pozzolan, and at least one of cement, Portland cement interground with burned shale, or cement kiln dust.
An embodiment of the present invention provides a method of cementing in a subterranean formation. The method may comprise introducing a cement composition into the subterranean formation, wherein the cement composition comprises cement kiln dust, a natural pozzolan, and water. The method further may comprise allowing the cement composition to set.
Another embodiment of the present invention provides a method of cementing in a subterranean formation. The method may comprise introducing a cement composition into the subterranean formation, wherein the cement composition comprises a cement, a natural pozzolan, and water, wherein the cement comprises Portland cement interground with burned shale. The method further may comprise allowing the cement composition to set.
Yet another embodiment of the present invention provides a cement composition comprising at least one additive selected from the group consisting of cement, cement kiln dust, Portland cement interground with burned shale, and a combination thereof. The cement composition may further comprise a natural pozzolan and water.
The features and advantages of the present invention will be readily apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.


DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention relates to cementing operations and, more particularly, in certain embodiments, to settable compositions comprising water, a natural pozzolan, and at least one of cement, Portland cement interground with burned shale, or cement kiln dust. There may be several potential advantages to the methods and compositions of the present invention, only some of which may be alluded to herein. One of the many potential advantages of the methods and compositions of the present invention is that the inclusion of the cement kiln dust and/or natural pozzolan in the settable composition may reduce the amount of a higher cost additive, such as Portland cement, resulting in a more economical settable composition.
The settable compositions of the present invention generally may comprise water and a natural pozzolan, in accordance with embodiments of the present invention. In addition, the settable compositions of the present invention further may comprise at least one of cement or cement kiln dust. For example, a settable composition of the present invention may comprise hydraulic cement, cement kiln dust, a natural pozzolan, and water. In certain embodiments, the cement may comprise Portland cement interground with burned shale. By way of example, a settable composition of the present invention may comprise cement, a natural pozzolan, and water, wherein the cement comprises Portland cement interground with burned shale. As described in more detail herein, embodiments of the settable compositions of the present invention may be foamed and/or extended as desired by those of ordinary skill in the art.
The settable compositions of the present invention should have a density suitable for a particular application as desired by those of ordinary skill in the art, with the benefit of this disclosure. In some embodiments, the settable compositions of the present invention may have a density in the range of about 8 pounds per gallon (“ppg”) to about 16 ppg. In the foamed embodiments, the foamed settable compositions of the present invention may have a density in the range of about 8 ppg to about 13 ppg.
The water used in the settable compositions of the present invention may include, 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 settable composition. In some embodiments, the water may be included in an amount sufficient to form a pumpable slurry. In some embodiments, the water may be included in the settable compositions of the present invention in an amount in the range of about 40% to about 200% by weight of cementitious components (“bwoc”). Cementitious components include those components that set and harden, either by themselves or in combination with another component, by reaction with water, such as hydraulic cement, cement kiln dust, a natural pozzolan, and the like. In some embodiments, the water may be included in an amount in the range of about 40% to about 150% bwoc.
Hydraulic cement is a component that may be included in embodiments of the settable compositions of the present invention. A variety of hydraulic cements may be utilized in accordance with the present invention, including, but not limited to, those comprising calcium, aluminum, silicon, oxygen, iron, and/or sulfur, which set and harden by reaction with water. Suitable hydraulic cements include, but are not limited to, Portland cements, pozzolana cements, gypsum cements, high alumina content cements, slag cements, silica cements, and combinations thereof. In certain embodiments, the hydraulic cement may comprise a Portland cement. In some embodiments, the Portland cements that are suited for use in the present invention are 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., Jul. 1, 1990. In addition, in some embodiments, cements suitable for use in the present invention may be classified as ASTM Type I, II, or III.
Where present the hydraulic cement generally may be included in the settable compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the hydraulic cement may be present in the settable compositions of the present invention in an amount in the range of 0% to about 99% bwoc. In some embodiments, the hydraulic cement may be present in the settable compositions of the present invention in an amount in the range of 0% to about 95% bwoc. In some embodiments, the hydraulic cement may be present in the settable compositions of the present invention in an amount in the range of about 20% to about 95% bwoc. In some embodiments, the hydraulic cement may be present in the settable compositions of the present invention in an amount in the range of about 50% to about 90% bwoc.
An example of a suitable hydraulic cement comprises a Portland cement interground with burned shale. The calcination of shale results in what is commonly referred to as “burned shale.” The calcination process may occur at temperatures as high as about 2,200° F. or higher. By way of example, shale may be calcined at temperatures of about 2,700° F. in accordance with embodiments of the present invention. The burned shale may then be interground with the Portland cement. For example, a mixture of Portland cement and burned shale may be ground with a ball mill. In certain embodiments, the hydraulic cement may comprise about 73% by weight Portland cement (such as Portland Class C cement) interground with about 27% burned shale. In certain embodiments, the burned shale that is interground with the Portland cement may comprise Eagleford shale. An example of a suitable Portland cement interground with burned shale is available from TXI Energy Services, Inc. under the trade name TXI Lightweight cement.
Another example of a suitable hydraulic cement comprises a pozzolana cement. In some embodiments, a pozzolana cement that may be suitable for use comprises 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, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Ed., Jul. 1, 1990. Class C fly ash comprises both silica and lime so that, when mixed with water, it sets to form a hardened mass. Class F fly ash generally does not contain sufficient lime, so an additional source of calcium ions is required for the Class F fly ash to form a settable composition with water. In some embodiments, lime may be mixed with Class F fly ash in an amount in the range of about 0.1% to about 25% 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, POZMIX® A cement additive, commercially available from Halliburton Energy Services, Inc., Duncan, Okla.
Where present, the fly ash generally may be included in the settable compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the fly ash may be present in the settable compositions of the present invention in an amount in the range of about 5% to about 75% bwoc. In some embodiments, the fly ash may be present in the settable compositions of the present invention in an amount in the range of about 10% to about 60% bwoc.
Another example of a suitable hydraulic cement comprise a slag cement. In some embodiments, a slag cement that may be suitable for use may comprise slag. Slag generally does not contain sufficient basic material, so slag cement further may comprise a base to produce a settable composition that may react with water to set to form a hardened mass. Examples of suitable sources of bases include, but are not limited to, sodium hydroxide, sodium bicarbonate, sodium carbonate, lime, and combinations thereof.
Where present, the slag cement generally may be included in the settable compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the slag cement may be present in the settable compositions of the present invention in an amount in the range of 0% to about 99% bwoc. In some embodiments, the slag cement may be present in the settable compositions of the present invention in an amount in the range of about 5% to about 75% bwoc.
CKD is another component that may be included in embodiments of the settable compositions of the present invention. The CKD should be included in the settable compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost reduction. In some embodiments, the CKD may be present in the settable compositions of the present invention in an amount in the range of about 1% to about 99% bwoc. In some embodiments, the CKD may be present in the settable compositions of the present invention in an amount in the range of about 5% to about 99% bwoc. In some embodiments, the CKD may be present in the settable compositions of the present invention in an amount in the range of about 5% to about 80% bwoc. In some embodiments, the CKD may be present in the settable compositions of the present invention in an amount in the range of about 10% to about 50% bwoc.
