# Patent

## Title
Low density cementitious compositions using limestone

## Abstract

A manufactured cementitious binder includes a hydraulic binder in an amount in the range of from 40 to 75% by weight of the cementitious binder; metakaolin in an amount in the range of from 1 to 30% by weight of the cementitious binder; silica fume in an amount up to 15% by weight of the cementitious binder; limestone in an amount of from 5 to 30% by weight of the cementitious binder, and a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious binder, the cementitious binder providing a cementitious settable composition when added with water, wherein for a density lower than 13 pounds per gallon and of at least 11 pounds per gallon obtained without a lightweight additive, said cementitious settable composition exhibits a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application claims priority and benefit under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 61/364,736, entitled “Low Density Cementitious Compositions Using Limestone,” filed on Jul. 15, 2010. The content of that application is incorporated herein in its entirety by reference.


FIELD
The present invention relates to cement, concrete and mortar compositions and, more particularly, to low density cementitious compositions.
BACKGROUND
Cementitious settable compositions are used in the treatment and drilling of well bores extending from the surface of the earth to subterranean formations. Generally, the drilling of a well for the recovery of oil, gas or water from a subterranean formation involves placing and securing a casing in the well bore by cementing. In this operation, cement is pumped downward from the surface of the earth to the bottom of the well. After the cement (i.e. the cementitious settable composition) has been pumped between the casing and the well, pumping is discontinued and the cement is permitted to set in place.
In cementing procedures in a well bore, it is sometimes desirable that the cement slurry has a low density. Aside from being costly due to a high ratio of cement to water, high density cement slurries require higher pumping pressures in order to place them at the desired positions in the well bore. Further, high density cement slurries impose high static and dynamic pressures upon not only the formation to be treated but upon the other formations as well. At the locations where these other formations are porous, the high pressures exerted in the well bore can result in loss of the cement slurry into the formations or loss of the water from the cement slurry into the formations. As a result, the cement can set in an unintended position in the well bore. Thus, when designing cementitious settable compositions for subterranean applications, design engineers should ensure that the compositions provide adequate compressive strength and zonal isolation. Aside from providing strength and zonal isolation one should ensure that the selected compositions meet all regulatory guidelines for zonal isolation for the respective area. Another area of concern is to ensure that the cementitious composition selected to provide zonal isolation has the capability to be seen by down-hole interpretation methods (bond logs). Yet another area of concern from a manufacturing standpoint is to ensure that the cementitious composition remains uniform and that materials that are used as fillers do not impact the intended development of mechanical strengths and the rheological properties of the cementitious composition.
In order to obtain cement slurries having adequate mechanical and rheological properties and a density equal to or less than about 13 pounds per gallon, it is known in the art to use lightweight additives such as, for example, microspheres (e.g. glass beads) and foaming agents, as a partial substitute for water. However, the use of lightweight additives significantly adds undesirable costs as well as industrial challenges to the preparation of slurries. Lightweight additives are generally the most expensive materials in low density cementitious compositions. Further, the use of foaming agents or other similar chemicals for reducing the density of cement slurries may create hazards and pose environmental concerns.
SUMMARY
Therefore, it is desirable to provide lightweight cementitious settable compositions or cement slurries that exhibit enhanced compressive performances while having the highest possible water content. The high water content enables one to produce the lowest slurry weight, which then requires the lowest amount of lightweight additives to achieve the desired density. A lightweight additive is defined hereinafter as any material other than water that is used to provide a cement slurry that has a low density and desired mechanical and rheological properties. Examples of lightweight additives include microspheres, foaming agents and the like. It will be appreciated that any microspheres, foaming agents and the like added to the composition or cement slurry in an amount not sufficient to provide a low density and desired mechanical and rheological properties would not be considered a lightweight additive.
Furthermore, it is desirable to provide lightweight cementitious settable compositions or cement slurries in which materials that are used as fillers do not compromise the development of mechanical strengths and the rheological properties of the compositions. It is believed that the impact of filler materials may become more important in lightweight cementitious settable compositions due to the high water content.
In particular, it is desirable to provide lightweight cementitious settable compositions that exhibit enhanced compressive performances at densities lower than 13 pounds per gallon (ppg) without using, or including a minimum amount of, lightweight additives such as microspheres, foaming agents or the like. Furthermore, it is desirable to provide cementitious settable compositions that exhibit enhanced compressive performances at densities equal to or lower than about 12 ppg without using, or including a minimum amount of, lightweight additives such as microspheres, foaming agents or the like. It is also desirable to provide cementitious settable compositions that exhibit enhanced compressive performances at densities lower than about 11 ppg including a reduced amount of lightweight additives such as microspheres, foaming agents or the like. In addition, it is desirable to provide cementitious settable compositions that exhibit enhanced compressive performances at densities equal to or lower than about 10 ppg, preferably equal to or lower than about 9 ppg, more preferably equal to or lower than about 8 ppg, including a minimum amount of lightweight additives such as microspheres, foaming agents or the like.
In one aspect of the invention, there is provided a manufactured cementitious binder that includes a hydraulic binder and One or more materials having pozzolanic or non-pozzolanic properties and that exhibits a minimum of 500 psi compressive strength at 24 hours (24 h) when cured at 100 F. The manufactured cementitious binder produces a low density cementitious settable composition or slurry that has excellent oil well-slurry properties such as very low fluid loss, very low segregation, good thickening time, good admixture response, good tensile strength and exceeds the safety standards set forth by the industry governing bodies without using, or using little amounts of, lightweight additives.
In one aspect of the invention, the cementitious binder produces a cementitious settable composition having a density of about 12 pounds per gallon with a 24 h compressive strength, when cured at 100 F, in the range of about 900 to 1000 psi without using lightweight additives such as microspheres, foaming agents or the like and that maintains the above slurry properties.
In one aspect of the invention, there is provided a manufactured cementitious binder including a hydraulic binder in an amount in the range of from about 40 to 75% by weight of the cementitious binder; metakaolin in an amount in the range of from about 1 to 30% by weight of the cementitious binder; silica fume in an amount up to about 15% by weight of the cementitious binder; limestone in an amount of from about 5 to 30% by weight of the cementitious binder, and a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious binder, wherein the cementitious binder provides a cementitious settable composition, when added with water and without a lightweight additive, that has a density lower than 13 pounds per gallon and greater than about 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.
In one aspect of the invention, there is provided a cementitious settable composition including: water; and a cementitious binder including a hydraulic binder in an amount in the range of from about 40 to 75% by weight of the cementitious binder; metakaolin in an amount in the range of from about 1 to 30% by weight of the cementitious binder; silica fume in an amount up to about 15% by weight of the cementitious binder; limestone in an amount of from about 5 to 30% by weight of the cementitious binder, and a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious binder, wherein, without a lightweight additive, the cementitious settable composition has a density lower than 13 pounds per gallon and greater than about 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.
In another aspect of the invention, there is provided a method of cementing including providing a cementitious settable composition including water; and a cementitious binder including a hydraulic binder in an amount in the range of from about 40 to 75% by weight of the cementitious binder; metakaolin in an amount in the range of from about 1 to 30% by weight of the cementitious binder; silica fume in an amount up to about 15% by weight of the cementitious binder; limestone in an amount of from about 5 to 30% by weight of the cementitious binder, and a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious binder, wherein, without a lightweight additive, the cementitious settable composition has a, density lower than 13 pounds per gallon and greater than about 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi; and introducing the cementitious settable composition into an underground formation.


DETAILED DESCRIPTION
Various aspects of the present invention relate to a manufactured cementitious binder, a method of manufacturing the cementitious binder, a cementitious settable composition (slurry) and a method of cementing. In accordance with one embodiment of the invention, the cementitious binder and/or cementitious settable composition may be used in a variety of applications including, for example, subterranean applications, surface applications and construction applications. Subterranean applications may include, for example, primary cementing, remedial cementing, and drilling operations. In primary cementing, for example, pipe strings such as casings and liners are cemented in well bores. Well bores may include oil well bores, gas well bores, water well bores, geothermal well bores, and the like. In performing primary cementing, cement compositions are pumped into the space between the walls of a well bore and the exterior surface of the pipe string disposed therein. The cement composition is permitted to set in the space, thereby forming an annular sheath of hardened, substantially impermeable cement therein that substantially 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. Cement compositions are also used in plugging and abandonment operations as well as in remedial cementing operations such as plugging permeable zones or fractures in well bores, plugging cracks and holes in pipe strings, and the like.
In one aspect of the invention, the manufactured cementitious binder is configured to provide a lightweight cementitious settable composition that possesses rapid high compressive strength without using, or including a reduced amount of, lightweight additives such as microspheres, foaming agents or the like. These cementitious characteristics are particularly desirable in cementing operations for subterranean applications. Indeed, when a cementitious settable composition is injected into the well bore and placed in the zone that is to be cemented, it is desirable that the composition presents relatively low viscosity and has effectively constant rheological properties. Once it is in place, an ideal cementitious composition should rapidly develop high compressive strength and maintain good zonal integrity.
Furthermore, as will be appreciated by one skilled in the art, there are numerous benefits provided by such a cementitious binder. For example, in addition to the significant cost reduction in manufacturing the binder and preparing the cementitious settable compositions, there will be no or little environmental concern or hazards associated with the preparation of the cementitious settable composition as it can be prepared by simply mixing the cementitious binder with water without using, or using a little amount of, lightweight additives.
In one embodiment of the invention, the cementitious binder provides a cementitious settable composition, when added with water, that has a density lower than 13 pounds per gallon (ppg) and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi, preferably at least 700 psi in one embodiment, more preferably at least 800 psi in another embodiment, and more preferably at least 900 psi in yet another embodiment without using lightweight additives such as microspheres, foaming agents or the like. In yet another embodiment of the invention, the cementitious binder provides a cementitious settable composition that has a density lower than about 12 pounds per gallon, that has a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi, preferably at least 700 psi in one embodiment, more preferably at least 800 psi in one embodiment, and more preferably at least 900 psi in another embodiment without using lightweight additives such as microspheres, foaming agents or the like. In yet another embodiment of the invention, the cementitious binder provides a cementitious settable composition that has a density lower than about 11 pounds per gallon, that has a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi, preferably at least 700 psi in one embodiment, more preferably at least 800 psi in one embodiment, and even more preferably at least 900 psi in another embodiment, including a reduced amount of, lightweight additives such as microspheres, foaming agents or the like. In yet another embodiment of the invention, the cementitious binder provides a cementitious settable composition that has a density lower than about 10 pounds per gallon has a 24 hour compressive strength at 100 F, as hardened, of at least 350 psi in one embodiment, preferably at least 500 psi in one embodiment, more preferably at least 700 psi in one embodiment, more preferably at least 800 psi in one embodiment, and even more preferably at least 900 psi in another embodiment, including a reduced amount of lightweight additives such as microspheres, foaming agents or the like. In yet another embodiment of the invention, the cementitious binder provides a cementitious settable composition that has a density lower than about 9 pounds per gallon, that has a 24 hour compressive strength at 100 F, as hardened, of at least 350 psi in one embodiment, preferably at least 500 psi in one embodiment, more preferably at least 700 psi in one embodiment, more preferably at least 800 psi in one embodiment, and even more preferably at least 900 psi in another embodiment, including a reduced amount of, lightweight additives such as microspheres, foaming agents or the like. In yet another embodiment of the invention, the cementitious binder provides a cementitious settable composition that has a density lower than about 8 pounds per gallon, has a 24 hour compressive strength at 100 F, as hardened, of at least 350 psi in one embodiment, preferably at least 500 psi in one embodiment, more preferably at least 700 psi in one embodiment, more preferably at least 800 psi in one embodiment, and even more preferably at least 900 psi in another embodiment, including a reduced amount of lightweight additives such as microspheres, foaming agents or the like.
The inventors have devised that such lightweight cementitious settable compositions, which rapidly possess high compressive strength, for example, a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi in one embodiment, preferably at least 700 psi in one embodiment, more preferably at least 800 psi in one embodiment, and more preferably at least 900 psi in another embodiment, without using, or including a reduced amount of, lightweight additives such as microspheres, foaming agents or the like, can be surprisingly obtained with a cementitious binder including a hydraulic cement, metakaolin, optionally silica fume, limestone, and a cementitious accelerator.
In particular, in an embodiment, the cementitious binder includes a hydraulic binder in an amount in the range of from about 40 to 75% by weight of the cementitious binder; metakaolin in an amount in the range of from about 1 to 30% by weight of the cementitious binder; silica fume in an amount up to about 15% by weight of the cementitious binder; limestone in an amount of from about 5 to 30% by weight of the cementitious binder, and a cementitious accelerator in a controlled amount of at least about 0.1% by weight of the cementitious binder. In this embodiment, the cementitious binder provides a cementitious settable composition, when added with water and without a lightweight additive, that has a density lower than 13 pounds per gallon and of at least 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.
In the following embodiments discussed hereinafter, compressive strength measurements (at 24 hours, 100 F and 72 hours, 140 F) are performed in accordance with the standard defined by API Specification 10A, Sec 7, 9.