A natural pozzolan is another component that may be included in embodiments of the settable compositions of the present invention. Natural pozzolans are generally present on the Earth's surface and set and harden in the presence of hydrated lime and water. Examples of natural pozzolans include pumicite, diatomaceous earth, volcanic ash, opaline shale, tuff, and combinations thereof. Generally, pumicite is a volcanic rock that exhibits cementitious properties, in that it may set and harden in the presence of hydrated lime and water. Hydrated lime may be used in combination with the pumicite, for example, to provide sufficient calcium ions for pumicite to set. The natural pozzolan may be used, among other things, to replace higher cost cementitious components, such as Portland cement, in embodiments of the settable compositions, resulting in more economical settable compositions. In some embodiments, the natural pozzolan may be present in an amount in the range of from about 0.1% to about 50% bwoc. In some embodiments, the natural pozzolan may be present in an amount in the range of from about 25% to about 50% bwoc.
Metakaolin is another component that may be included in embodiments of the settable compositions of the present invention includes 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° to about 800° C. In some embodiments, the metakaolin may be present in the settable compositions of the present invention in an amount in the range of about 5% to about 95% bwoc. In some embodiments, the metakaolin may be present in an amount in the range of about 10% to about 50% bwoc.
Shale is another component that may be included in embodiments of the settable compositions of the present invention. As set forth above, burned shale may be interground with Portland cement, in accordance with embodiments of the present invention. Among other things, shale included in the settable compositions may react with excess lime to form a suitable cementing material, for example, calcium silicate hydrate. A variety of shales are suitable, including those comprising silicon, aluminum, calcium, and/or magnesium. An example of a suitable shale comprises vitrified shale. Suitable examples of vitrified shale include, but are not limited to, PRESSUR-SEAL FINE LCM material and PRESSUR-SEAL COARSE LCM material, which are commercially available from TXI Energy Services, Inc., Houston, Tex. Generally, the shale may have any particle size distribution as desired for a particular application. In certain embodiments, the shale may have a particle size distribution in the range of about 37 micrometers to about 4,750 micrometers.
Where present, the shale may be included in the settable compositions of the present invention in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the shale may be present in an amount in the range of about 5% to about 75% bwoc. In some embodiments, the shale may be present in an amount in the range of about 10% to about 35% bwoc. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the shale to include for a chosen application.
Zeolite is another component that may be included in embodiments of the settable compositions of the present invention. Zeolites generally are porous alumino-silicate minerals that may be either a natural or synthetic material. Synthetic zeolites are based on the same type of structural cell as natural zeolites, and may comprise aluminosilicate hydrates. As used herein, the term “zeolite” refers to all natural and synthetic forms of zeolite. Examples of suitable zeolites are described in more detail in U.S. Patent Publication No. 2007/10056475 A1. An example of a suitable source of zeolite is available from the C2C Zeolite Corporation of Calgary, Canada. In some embodiments, the zeolite may be present in the settable compositions of the present invention in an amount in the range of about 5% to about 65% bwoc. In certain embodiments, the zeolite may be present in an amount in the range of about 10% to about 40% bwoc.
Lime is another component that may be included in embodiments of the settable compositions of the present invention. In certain embodiments, the lime may be hydrated lime. Where present, the lime may be present in the settable compositions in an amount in the range of from about 1% to about 40% bwoc. In some embodiments, the lime may be present in the settable compositions in an amount in the range of from about 5% to about 20% bwoc.
A set retarding additive is another component that may be included in embodiments of the settable compositions of the present invention. As used herein, the term “set retarding additive” refers to an additive that retards the setting of the settable compositions of the present invention. Examples of suitable set retarding additives include, but are not limited to, ammonium, alkali metals, alkaline earth metals, metal salts of sulfoalkylated lignins, hydroxycarboxy acids, copolymers that comprise acrylic acid or maleic acid, and combinations thereof. One example of a suitable sulfoalkylate lignin comprises a sulfomethylated lignin. Suitable set retarding additives are disclosed in more detail in U.S. Pat. No. Re. 31,190, the entire disclosure of which is incorporated herein by reference. Suitable set retarding additives are commercially available from Halliburton Energy Services, Inc. under the trade names HR® 4, HR® 5, HR® 7, HR® 12, HR® 15, HR® 25, HR® 601, SCRTM 100, and SCRTM 500 retarders. Generally, where used, the set retarding additive may be included in the settable compositions of the present invention in an amount sufficient to provide the desired set retardation. In some embodiments, the set retarding additive may be present in an amount in the range of about 0.1% to about 5% bwoc.
Optionally, other additional additives may be added to the settable compositions of the present invention as deemed appropriate by one skilled in the art, with the benefit of this disclosure. Examples of such additives include, but are not limited to, strength-retrogression additives, set accelerators, weighting agents, lightweight additives, gas-generating additives, mechanical property enhancing additives, lost-circulation materials, filtration-control additives, dispersants, defoaming agents, foaming agents, thixotropic additives, and combinations thereof. Specific examples of these, and other, additives include crystalline silica, amorphous silica, fumed silica, salts, fibers, hydratable clays, microspheres, rice husk ash, elastomers, resins, latex, combinations thereof, and the like. A person having ordinary skill in the art, with the benefit of this disclosure, will readily be able to determine the type and amount of additive useful for a particular application and desired result.
As mentioned above, the settable compositions of the present invention may be foamed, for example, further comprising a gas and a surfactant, in accordance with embodiments of the present invention. A foamed settable composition may be used, for example, where it is desired for the settable composition to be lightweight. For example, a foamed settable composition of the present invention may comprise hydraulic cement, cement kiln dust, a natural pozzolan, a gas, a surfactant and water. By way of further example, a foamed settable composition of the present invention may comprise cement, a natural pozzolan, a gas, a surfactant, and water, wherein the cement comprise Portland cement interground with burned shale. Other suitable additives, such as those discussed previously, also may be included in the foamed settable compositions of the present invention as desired by those of ordinary skill in the art, with the benefit of this disclosure.
The gas used in the foamed settable compositions of the present invention may be any gas suitable for foaming a settable composition, including, but not limited to, air, nitrogen, or combinations thereof. Generally, the gas should be present in the foamed settable compositions of the present invention in an amount sufficient to form the desired foam. In certain embodiments, the gas may be present in the foamed settable compositions of the present invention in an amount in the range of about 10% to about 80% by volume of the composition.
Where foamed, the settable compositions of the present invention further comprise a surfactant. In some embodiments, the surfactant comprises a foaming and stabilizing surfactant. As used herein, a “foaming and stabilizing surfactant composition” refers to a composition that comprises one or more surfactants and, among other things, may be used to facilitate the foaming of a settable composition and also may stabilize the resultant foamed settable composition formed therewith. Any suitable foaming and stabilizing surfactant composition may be used in the settable compositions of the present invention. Suitable foaming and stabilizing surfactant compositions may 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 hydroxysultaine surfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodium chloride, and water; hydrolyzed keratin; mixtures of an ethoxylated alcohol ether sulfate surfactant, an alkyl or alkene amidopropyl betaine surfactant, and an alkyl or alkene dimethylamine oxide surfactant; aqueous solutions of an alpha-olefinic sulfonate surfactant and a betaine surfactant; and combinations thereof. In one certain embodiment, the foaming and stabilizing surfactant composition comprises a mixture of an ammonium salt of an alkyl ether sulfate, a cocoamidopropyl betaine surfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodium chloride, and water. A suitable example of such a mixture is ZONESEAL® 2000 foaming additive, commercially available from Halliburton Energy Services, Inc. Suitable foaming and stabilizing surfactant compositions are described in U.S. Pat. Nos. 6,797,054, 6,547,871, 6,367,550, 6,063,738, and 5,897,699, the entire disclosures of which are incorporated herein by reference.