It has been found that cementitious binder compositions including limestone in an amount of at least 5% by weight of the cementitious binder, significantly enhance the performances of low density settable cementitious compositions. The inventors have devised that by incorporating limestone in a predefined amount in the cementitious binder, it is possible to significantly enhance the performances of low density settable cementitious compositions without using, or using reduced amounts, of lightweight additives. In addition, the inventors have devised that the use of limestone in combination with additional materials including metakaolin, a hydraulic binder, optionally silica fume and a cementitious accelerator in predefined amounts by weight of the cementitious binder also significantly enhances the performances of low density settable cementitious compositions. The performances of low density settable cementitious compositions, as defined herein, include, for example, rapid high compressive strength at 24 h (i.e. at least 500 psi at 100 F for a cementitious settable composition having a density lower than 13 ppg) without using, or including a minimum amount of, lightweight additives such as microspheres, foaming agents or the like. In an embodiment, limestone is present in about 10 to 30% by weight of the cementitious binder. In yet another embodiment of the invention, limestone is present in an amount greater than 15% and lower than about 25% by weight of the cementitious binder.
One skilled in the art will appreciate that the acceleration of strength development and reduced shrinkage of the settable cementitious composition is particularly beneficial for low density settable cementitious compositions that are used in subterranean applications. For example, it is desirable that low density settable cementitious compositions used in well bore applications develop early compressive strength to obtain good well bore isolation and/or maintain mechanical integrity of the well bore. In addition, the normal shrinkage of cement can pose problems during cementing in oil and gas wells. Shrinkage can play a major role in the long-term cemented annular isolation. The long term seal of the annulus is jeopardized if the set cement pulls away from the pipe, casing, or from the well bore. It is thus desirable to carefully control shrinkage.
Limestone is a sedimentary rock that is mainly constituted of calcium carbonate (CaCO3). In accordance with various embodiments of the invention, limestone is used as a filler to prepare low density cementitious compositions. However, because limestone has a better chemical consistency/uniformity than present fillers that are conventionally used to prepare cementitious compositions, such as, for example, cement kiln dust (CKD), diatomaceous earth, ground expanded shale, ground pumice and fly ash, it has been found, unexpectedly, that limestone can be used to prepare low density cementitious compositions, for example having a density lower than 13 ppg, and from about 12 ppg to 8 ppg, that exhibit significantly enhanced mechanical and rheological properties.
For example, in comparison with cement kiln dust (CKD), fly ash or other by products, as well as other natural products, including diatomaceous earth, ground expanded shale, and ground pumice, limestone is a more inert material and includes, in a far less amount, mineral phases or chemicals that may interact with other materials/phases of the cementitious composition (e.g. Portland cement) and/or with admixtures(s) (e.g. accelerator(s)) that may be added during preparation of the slurry. For example, unlike limestone, cement kiln dust may include non-negligible amounts of chlorides and/or alkalies and mineral phases that may interact with various phases of Portland cement and admixtures, impacting setting characteristics, rheology and strength development. The content of these phases in the cement kiln dust are known to vary significantly during production of clinker because they are strongly influenced by the raw ingredients fed to the kiln assembly, the type of fuels and raw materials that are used in the burner assembly of the cement kiln and the operation of the dust filter that collects the cement kiln dust. The lack of consistency and/or uniformity of cement kiln dust, fly ash or other by products, as well as other natural products, including diatomaceous earth, ground expanded shale, and ground pumice compared to limestone can impact the consistency of performance of the cementitious binder (setting characteristics, rheology, strength development), properties that are of significant importance especially in high end applications like well cementing as will be appreciated by one skilled in the art.
Furthermore, unlike cement kiln dust, fly ash or other by-products, as well as other natural products, including diatomaceous earth, ground expanded shale, and ground pumice, it is also possible to better control the granulometry and, therefore, the uniformity of limestone particles during grinding. It is noted that, unlike sand (quartz), which is also a very inert material, limestone can be much more easily grinded to achieve a desired granulometry. This results in significant enhancements in rheological and mechanical properties of cementitious compositions including limestone compared to those obtained with, for example, cement kiln dust. Cement kiln dust is a by-product material that has generally very fine particle sizes. The granulometry of cement kiln dust cannot easily be changed after it is collected. In one embodiment, the limestone particles used for the preparation of the low density cementitious compositions have a size in a range from about 1 μm to about 10 μm, and in one embodiment from about 2 μm to about 8 μm, in another embodiment from about 3 μm to about 6 μm.
In one embodiment, it is desirable that the content of calcium carbonate CaCO3 in the limestone be at least 60% by weight of limestone. In another embodiment, the content of calcium carbonate within the limestone is at least 70% by weight of limestone. In another embodiment, the content of calcium carbonate within the source of calcium carbonate is at least 90% by weight of limestone. The use of a high calcium carbonate in limestone, e.g. greater than at least 60%, is desirable to preserve the desired mechanical and rheological properties of the cementitious compositions and to limit the presence of other mineral phases or chemicals that may interact with other materials/phases of the cementitious composition (e.g. Portland cement) and/or with admixtures(s) (e.g. accelerator(s)) that may be added during preparation of the slurry.
While the use of limestone is desirable to prepare low density cementitious compositions, for example at densities lower than 13 ppg, it is also envisioned to partially add in the composition additional fillers, including for example, cement kiln dust, fly ash or other by-products, as well as other natural products, including diatomaceous earth, ground expanded shale, and ground pumice, in other embodiments of the invention. In one embodiment, the amount of these additional fillers is selected such that the performances of the cementitious compositions at low densities, for example, lower than 13 ppg, and in particular from about 12 ppg to 8 ppg, are not compromised. For example, in one embodiment, the amount of limestone in the cementitious composition is greater than the amount of additional filler(s) and/or material(s) that may be added to the composition in addition to an hydraulic binder, metakaolin and silica fume.