Generally, the surfactant may be present in the foamed settable compositions of the present invention in an amount sufficient to provide a suitable foam. In some embodiments, the surfactant may be present in an amount in the range of about 0.8% and about 5% by volume of the water (“bvow”).
As mentioned above, the settable compositions may be extended in accordance with embodiments of the present invention, in that the present invention provides extended settable compositions that are capable of remaining in a pumpable fluid state for an extended period of time. For example, the extended settable compositions may be capable of remaining in a pumpable fluid state for at least about 1 day or longer (e.g., at least about 5 days). When desired for use, the extended settable composition may be activated (e.g., by addition of a cement set accelerator) to thereby set into a hardened mass. By way of example, the extended settable composition, after activation, may set to a compressive strength (as determined using the procedure set forth in API Recommended Practice 10B) at 140° F. of at least 100 psi in 72 hours, alternatively at least 500 psi. Among other things, the extended settable compositions of the present invention may be suitable for use in well bore applications, for example, where it is desired to prepare the cement composition in advance. By way of example, the extended settable compositions may facilitate preparation of the settable composition at a convenient location and then transport to the Job site for use in the cementing operation.
An example of a suitable extended settable composition of the present invention comprises water, a natural pozzolan, a set retarding additive, and at least one of cement, Portland cement interground with burned shale, or cement kiln dust. Optionally, a suspending agent may be included in the extended settable composition as desired. Other suitable additives, such as those discussed previously, also may be included in the extended settable compositions of the present invention as desired by those of ordinary skill in the art, with the benefit of this disclosure.
Set retarding additives are included in the extended settable compositions of the present invention, in accordance with embodiments of the present invention. Examples of suitable set retarding additives include, but are not limited to, organic acids, lignosulfonates, synthetic retarders and combinations thereof. It has been discovered that certain set retarding additives, such as phosphonated compounds, may not be desirable in certain applications because the settable composition may become over retarded such that the composition does not activate and develop reasonable compressive strength. Examples of organic acids that may be included in the extended settable compositions of the present invention include, but are not limited to, tartaric acid, gluconic acid, carboxylic acids (e.g., citric acid), hydroxy carboxy acids, and combinations thereof. One example of a suitable tartaric acid is HR®-25 cement retarder available from Halliburton Energy Services, Inc. Examples of lignosulfonates that may be included in the extended settable compositions of the present invention include, but are not limited to, a sulfomethylated lignin, calcium lignosulfonates, sodium lignosulfonates, and combinations thereof. Examples of suitable lignosulfonates include HR®-4, HR®-5, and HR®-7 cement retarders available from Halliburton Energy Services, Inc. Examples of synthetic retarders that may be included in the extended settable compositions of the present invention include, but are not limited to, copolymers of acrylic acid and acrylamido-methylpropane sulfonate polymer and copolymers of maleic anhydride and acrylamido-methyl-propane sulfonate polymer. Examples of suitable synthetic retarders include SCRTM-100 and SCRTM-500 cement retarders available from Halliburton Energy Services, Inc. Examples of suitable synthetic retarders are described in U.S. Pat. Nos. 4,941,536, 5,049,288, 5,472,051, and 5,536,311, the disclosures of which are incorporated herein by reference.
The set retarding additive should be included in the extended settable compositions of the present invention in an amount sufficient for the settable composition to remain in a pumpable fluid state for an extended period of time (e.g., at least about 1 day). In certain embodiments, the set retarding additive may be included in the extended settable composition in an amount in the range of about 0.1% to about 5% bwoc. In certain embodiments, the set retarding additive may be included in the extended settable composition in an amount in the range of about 0.1% to about 1.5% bwoc. Where the set retarding additive comprises tartaric acid, the tartaric acid may be in the extended settable composition in an amount in the range of about 0.2% to about 0.35% bwoc, for example. Where the set retarding additive comprises a sulfomethylated lignin, the sulfomethylated lignin may be, for example, included in the extended settable composition in an amount in the range of about 0.2% to about 1% bwoc. Those of ordinary skill in the art, with the benefit of this disclosure, should be able to determine an appropriate set retarding additive and amount thereof for a particular application.
As previously mentioned, at a desired time for use, the extended settable composition may be activated, for example, by addition of a cement set accelerator. Examples of suitable cement set accelerators include, but are not limited to, calcium chloride, triethanolamine, sodium silicate, zinc formate, calcium acetate, and combinations thereof. An example of a suitable sodium silicate is ECONOLITETM additive, available from Halliburton Energy Services, Inc. The cement set accelerator should be added to the extended settable composition in an amount sufficient to activate the extended settable composition to set into a hardened mass. In certain embodiments, the cement set accelerator may be added to the extended settable composition in an amount in the range of about 0.1% to about 4% bwoc.
As mentioned above, cement kiln dust and/or a natural pozzolan may be used in embodiments of the present invention to replace higher cost additives (such as Portland cement), resulting in a more economical settable composition. Accordingly, an embodiment of the present invention may include a method of maximizing performance and minimizing cost of the cement composition. An embodiment of the method may comprise: determining one or more desired cement composition parameters for one or more properties selected from the group consisting of compressive strength, pump time, fluid loss, free water content, and rheology; determining a component cost for at least one additive selected from the group consisting of cement kiln dust, a natural pozzolan, a lightweight material, and combinations thereof, designing a cement composition to have the one or more desired cement composition parameters by adjusting the amount of the cement kiln dust, the natural pozzolan, and/or the lightweight material in the cement composition.
The method may include determining one or more desired cement composition parameters for one or more properties selected from the group consisting of compressive strength, pump time, fluid loss, free water content, and rheology. For example, one or more of the properties may be determined to provide a cement composition suitable for use in subterranean cementing. In one embodiment, the one or more desired cement composition parameters may include at least one of a minimum 24-hour compressive strength, a minimum pump time, a minimum fluid loss, a minimum free water content, or a pumpable slurry. In one particular example, properties could be determined for the cement composition to meet or exceed API Specification 10's physical requirements for a particular API cement.
The method further may comprise determining a component cost for at least one additive selected from the group consisting of cement kiln dust, a natural pozzolan, and a lightweight material. Lightweight materials may be included in a cement composition, for example, to provide a lower density. Examples of lightweight materials include, but are not limited to bentonite, gilsonite, expanded perlite, and microspheres (e.g., glass spheres).