In one embodiment, as an alternative to limestone, it is also envisioned to provide a source of calcium carbonate CaCO3 that has a content of calcium carbonate that is at least 60% by weight of the source of calcium carbonate. The source of calcium carbonate can include any material that can provide CaCO3 in a soluble or insoluble form. In various embodiments, a calcium carbonate source can be derived from limestone, dolomitic limestone, aragonite, calcite, chalk, marl and the like and any combination thereof. Suitable sources of calcium carbonate include, but are not limited to, limestone cement, masonry cement, cement raw mix, high grade manufactured limestone like Omya product Betocarb® and any combination thereof. In another embodiment, the content of calcium carbonate within the source of calcium carbonate is at least 70% by weight of the source of calcium carbonate. In another embodiment, the content of calcium carbonate within the source of calcium carbonate is at least 80% by weight of the source of calcium carbonate. In another embodiment, the content of calcium carbonate within the source of calcium carbonate is at least 90% by weight of the source of calcium carbonate.
In accordance with one embodiment of the invention, the cementitious binder includes a source of calcium carbonate in an amount in the range of about 5 to 30% by weight of the cementitious binder, when added with water, that has a density lower than about 12 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi without using lightweight additives such as microspheres, foaming agents or the like. Preferably, in an embodiment, the amount of the source of calcium carbonate is present in about 10 to 30% by weight of the cementitious binder. In yet another embodiment of the invention, the source of calcium carbonate is present in an amount greater than 15% and lower than about 25% by weight of the cementitious binder.
In one embodiment, the amount of the source of calcium carbonate in the cementitious composition is greater than the amount of additional filler(s) and/or material(s) that may be added to the composition in addition to an hydraulic binder, metakaolin and silica fume.
The cementitious binder, according to one embodiment of the invention, may further include a hydraulic binder. Examples of hydraulic binders that could be used in embodiments of the invention are, but not limited to, Portland cements, blended cements, masonry cements compliant with ASTM and/or AASHTO specifications (including Types I, II, III, IV, V Portland cements) as well as API compliant cements. The inventors have devised that the high fineness of some cements enhance water retention and strength development of the cementitious settable composition. In one embodiment, the hydraulic binder includes Type III Portland cement. It is desirable to control the amount of hydraulic binder in the cementitious binder to achieve early high compressive strength for low density cementitious settable compositions. The cementitious binder includes a hydraulic cement in an amount in the range of about 40 to 75%.
Preferably, in one embodiment of the invention, the cementitious binder further includes metakaolin in an amount in the range of from about 1 to 30% by weight of the cementitious binder. Preferably, in one embodiment of the invention, metakaolin is present in the cementitious binder in an amount in the range of from about 8 to 25% by weight of the cementitious binder. More preferably, in one embodiment of the invention, metakaolin is present in the cementitious binder in an amount in the range of from about 8 to 18% by weight of the cementitious binder.
Metakaolin acts as a pozzolanic material in the cementitious binder and should preferably have an average particle size lower than about 3 μm, preferably lower than about 1.7 μm in one embodiment. A pozzolanic material is a siliceous or aluminosiliceous material that possesses little or no cementitious value, but will, in the presence of water and in finely divided form, chemically react with the calcium hydroxide produced during the hydration of Portland cement to form materials with cementitious properties. It has been found that cementitious binders including metakaolin, which has a small particle size, significantly enhance the early compressive strength of cementitious settable compositions having a density lower than 13 ppg, for example lower than 12 ppg, or lower than 11 ppg or lower than 10 ppg.
In other embodiments of the invention, it is envisioned that other types of pozzolanic materials could be used in addition to or instead of metakaolin.
For example, in one embodiment of the invention, the cementitious binder may also include silica fume in an amount up to about 15% by weight of the cementitious binder. Silica fume is a by-product formed in the production of silicon or ferro-silicon alloys and is collected by filtration of gases leaving the electric arc furnace. Typically it contains at least 75%, by weight, of silicon dioxide and consists of very fine spherical particles less than about 0.1 μm. It has been determined that, due to its very high surface area, a small amount of silica fume was beneficial in obtaining cementitious settable compositions having low free fluid and segregation. In addition, it has been determined that high surface area materials such as silica fume and diatomaceous earth produce synergistic effects with other ultra fine materials that enhance early (e.g. 24 h) compressive strengths for low density cementitious settable compositions.
The cementitious composition also includes a cementitious accelerator to accelerate hydration. A cementitious accelerator is defined herein as any admixture(s) that is/are added to the binder and is/are adapted to accelerate hydration of the cementitious composition in a controlled manner. As will be appreciated by one skilled in the art, controlling hydration of the cementitious composition is desirable to obtain the intended mechanical and rheological properties. Thus, according to various embodiments of the invention, the cementitious accelerator is selected and added to the cementitious composition in a controlled amount to accelerate hydration. The cementitious accelerator defined herein and encompassed by various embodiments of the invention departs from chemical(s) and/or component(s) present in other products (e.g. by-products), which chemical(s) and/or component(s) may exhibit accelerating properties in some circumstances but are not provided in a controlled amount to the composition. For example, the cementitious accelerator defined herein departs from chlorides and/or alkalies that might be present in cement kiln dust, which might be added to the cementitious composition in one embodiment. As will be appreciated by one skilled in the art, chlorides and/or alkalies present in the cement kiln, dust may significantly vary depending on, for example, the raw ingredients fed to the kiln assembly, the type of fuels and raw materials that are used in the burner assembly of the cement kiln and the operation of the dust filter that collects the cement kiln dust. Therefore, as will be appreciated by one skilled in the art, any composition including cement kiln dust would not include a controlled amount of chlorides and/or alkalies and, therefore, a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious composition.
The cementitious accelerator can be separately, added during or after co-grinding and/or blending the various elements of the cementitious binder. For example, the cementitious accelerator can be added at the time of preparing the slurry. Thus, the cementitious accelerator can be added to the mixture including hydraulic binder, metakaolin, optional silica fume and limestone at the time of preparing the slurry.
Examples of suitable cementitious accelerators are, but not limited to, a source of chlorides in which chlorides are provided in a controlled amount, triethanolamine, sodium thiocyanate, calcium formate, calcium nitrite, calcium nitrate, alkali salts, non chloride based accelerators such as Grace Construction Products Polarset® or any combination thereof. This is not limiting. Additional cementitious accelerators may be used in other embodiments of the invention. The cementitious binder includes an accelerator in an amount of at least 0.5%. For example, in one embodiment, the accelerator is in an amount from about 0.5% to 4% by weight of the cementitious binder. In yet another embodiment, the accelerator is preferably in an amount from 0.6% to 3%. In yet another embodiment, the accelerator is preferably in an amount from 0.8% to 2.5%.