The method further may comprise designing a cement composition to have the one or more desired cement composition parameters by adjusting the amount of the cement kiln dust, the natural pozzolan, and/or the lightweight material in the cement composition. Designing the cement composition may include determining a cement composition that will have the desired parameters that were determined. In designing the cement composition, the amount of the cement kiln dust, the natural pozzolan, and/or the lightweight materials should be adjusted in accordance with embodiments of the present invention. By adjusting the amount of these materials, the price of the cement composition may be minimized while providing a cement composition suitable for use in subterranean cementing, in that it has the specified parameters. In certain embodiments, lightweight materials (e.g., certain microspheres) may be a higher cost additive than the cement kiln dust and/or the natural pozzolan. Accordingly, adjusting the relative amounts of these additives may result in a lower cost cement composition. For example, reducing the amount of the lightweight additive with respect to the natural pozzolan and the cement kiln dust may reduce the cost of the cement composition. In addition, as the cement kiln dust and the natural pozzolan may also be less expensive than other components typically used in cement compositions (such as Portland cement), increasing the amounts of these components relative to other components should reduce the cost of the cement composition. In one embodiment, the amount of both the cement kiln dust and the natural pozzolan are adjusted. In another embodiment, the amount of both the cement kiln dust and the lightweight material are adjusted. It should be understood that the amount of the lightweight additive may be reduced to 0% bwoc to provide a lower cost cement composition, in accordance with embodiments of the present invention.
The settable compositions, including the extended settable compositions, of the present invention may be used in a variety of subterranean applications, including, but not limited to, primary cementing, remedial cementing, and drilling operations.
An example of a method of the present invention comprises providing a settable composition of the present invention; placing the settable composition into a well bore. In some embodiments, the settable compositions of the present invention may be foamed. As desired by one of ordinary skill in the art, with the benefit of this disclosure, the settable compositions of the present invention useful in this method may comprise any of the above-listed additives, as well any of a variety of other additives suitable for use in subterranean applications.
Another example of a method of the present invention is a method of cementing a pipe string (e.g., casing, expandable casing, liners, etc.) disposed in a well bore. An example of such a method may comprise providing a settable composition of the present invention; introducing the settable composition into the annulus between the pipe string and a wall of the well bore; and allowing the settable composition to set in the annulus to form a hardened mass. Generally, in most instances, the hardened mass should fix the pipe string in the well bore. In some embodiments, the settable compositions of the present invention may be foamed. As desired by one of ordinary skill in the art, with the benefit of this disclosure, the settable compositions of the present invention useful in this method may comprise any of the above-listed additives, as well any of a variety of other additives suitable for use in subterranean application.
Another example of a method of the present invention is a method of sealing a portion of a gravel pack or a portion of a subterranean formation. An example of such a method may comprise providing a settable composition of the present invention; introducing the settable composition into the portion of the gravel pack or the portion of the subterranean formation; and allowing the settable composition to form a hardened mass in the portion. The portions of the subterranean formation may include permeable portions of the formation and fractures (natural or otherwise) in the formation and other portions of the formation that may allow the undesired flow of fluid into, or from, the well bore. The portions of the gravel pack include those portions of the gravel pack, wherein it is desired to prevent the undesired flow of fluids into, or from, the well bore. Among other things, this method may allow the sealing of the portion of the gravel pack to prevent the undesired flow of fluids without requiring the gravel pack's removal. In some embodiments, the settable compositions of the present invention may be foamed. As desired by one of ordinary skill in the art, with the benefit of this disclosure, the settable compositions of the present invention useful in this method may comprise any of the above-listed additives, as well any of a variety of other additives suitable for use in subterranean applications.
Another example of a method of the present invention is a method of sealing voids located in a pipe string (e.g., casing, expandable casings, liners, etc.) or in a cement sheath. Generally, the pipe string will be disposed in a well bore, and the cement sheath may be located in the annulus between the pipe string disposed in the well bore and a wall of the well bore. An example of such a method may comprise providing a settable composition; introducing the settable composition into the void; and allowing the settable composition to set to form a hardened mass in the void. In some embodiments, the settable compositions of the present invention may be foamed. As desired by one of ordinary skill in the art, with the benefit of this disclosure, the settable compositions of the present invention useful in this method may comprise any of the above-listed additives, as well any of a variety of other additives suitable for use in subterranean applications.
When sealing a void in a pipe string, the methods of the present invention, in some embodiments, further may comprise locating the void in the pipe string; and isolating the void by defining a space within the pipe string in communication with the void; wherein the settable composition may be introduced into the void from the space. The void may be isolated using any suitable technique and/or apparatus, including bridge plugs, packers, and the like. The void in the pipe string may be located using any suitable technique. When sealing a void in the cement sheath, the methods of the present invention, in some embodiments, further may comprise locating the void in the cement sheath; producing a perforation in the pipe string that intersects the void; and isolating the void by defining a space within the pipe string in communication with the void via the perforation, wherein the settable composition is introduced into the void via the perforation. The void in the pipe string may be located using any suitable technique. The perforation may be created in the pipe string using any suitable technique, for example, perforating guns. The void may be isolated using any suitable technique and/or apparatus, including bridge plugs, packers, and the like.
Another example of a method of the present invention is a method of changing the direction of drilling a well bore. An example of such a method may comprise providing a settable composition; introducing the settable composition into the well bore at a location in the well bore wherein the direction of drilling is to be changed; allowing the settable composition to set to form a kickoff plug in the well bore; drilling a hole in the kickoff plug; and drilling of the well bore through the hole in the kickoff plug. In some embodiments, the settable compositions of the present invention may be foamed. As desired by one of ordinary skill in the art, with the benefit of this disclosure, the settable compositions of the present invention useful in this method further may comprise any of the above-listed additives, as well any of a variety of other additives suitable for use in subterranean applications.
Generally, the drilling operation should continue in the direction of the hole drilled through the kickoff plug. The well bore and hole in the kickoff plug may be drilled using any suitable technique, including rotary drilling, cable tool drilling, and the like. In some embodiments, one or more oriented directional drilling tools may be placed adjacent to the kickoff plug. Suitable directional drilling tools include, but are not limited to, whip-stocks, bent sub-downhole motorized drill combinations, and the like. The direction drilling tools then may be used to drill the hole in the kickoff plug so that the hole is positioned in the desired direction. Optionally, the directional drilling tool may be removed from the well bore subsequent to drilling the hole in the kickoff plug.
To facilitate a better understanding of the present invention, 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 scope of the invention.
EXAMPLE 1
Twenty-nine different cement slurries (i.e., Slurries 1-29) were prepared. Slurries 1-14 and the resulting set cements were then tested to determine their respective 24-hour compressive strengths. As set forth below, the respective test results for Slurries 1-14 demonstrate that slurries comprising cement, cement kiln dust, and pumicite may provide suitable compressive strengths for certain applications. The remainder of the slurries were used for additional testing in Example 2 below.
Slurries 1-29 were prepared by dry blending dry components with cement prior to adding water to form the respective slurry. Slurries 1-10, 13-29 included Holcem ASTM Type III cement. Slurries 11 and 12 included TXI Lightweight cement. The pumicite included in Slurries 4, 7, and 9-29 was 200-mesh pumicite. Liquid additives, if any, were added to the water prior to combination with the cement. Sufficient water was included in Slurries 1-3 and 24-27 to provide a density of 12.5 lb/gal. Sufficient water was included in Slurries 4-23 to provide a density of 12 lb/gal. Sufficient water was included in Slurries 28 and 29 to provide a density of 11 lb/gal. The particular composition of each slurry is provided in the table below.
After Slurries 1-14 were prepared, the slurries were subjected to 24-hour compressive strength tests at 185° F. in accordance with API Recommended Practice 10B. The results of this series of tests are provided in the table below.
















TABLE 1














185° F.











24-Hour









Glass

Comp.



Water1
Cement2
CKD
Pumicite
Silica3
Lime
Beads4
Bentonite
Strength


Slurry
(gal/sk)
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(psi)
























1
11.35
75
25
—
10
—
—
—
905


2
10.35
65
35
—
—
—
—
—
471


3
10.52
75
25
—
—
—
—
—
556


4
11.92
50
25
25
—
5
—
—
549


5
12.41
75
25
—
—
—
—
—
447


6
12.23
65
35
—
—
—
—
—
319


7
12.62
75
12.5
  12.5
—
5
—
—
441


8
13.42
75
25
—
10
—
—
—
261


9
12.92
50
25
25
10
5
—
—
920


10
12.37
75
—
25
—
5
—
—
1012


11
12.19
50
25
25
10
5
—
—
939


12
12.19
50
25
 255
10
5
—
—
786


13
12.92
50
25
 255
10
5
—
—
805


14
12.47
50
25
25
10
—
—
—
734


15
11.89
65
17
17
—
—
—
—
—


16
11.89
65
17
17
—
—
—
—
—


17
12.65
65
12
23
8
—
—
—
—


18
12.94
65
29
 6
8
—
—
—
—


19
12.76
65
6
29
10
—
—
—
—


20
13.1
75
10
25
—
—
—
—
—


21
13.38
75
13
25
—
—
—
—
—


22
10.91
57
5
38
—
—
—
—
—


23
13.28
58
7
35
—
—
—
—
—


24
12.98
50
5
42
—
—
—
3
—


25
10.91
50
5
42
—
—
—
3
—


26
10.91
50
5
42
—
—
—
3
—


27
10.91
50
5
42
—
—
—
3
—


28
10.85
50
5
35
—
—
10
—
—


29
10.85
50
5
35
—
—
10
—
—





1The amount of water is provided in gallons per 100-pound sack of dry blend.


2Holcem ASTM Type III Cement was used in each slurry, except TXI Lightweight cement was used in Slurries 11 and 12.


3The amorphous silica included in the slurries was Silicalite TM cement additive, available from Halliburton Energy Services.


4The glass beads included in certain slurries were HGS 6000 hollow glass beads, available from 3M located in Minnesota.


5Slurries 12 and 13 contained a composite of 5-, 10-, 200-, and 325-mesh pumicite in equal amounts.