The lightweight cementitious settable compositions of embodiments of the invention exhibit enhanced compressive performances at densities lower than 13 pounds per gallon (ppg) without using, or including a minimum amount of, lightweight additives such as microspheres, foaming agents or the like. In particular, the cementitious binder provides a cementitious settable composition, when only water is added, that has a density lower than about 12 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi. The water used in the cementitious settable compositions of embodiments of the present invention may include 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 adversely affect other components in the cementitious 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 cementitious settable compositions of embodiments of the present invention in an amount in the range of from about 40% to about 200% by weight. As used herein, the term “by weight,” when used herein to refer to the percent of a component in the cementitious settable composition, means by weight included in the cementitious settable compositions of the present invention relative to the weight of the dry components in the cementitious settable composition. In some embodiments, the water may be included in an amount in the range of from about 40% to about 150% by weight.
Cementitious settable compositions of embodiments of the invention having a density lower than about 10 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi can be obtained by using a reduced amount of lightweight additives, such as microspheres. The higher strength and good slurry properties obtained by the cementitious settable composition of this embodiment at 12 ppg and at a density lower than 13 ppg enables slurry density decrease by increasing the water content (while maintaining acceptable slurry properties). A formulation of ultralight cementitious settable composition (e.g. 10 ppg, 9 ppg and 8 ppg) is done by first determining the water content required to achieve a desired compressive strength in a cementitious settable composition without lightweight additives such as microspheres. The required amount of lightweight additives (e.g. microspheres) is then calculated to achieve the target weight of the cementitious settable composition. Up to a certain content, the lightweight additives, such as microspheres, are considered as fillers that have minimal impact on water content and rheology and therefore will maintain any designed target strength.
A variety of microspheres may be utilized in accordance with embodiments of the present invention, including hollow, solid, and/or porous microspheres. Suitable microspheres may include a variety of materials, including, but not limited to, microspheres that comprise glass, soda lime borosilicate glass, fly ash, ceramic, polystyrene, other polymeric materials, and mixtures thereof. In some embodiments of the lightweight cementitious settable compositions of the present invention, the microspheres are hollow, glass microspheres. In some embodiments, the microspheres may comprise a crosslinked polymeric material, such as polystyrene crosslinked with divinyl benzene (e.g., plastic beads). The microspheres may be obtained from any suitable source. Examples of suitable fly ash microspheres are commercially available from Halliburton Energy Services, Inc., Duncan, Okla., under the tradename SPHERELITETM microspheres. Suitable hollow, soda lime borosilicate glass microspheres include 3MTM SCOTCHLITETM glass bubbles. In a preferred embodiment, borosilicate glass microspheres (3MTM beads) produced by the 3MTM company can be beneficially used to produce lightweight cementitious settable compositions that produce enhanced 24 h compressing strengths.
In one embodiment of the invention, the microspheres may be added in the cement finish mill, in the cement separator, in the cement cooler or by using a separate blender from the cement grinding operation. In these embodiments, the resulting premix would include microspheres before being delivered to the user. Alternatively, in another embodiment, microspheres may be blended with the cementitious binder/premix by the user to further lower the density of the cementitious settable composition, for example, to obtain a density lower than about 10 ppg, or lower than about 9 ppg (for example about 8 ppg).
It is envisioned in one embodiment of the invention to foam the cementitious settable composition with a gas to further lower its density. The gas used in the foamed settable compositions according to embodiments 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 cementitious settable compositions according to embodiments of the present invention in an amount sufficient to form the desired foam. The cementitious settable compositions of embodiments of the present invention further include a surfactant. In some embodiments, the surfactant includes a foaming and stabilizing surfactant composition to facilitate the foaming of a cementitious settable composition and to stabilize the resultant foamed cementitious settable composition formed therewith. Any suitable foaming and stabilizing surfactant composition may be used in the cementitious settable compositions according to embodiments of the present invention.
In one embodiment, the low density cementitious compositions are prepared by co-grinding the hydraulic binder (e.g. Portland cement), limestone, metakaolin and optional silica fume. In one embodiment, all products are added to the finish mill. In another embodiment, the hydraulic binder, limestone and silica fume are co-ground and then blended with metakaolin. In another embodiment of the invention, the hydraulic binder and limestone are co-ground and then blended with silica fume and metakaolin. In yet another embodiment of the invention, the hydraulic binder is blended with all other components, including limestone, metakaolin and silica fume. The accelerator and/or other adjuvants can be added by a blending process after the finish mill before it goes to the silo or simply blended with a blender or added when preparing the slurry.
Embodiments of the present invention will be further illustrated in more detail using the following, but not limitative, examples. A series of sample settable cementitious compositions were prepared at room temperature and subjected to 24 hour compressive strength tests at 100 F (or 38° C.). Results are given for densities in ppg (1 pound/gallon [US]=119.826 426 81 kilogram/cubic meter). Pressures are given in psi (1 pound/square inch=6 894.757 28 pascal).
Example 1
Table 1 presents various low density cementitious compositions that were prepared with no lightweight additives (no bubbles, foaming agents or the like) in accordance with one embodiment of the invention. A series of samples were prepared at room temperature and subjected to 24 h compressive strength at 100 F in accordance with API specification 10.
In Table 1, the chloride based accelerator is CaCl2 and the alkali based accelerator is K2SO4. Limestone 1 and limestone 2 have respectively an average limestone particles granulometry of about 3 μm and 6 μm. OPC is a hydraulic binder corresponding to Type III Portland cement.
As can be seen in Table 1, the use of calcium carbonate can produce lightweight cementitious compositions that have a density lower than 13 ppg and a compressive strength greater than 500 psi at 24 h/100 F. Samples 5 and 10 are comparative examples, which show that the absence of an accelerator does not provide a compression strength of at least 500 psi.
