EXAMPLE 2
Additional tests were performed using Slurries 1, 9, and 15-97 from Example 1. In addition to the components identified in Example 1, D-AirTM 3000 defoaming additive and FWCATM free water control additive were also added to each of these slurries in the amount indicated in the table below. Additionally, each of these slurries also included HR®-601 retarder in the amount indicated in the table below, except for Slurry 913 in which HR®-5 retarder was included. Slurries 16-19, 21-26, 28, and 29 further included Halad® 344 fluid loss control additive in the amount indicated in the table below.
After preparation, the slurries and resulting set cements were then tested to determine their respective fluid loss properties, thickening times, and free water content, in accordance with API Recommended Practice 10B. In addition, an ultrasonic cement analyzer (“UCA”) was used to determine a UCA72 hrs value and a UCAcrush value. [The UCA tests were performed in accordance with API Recommended Practice 10B.
The results of this series of tests are provided in the table below.
















TABLE 2










Fluid
Thick.
Free









Loss
Time
Water
UCA
UCA




Set


155° F.
70 bc
45 inc.
72 hr
Crush



Defoamer
Retarder
FWCA
FLCA
(cc/30
155° F.
155° F.
190° F.
72 hr


Slurry
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
min)
(hr:min)
(%)
(psi)
(psi)
























 1a
0.25
1
0.3
—
280
5:50
0
679
691


 1b
0.25
0.5
0.3
—
240
3:35
0
544
680


 1c
0.25
0.75
0.3
—
290
3:54
—
—
—


 9a
0.5
1
0.3
—
294
6:40
Trace
1118.8
1127


 9b
0.5
1
0.3
—
235
—
1.6
—
—


 9c
0.5
0.5
0.3
—
321
3:03
Trace
1066
1092


 9d
0.5
0.75
0.3
—
290
4:09
0
—
—


15
0.25
0.75
0.3
—
407
—
—
—
—


16
0.25
0.75
0.2
0.2
254
—
—
—
—


17
0.25
0.75
0.25
0.15
259
—
—
—
739


18
0.25
0.75
0.25
0.15
—
—
—
392
472


19
0.25
0.75
0.3
0.1
366
—
—
—
—


20
0.25
0.75
0.3
—
438
—
—
—
—


21
0.25
0.75
0.3
0.1
460
—
—
—
—


22
0.25
0.5
0.3
0.15
394
—
2 ml
—
—


23
0.25
0.3
0.3
0.3
143
—
Trace
—
—


24
0.25
0.3
0.3
0.2
280
3:27
0
—
1024


25
0.25
0.4
0.3
0.2
132
3:40
0
—
—


26
0.25
0.5
0.3
0.1
208
3:34
0
2610
2110


27
0.25
0.5
0.3
—
281
3:55
0
—
—


28
—
0.3
0.3
0.2
256
5:16
0
1193
 —1


29
0.25
0.4
0.3
0.2
235
5:52
0
1400
 —1





1The 72-hour UCA crush strengths were not determined for Slurries 28 and 29 because the slurry cracked.






The 24-hour UCA compressive and crush strengths were also determined for Slurries 28 and 29. For Slurry 28, the 24-hour UCA compressive and crush strengths were 1107 psi and 1021 psi, respectively. For Slurry 29, the 24-hour UCA compressive and crush strengths were 1500 psi and 1024 psi, respectively.
Additionally, the rheological properties of the slurries were also determined using a Fann Model 35 viscometer at the temperature indicated in the table below using a bob and sleeve and spring #1. The plastic viscosity and the yield points of the slurries were calculated from Best Rheology using the Generalized Hershel Bulkley Model. The results of this series of tests are provided in the table below.









TABLE 3









Rotational Viscometer



(Bob & Sleeve; Spring #1)



















Temp.








Plastic
Yield


Slurry
(° F.)
600
300
200
100
60
30
6
3
Viscosity
Point





















 1a
80
116
73
56
37
27
18
9
8
54
19



155
162
130
95
64
52
41
30
28
99
31


 1b
80
147
95
72
46
35
25
16
15
74
21



155
151
125
90
59
46
36
25
24
99
26


 1c
80
131
72
48
37
27
20
19
18
53
20



155
142
123
90
64
53
44
32
30
88
37


 9a
80
126
78
60
38
27
18
9
8
60
18



155
129
95
69
44
34
26
18
17
77
18


 9b
80
120
76
56
34
24
15
6
4
63
13



155
68
45
29
16
11
6
2
2
44
1


 9c
80
115
70
53
33
24
16
8
8
56
14



155
100
74
53
34
27
21
14
13
60
14


 9d
80
129
84
62
39
29
20
10
8
68
16



155
122
94
70
46
36
28
20
19
72
22


15
80
86
51
40
25
18
12
5
4
39
13



155
105
80
59
40
32
25
18
17
60
21


16
80
68
38
28
16
11
6
2
1
22
5



155
61
45
28
15
10
6
2
1
45
0


17
80
92
55
40
24
16
9
3
3
47
8



155
89
57
40
23
15
9
4
3
51
6


18
80
96
55
41
25
17
11
3
2
45
10



155
79
53
37
21
15
10
4
4
48
5


19
80
110
58
46
29
20
12
5
5
44
14



155
107
79
54
33
24
17
11
10
69
10


20
80
85
61
48
35
28
15
9
7
39
22



155
101
72
52
33
26
19
13
12
59
13


21
80
83
51
38
24
17
10
4
3
41
10



155
86
61
41
25
18
13
8
8
54
7


22
80
115
72
56
36
25
16
5
4
54
18



155
95
70
47
27
19
12
4
3
64
6


23
80
114
73
57
36
25
15
7
6
55
8



155
75
52
35
20
13
8
3
2
48
4


24
80
129
86
65
40
28
18
5
4
69
17



155
90
57
46
29
21
13
5
4
42
15


25
80
207
131
103
67
49
31
11
8
96
35



155
155
115
81
49
34
21
7
5
99
16


26
80
202
120
94
61
44
29
13
11
89
31



155
159
121
85
50
35
23
10
8
107
14


27
80
184
126
96
62
46
32
18
17
96
30



155
165
146
103
91
71
55
40
37
83
63


28
80
265
178
141
93
69
45
17
15
128
50



155
194
158
114
69
48
30
10
7
134
24


29
80
281
198
163
100
75
49
18
15
147
51



155
216
175
124
77
56
41
14
9
147
28









Example 2 thus indicates that slurries containing pumicite may provide suitable properties for certain applications.
EXAMPLE 3
Additional tests were performed using Slurries 9-11 from Example 1. In particular, each of Slurries 9-11 were extended using a set retarder (HR®-5 retarder). After remaining in a liquid state for 24 hours, each slurry was activated using calcium chloride in an amount of 4% bwoc. The 72-hour compressive strength of the resultant set cement was then determined at the temperature indicated in the table below, in accordance with API Recommended Practice 10B. The results of this series of tests are provided in the table below.














TABLE 4












185° F.









72-Hour






Set

Calcium
Comp.



Cement1
CKD
Pumicite
Retarder
Hours
Chloride
Strength


Slurry
(% bwoc))
(% bwoc)
(% bwoc)
(% bwoc)
Liquid
(% bwoc)
(psi)






















9
50
25
25
1.5
24
4
1074


10
75
—
25
1
24
4
959


11
50
25
25
1
24
4
626





1Holcem ASTM Type III Cement was used in Slurries 9 and 10, and TXI Lightweight cement was used in Slurry 11.






Example 3 thus indicates that slurries containing cement, CKD, and pumicite may be extended, for example, by use of appropriate set retarders.
EXAMPLE 4
Additional tests were performed using Slurries 9-11 from Example 1. In particular, each of Slurries 9-11 were foamed with air from a base density of 12 ppg to the density indicated in the table below. The foaming additive included in each slurry was Zoneseal® 2000 foaming additive in an amount of 2% by volume of water. The 72-hour compressive strength of the resultant set cement was then determined at the temperature indicated in the table below, in accordance with API Recommended Practice 10B. The results of this series of tests are provided in the table below.

















TABLE 5















185° F.












72-Hour








Foaming
Base
Foam
Target
Comp.



Cement1
CKD
Pumicite
Silica2
Lime
Additive
Density
Density
Density
Strength


Slurry
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(% bvow)
(ppg)
(ppg)
(ppg)
(psi)

























9
50
25
25
10
5
2
12
9.52
10
411


10
75
—
25
—
5
2
12
9.36
10
343


11
50
25
25
10
5
2
12
9.76
10
561





1Holcem ASTM Type III Cement was used in Slurries 9 and 10, and TXI Lightweight cement was used in Slurry 11.


2The amorphous silica included in the slurries was Silicalite TM cement additive, available from Halliburton Energy Services.






Examples 4 thus indicates that slurries containing cement, CKD, and pumicite may be foamed, for example, by use of appropriate foaming additives.
EXAMPLE 5
Five additional slurries (i.e., Slurries 30-34) were prepared. The slurries and resulting set cements were then tested to determine their respective mechanical properties, fluid-loss properties, rheological properties, and the like. As set forth below, the respective test results for the five different slurries demonstrate that slurries comprising pumicite may provide suitable compressive strengths for certain applications.
Slurries 30-34 were prepared by dry blending dry components with cement prior to adding water to form the respective slurry. Liquid additives, if any, were added to the water prior to combination with the cement. Sufficient water was included in Slurries 30-32 to provide a density of 10.5 ppg, and sufficient water was included in Slurries 33 and 34 to provide a density of 12 ppg. In addition to other components, each slurry included Holcem ASTM Type III cement, 200-mesh Pumicite, and Joppa cement kiln dust. The composition of each slurry is listed in the table below.















TABLE 6












Silica
Glass



Density
Water
Cement
Pumicite
CKD
Bentonite
Flour2
Beads3


Slurry
(ppg)
(gal/sk)1
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)
(% bwoc)























30
10.5
10.05
50
32
5
—
—
13


31
10.5
10.07
50
32
5
—
—
13


32
10.5
10.06
50
32
5
—
—
13


33
12
15
50
42
5
3
17
—


34
12
12.98
50
42
5
3
—
—





1The amount of water is provided in gallons per 100-pound sack of dry blend.


2The silica flour included in Slurry 33 was SSA-1 TM strength stabilizing additive, available from Halliburton Energy Services.


3The glass beads included in certain slurries were 8000# psi beads with a specific gravity of 42, available from 3M located in Minnesota.






Slurry 30 further included D-AirTM 3000 defoaming additive (0.25% bwoc), FWCATM free water control additive (0.15% bwoc), HR®-601 retarder (0.6% bwoc), and Halad®-344 fluid loss control additive (0.6% bwoc).
Slurry 31 further included D-AirTM 3000 defoaming additive (0.25% bwoc), FWCATM free water control additive (0.15% bwoc), HR®-601 retarder (0.3% bwoc), and Halad®-344 fluid loss control additive (0.4% bwoc).
Slurry 32 further included D-AirTM 3000 defoaming additive (0.25% bwoc), FWCATM free water control additive (0.15% bwoc), HR®-601 retarder (0.4% bwoc), and Halad®-344 fluid loss control additive (0.4% bwoc).
Slurry 33 further included D-AirTM 3000 defoaming additive (0.25% bwoc), FWCATM free water control additive (0.25% bwoc), HR®-601 retarder (0.3% bwoc), and Halad®-344 fluid loss control additive (0.5% bwoc), and SA-541TM suspending aid (0.3% bwoc).
Slurry 34 further included D-AirTM 3000 defoaming additive (0.25% bwoc), FWCATM free water control additive (0.3% bwoc), HR®-601 retarder (0.3% bwoc), and Halad® 344 fluid loss control additive (0.2% bwoc).
After the slurries were prepared, the slurries and resulting set cements were then tested to determine their respective fluid loss properties, thickening times, and free water content at the temperatures indicated in the table below in accordance with API Recommended Practice 10B. In addition, the UCA was used to determine the time to 50 psi, time to 500 psi, a UCA72 hrs value, and a UCAcrush value. The UCA tests were performed in accordance with API Recommended Practice 10B. Additionally, the rheological properties of the slurries were also determined using a Fann Model 35 viscometer at the temperature indicated in the table below using a bob and sleeve and spring #1. The plastic viscosity and the yield points of the slurries were calculated from Best Rheology using the Generalized Hershel Bulkley Model. The results of this series of tests are provided in the table below.

















TABLE 7






Fluid












Loss
Thick.
Free
UCA
UCA
190° F.
190° F.