TABLE 1











Silica
Accelerator 1

24 h 




OPC
Limestone 1
Limestone 2
Metakaolin
Fume
chloride
Accelerator 2
strength



Density,
(% by
(% by
(% by
(% by
(% by
based
alkali based
100 F.


Sample
ppg
weight)
weight)
weight)
weight)
weight)
(% by weight)
(% by weight)
(psi)
























1
11.5
61
22.8

12
3
0.9
0
563


2
11.5
61
22.7

12
3
1.2
0
592


3
11.6
61
22.6

12
3
1.7
0
599


4
11.8
61
22.6

12
3
0.9
0.7
753


5
11.9
62
23

12
3
0
0
309


6
11.8
62
22.1

12
3
0.9
0
589


7
11.7
62
21.4

12
3
0.9
0.7
688


8
11.6
62
2
18.7
12
3
1.3
1
804


9
11.7
62
4
16.7
12
3
1.3
1
856


10
11.6
62

23
12
3
0
0
287


11
11.9
62

22.4
12
3
0.6
0
650


12
11.5
62

22.1
12
3
0.9
0
544


13
11.6
62

21.4
12
3
0.9
0.7
629


14
11.8
62

21
12
3
1
1
930


15
11.6
62

21
12
3
1.3
0.7
660


16
11.6
62

20.7
12
3
1.3
1
760


17
11.7
62

20.7
12
3
1.3
1
1096


18
11.6
64

18.7
12
3
1.3
1
840


19
11.6
66

16.7
12
3
1.3
1
912


20
12.8
55

28
12
3
1
1
1940


21
12.9
62

21
12
3
1
1
2490









Example 2
Referring now to Table 2, this Table shows the impact of the amount of the source of calcium carbonate on the 24 h compressive strength of various cementitious settable compositions cured at 100 F, including Portland Cement, metakaolin and silica fume. The compositions were prepared without using lightweight additives such as microspheres, foaming agents or the like. In Table 2, the ratio of hydraulic binder/source of calcium carbonate is varied for a fixed amount of metakaolin and silica fume. As can be seen in Table 2, the use of a source of limestone carbonate provides low density cementitious settable compositions, with a density between 11 and 12 ppg, that show a 24 h compressive strength higher than 500 psi when cured at 100 F. All tests were conducted in accordance to API Specification 10.
Samples 25-28 are comparative sample compositions, each providing a compression strength of lower than 500 psi, even when the accelerator content is in the order of 2% by weight of the cementitious binder.















TABLE 2










Silica
Accelerator 1

24 h 




OPC
Limestone 2
Metakaolin
Fume
Chloride
Accelerator 2
strength



Density,
(% by
(% by 
(% by 
(% by
based
alkali based
100 F.


Sample
ppg
weight)
weight) 
weight)
weight)
(% by weight)
(% by weight)
(psi)























22
10.5
55
28
12
3
1
1
170


23
10.4
62
21
12
3
1
1
200


24
10.3
75
8
12
3
1
1
170


25
11.2
35
45
9
9
1
1
185


26
11.2
40
45
8
5
1
1
175


27
11
40
30
8
20
1
1
295


28
11.7
40
43
12
3
1
1
480


29
11.7
55
28
12
3
1
1
730


30
11.8
62
21
12
3
1
1
930


31
11.9
75
8
12
3
1
1
1190


32
11.5
55
28
12
3
1
1
540


33
11.6
62
21
12
3
1
1
660


34
11.3
75
8
12
3
1
1
620


35
11.6
45
28
18
7
1
1
900


36
11.9
55
18
18
7
1
1
1210


37
11.8
62
11
18
7
1
1
1330









Example 3
Table 3 shows the impact of the amount of metakaolin on the 24 h compressive strength of various low density cementitious settable compositions cured at 100 F, including a Portland cement (OPC), limestone and optionally silica fume. In Table 3, the amount of metakaolin is varied for a fixed amount of the source of limestone carbonate. The compositions were prepared without using lightweight additives such as microspheres, foaming agents and the like.
Example 4
Table 4 shows the impact of the amount of silica fume on the 24 h compressive strength of various low density cementitious settable compositions (between 11 and 12 ppg) cured at 100 F, including Portland cement (OPC), metakaolin and limestone. In Table 4, the relative amount of metakaolin and silica fume is varied for a fixed amount of the source of limestone carbonate. The compositions were prepared without using lightweight additives such as microspheres, foaming agents and the like. All tests were conducted in accordance with API Specification 10.
Example 5
A series of ultra lightweight cementitious compositions (about 10 ppg and 8 ppg) were prepared at room temperature and subjected to 24 h compressive strength at 100 F in accordance with API specification 10. The compositions were prepared with lightweight microsphere additives. The compressive strength results are presented in Table 5.
As can be seen in Table 5, each of the lightweight cementitious compositions prepared at about 10 ppg exhibits a 24 h compression strength greater than 500 psi, and even greater than 800 psi for a microspheres content of less than 15%. Furthermore, it is possible to obtain a 24 h compression strength greater than 500 psi for a cementitious composition prepared at about 8 ppg with a microspheres content lower than 35%.















TABLE 3










Silica
Accelerator 1

24 h 




OPC
Limestone 2
Metakaolin
Fume
Chloride
Accelerator 2
strength



Density,
(% by
(% by
(% by 
(% by
based
alkali based
100 F.


Sample
ppg
weight)
weight)
weight)
weight)
(% by weight)
(% by weight)
(psi)























38
11.6
54
21
23
0
1
1
1810


39
11.6
59
21
18
0
1
1
1080


40
11.7
62
21
15
0
1
1
1030


41
11.7
65
21
12
0
1
1
900


42
11.8
68
21
9
0
1
1
810
























TABLE 4










Silica 
Accelerator 1

24 h 




OPC
Limestone 2
Metakaolin
Fume
Chloride 
Accelerator 2
strength



Density,
(% by
(% by
(% by
(% by
based
alkali based
100 F.


Sample
ppg
weight)
weight)
weight)
weight)
(% by weight)
(% by weight)
(psi)























43
11.7
62
21
15
0
1
1
1030


44
11.7
62
21
10
5
1
1
840


45
11.8
62
21
8
7
1
1
710


46
11.9
62
21
6
9
1
1
660


47
11.6
59
21
18
0
1
1
1080


48
11.8
59
21
13
5
1
1
930


49
11.8
59
21
11
7
1
1
800


50
11.6
59
21
9
9
1
1
730

























TABLE 5










Silica
Accelerator 1


24 h




OPC
Limestone 2
Metakaolin
Fume
Chloride
Accelerator 2
microspheres
strength



Density,
(% by
(% by 
(% by
(% by
based
alkali based
(% as final
100 F.


Sample
ppg
weight)
weight)
weight)
weight)
(% by weight)
(% by weight)
blend)
(psi)
























51
8.1
61
21
12
3
1
1
34.0
650


52
10.0
62
21
12
3
1
1
14.8
960


53
10.1
59
21
13
5
1
1
14.7
950


54
10.1
59
21
18
0
1
1
14.7
1250


55
10.1
59
21
11
7
1
1
14.8
1000


56
10.1
62
21
15
0
1
1
14.8
1100


57
10.1
62
21
11
4
1
1
14.8
990


58
10.3
62
20.7
12
3
1.3
1
13.0
830


59
10.2
66
20
12
3
1.3
1
14.3
896









Comparative Example 1
A low density cementitious settable composition was prepared using a conventional low density cementitious binder with an amount of water of 54% by weight of the cementitious settable composition. Table 6 shows the compressive strength performance obtained with this cementitious binder at 12 ppg.









TABLE 6







Conventional low density




cementitious binder








Compressive strength 
371



(24 h/100 F.) (psi)









As can be seen in Table 6, for the same amount of water (54%), the conventional cementitious binder provides a cementitious settable composition at 12 ppg having a 24 h compressive strength that is much lower than that obtained with the cementitious binder according to one embodiment (930 psi—see example 14).
Comparative Example 2
A low density cementitious settable composition was prepared using a conventional low density cementitious binder. Lightweight additives (borosilicate glass beads (3MTM beads) were added to reach a density of about 10 ppg. Table 7 shows the compressive strength performance obtained with this conventional cementitious binder at about 10 ppg.