200° F.
Time1
Water2
24 hr
Crush
Time
Time



(cc/30
70 bc
45 inc.
190° F.
24 hr
to
to
80°
155°
200°


Slurry
min)
(hr:min)
(%)
(psi)
(psi)
50 psi
500 psi
PV/YP
PV/YP
PV/YP

























30
58
11:45 
0
873
2140
6:58
7:35
150/35
—
102/29 


31
88
3:26
0
1027
2040
5:14
5:28
131/29
—
85/27


32
—
5:49
—
—
—
—
—
—
—
—


33
80
6:03
Trace
836
1024
4:51
5:52
 65/13
—
60/15


34
280
3:27
0
1374
1367
4:52
8:37
 69/17
42/15
—





1The thickening time tests were performed at 217° F., except the thickening time for Slurry 34 was determined at 155° F.


2The free-water tests were performed at 200° F. for Slurries 30-33. The free-water test for Slurry 34 was determined at 155° F.






Example 5 thus indicates that slurries containing pumicite may provide suitable properties for certain applications.
Therefore, the present invention is 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, 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. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. While 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 All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is 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. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee.

## Claims

1. A method of cementing in a subterranean formation comprising:
introducing a cement composition into the subterranean formation, wherein the cement composition comprises:
Portland cement interground with burned shale,
cement kiln dust,
a natural pozzolan, and
water; and

allowing the cement composition to set.

2. The method of claim 1 wherein the introducing the cement composition into the subterranean formation comprises introducing the cement composition into a space between a pipe string and the subterranean formation.

3. The method of claim 2 comprising introducing the pipe string into a well bore penetrating the subterranean formation.

4. The method of claim 1 wherein the cement composition is foamed and further comprises a gas and a surfactant.

5. The method of claim 1 wherein the cement composition comprises at least one cement selected from the group consisting of a pozzolana cement, a gypsum cement, a high alumina content cement, a slag cement, a silica cement, and a combination thereof.

6. The method of claim 1 wherein the natural pozzolan comprises pumicite.

7. The method of claim 1 wherein the natural pozzolan is present in an amount of about 0.1% to about 50% by weight of cementitious components.

8. The method of claim 1 wherein the cement composition comprises at least one additive selected from the group consisting of a strength-retrogression additive, a set accelerator, a set retarder, a weighting agent, a lightweight additive, a weighting additive, a gas-generating additive, a mechanical property enhancing additive, a lost-circulation material, a filtration-control additive, a dispersant, a defoaming agent, a foaming agent, a thixotropic additive, and a combination thereof.

9. The method of claim 1 wherein the cement composition comprises at least one additive selected from the group consisting of fly ash, slag, metakaolin, shale, zeolite, lime, crystalline silica, amorphous silica, fumed silica, a salt, fiber, hydratable clay, a microsphere, rice husk ash, an elastomer, a resin, latex, and combinations thereof.

10. The method of claim 1 comprising:
determining one or more desired cement composition parameters for at least one property selected from the group consisting of compressive strength, pump time, fluid loss, free water content, rheology, and a combination thereof
determining a component cost for at least one additive selected from the group consisting of the cement kiln dust, the natural pozzolan, a lightweight material, and a combination thereof; and
designing the cement composition to have the one or more desired cement composition parameters by adjusting the amount of the cement kiln dust, the natural pozzolan, and/or the lightweight material in the cement composition.

11. The method of claim 10 wherein adjusting the amount comprises adjusting the amount of the cement kiln dust and the lightweight material in the cement composition.

12. The method of claim 10 wherein adjusting the amount comprises adjusting the amount of the cement kiln dust and the natural pozzolan in the cement composition.

13. The method of claim 1 wherein the cement composition is extended and further comprises a set retarding additive.

14. A method of cementing in a subterranean formation comprising:
introducing a cement composition into the subterranean formation, wherein the cement composition comprises:
Portland cement interground with burned shale,
cement kiln dust,
a natural pozzolan comprising at least one pozzolan selected from the group consisting of pumicite, diatomaceous earth, volcanic ash, opaline shale, tuff, and a combination thereof, and
water; and

allowing the cement composition to set.

15. The method of claim 14 wherein the introducing the cement composition into the subterranean formation comprises introducing the cement composition into a space between a pipe string and the subterranean formation.

16. The method of claim 15 further comprising introducing the pipe string into a well bore penetrating the subterranean formation.

17. The method of claim 14 wherein the cement composition is foamed and further comprises a gas and a surfactant.

18. The method of claim 14 wherein the cement composition further comprises at least one cement selected from the group consisting of, a pozzolana cement, a gypsum cement, a high alumina content cement, a slag cement, a silica cement, and a combination thereof.

19. The method of claim 14 wherein the natural pozzolan is present in an amount of about 0.1% to about 50% by weight of cementitious components.

20. The method of claim 14 wherein the cement composition further comprises at least one additive selected from the group consisting of a strength-retrogression additive, a set accelerator, a set retarder, a weighting agent, a lightweight additive, a weighting additive, a gas-generating additive, a mechanical property enhancing additive, a lost-circulation material, a filtration-control additive, a dispersant, a defoaming agent, a foaming agent, a thixotropic additive, and a combination thereof.

21. The method of claim 14 wherein the cement composition further comprises at least one additive selected from the group consisting of fly ash, slag, metakaolin, shale, zeolite, lime, crystalline silica, amorphous silica, fumed silica, a salt, fiber, hydratable clay, a microsphere, rice husk ash, an elastomer, a resin, latex, and a combination thereof.

22. The method of claim 14 further comprising:
determining one or more desired cement composition parameters for at least one property selected from the group consisting of compressive strength, pump time, fluid loss, free water content, rheology, and a combination thereof
determining a component cost for at least one additive selected from the group consisting of the cement kiln dust, the pumicite, a lightweight material, and a combination thereof; and
designing the cement composition to have the one or more desired cement composition parameters by adjusting the amount of the cement kiln dust, the natural pozzolan, and/or the lightweight material in the cement composition.

23. The method of claim 22 wherein adjusting the amount comprises adjusting the amount of the cement kiln dust and the lightweight material in the cement composition.

24. The method of claim 22 wherein adjusting the amount comprises adjusting the amount of the cement kiln dust and the natural pozzolan in the cement composition.

25. The method of claim 14 wherein the cement composition is extended and further comprises a set retarding additive.

26. A method of cementing in a subterranean formation comprising:
providing a cement composition that comprises:
Portland cement interground with burned shale,
cement kiln dust,
pumicite,
lime, and
water;

introducing the cement composition into the subterranean formation; and
allowing the cement composition to set.