TABLE 7







Conventional low density




cementitious binder


















% glass beads added
20.5



% water
41



Strength (24 h/100 F.) (psi)
717









As can be seen in Table 7, it is necessary to significantly increase the amount of lightweight additives (over 20%) in the conventional cementitious binder to provide a cementitious settable composition at about 10 ppg having a 24 h compressive strength greater than 700 psi. This compressive strength remains lower than that obtained with the cementitious binder according to one embodiment of the invention (see Table 5). The use of additional lightweight additives results in a significant increase in the cost of the cementitious binder as they are the most expensive materials in lightweight cementitious formulations.
The cementitious settable compositions according to embodiments of the invention may be used in a variety of applications. For example, the cementitious settable compositions may be used in primary cementing, remedial cementing, and drilling operations.
In accordance with one embodiment of the invention, the cementitious settable composition is introduced in the underground formation in a well bore between a casing and a wall of the well bore to perform primary cementing. In another embodiment, the cementitious settable composition may be introduced in the underground formation to repair the casing and/or to achieve zonal isolation. For example, the cementitious settable composition may be used for purposes including, but not limited to, sealing off perforations, repairing casing leaks (including leaks from damaged areas of the casing), plugging back or sealing off the lower section of a wellbore, and sealing the interior of a wellbore during abandonment operations. Examples of specific applications include, but are not limited to, cementing casing and liner strings, inflatable packers, squeezing perforations and casing leaks.
It is also envisioned in other embodiments of the invention to use the cementitious settable compositions in applications other than subterranean applications. For example, the cementitious settable compositions may be used in construction cementing where compositions having low densities and enhanced compressive strengths are desired. However, this is not limiting. For example, it is also envisioned in one embodiment of the invention to use the binder to prepare settable compositions at densities greater than about 13 ppg for use in a variety of applications, including surface applications and construction applications.
While the invention may be adaptable to various modifications and alternative forms, specific embodiments have been shown by way of example and described herein. However, it should be understood that the invention is not intended to be limited to the particular forms disclosed. Rather, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. Moreover, the different aspects of the disclosed compositions and methods may be utilized in various combinations and/or independently. Thus the invention is not limited to only those combinations shown herein, but rather may include other combinations.

## Claims

1. A manufactured cementitious binder comprising:
a hydraulic binder in an amount in the range of from 40 to 75% by weight of the cementitious binder;
metakaolin in an amount in the range of from 1 to 30% by weight of the cementitious binder;
silica fume in an amount up to 15% by weight of the cementitious binder;
limestone in an amount of from 5 to 30% by weight of the cementitious binder, and
a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious binder,
the cementitious binder providing a cementitious settable composition when added with water, wherein for a density lower than 13 pounds per gallon and of at least 11 pounds per gallon obtained without a lightweight additive, said cementitious settable composition exhibits a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.

2. The binder of claim 1, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 700 psi.

3. The binder of claim 2, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 800 psi.

4. The binder of claim 1, wherein the cementitious accelerator is in an amount from 0.6% to 3% by weight of the cementitious binder.

5. The binder of claim 4, wherein the cementitious accelerator is in an amount from 0.8% to 2.5% by weight of the cementitious binder.

6. The binder of claim 1, comprising microspheres in an amount less than 15% by weight of the cementitious binder, wherein the cementitious binder provides a cementitious settable composition, when added with water, that has a density lower than 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.

7. The binder of claim 6, wherein the cementitious settable composition has a density of about 10 pounds per gallon.

8. The binder of claim 6, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 700 psi.

9. The binder of claim 1, comprising microspheres in an amount less than 35% by weight of the cementitious binder, wherein the cementitious binder provides a cementitious settable composition, when added with water, that has a density of about 8 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.

10. The binder of claim 1, wherein metakaolin is present in the cementitious binder in an amount in the range of from 8 to 25% by weight of the cementitious binder.

11. The binder of claim 1, wherein a content of calcium carbonate CaCO3 in the limestone is at least 60% by weight of limestone.

12. The binder of claim 1, wherein limestone is in an amount of from 10 to 25% by weight of the cementitious binder.

13. A cementitious settable composition comprising:
water; and
a cementitious binder including
a hydraulic binder in an amount in the range of from 40 to 75% by weight of the cementitious binder;
metakaolin in an amount in the range of from 1 to 30% by weight of the cementitious binder;
silica fume in an amount-up to 15% by weight of the cementitious binder;
limestone in an amount of from 5 to 30% by weight of the cementitious binder, and
a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious binder,

wherein, without a lightweight additive, the cementitious settable composition has a density lower than 13 pounds per gallon and of at least 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.

14. The composition of claim 13, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 700 psi.

15. The composition of claim 14, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 800 psi.

16. The composition of claim 15, wherein the cementitious binder comprises microspheres in an amount less than 15% by weight of the cementitious binder, wherein the cementitious settable composition has a density lower than 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.

17. The composition of claim 16, wherein the settable composition has a density of about 10 pounds per gallon.

18. The composition of claim 17, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 700 psi.

19. The composition of claim 17, wherein metakaolin is present in the cementitious binder in an amount in the range of from 8 to 25% by weight of the cementitious binder.

20. The composition of claim 19, wherein metakaolin is present in the cementitious binder in an amount in the range of from 8 to 18% by weight of the cementitious binder.

21. The composition of claim 13, wherein limestone is in an amount of from about 10 to 25% by weight of the cementitious binder.

22. A method of cementing comprising:
providing a cementitious settable composition comprising:
water; and
a cementitious binder including
a hydraulic binder in an amount in the range of from 40 to 75% by weight of the cementitious binder;
metakaolin in an amount in the range of from 1 to 30% by weight of the cementitious binder;
silica fume in an amount up to 15% by weight of the cementitious binder;
limestone in an amount of from 5 to 30% by weight of the cementitious binder, and
a cementitious accelerator in a controlled amount of at least 0.5% by weight of the cementitious binder,

wherein, without a lightweight additive, the cementitious settable composition has a density lower than 13 pounds per gallon and of at least 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi; and

introducing the cementitious settable composition into an underground formation.

23. The method of claim 22, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 700 psi.

24. The method of claim 22, wherein the settable composition has a 24 hour compressive strength at 100 F, as hardened, of at least 800 psi.

25. The method of claim 22, wherein the cementitious binder comprises microspheres in an amount less than 15% by weight of the cementitious binder, wherein the cementitious binder provides a cementitious settable composition, when added with water, that has a density lower than about 11 pounds per gallon and a 24 hour compressive strength at 100 F, as hardened, of at least 500 psi.

26. The method of claim 22, wherein the underground formation is a well bore.