US20050155763A1 - Settable fluids comprising particle-size distribution-adjusting agents and methods of use - Google Patents

Settable fluids comprising particle-size distribution-adjusting agents and methods of use Download PDF

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Publication number
US20050155763A1
US20050155763A1 US10/759,678 US75967804A US2005155763A1 US 20050155763 A1 US20050155763 A1 US 20050155763A1 US 75967804 A US75967804 A US 75967804A US 2005155763 A1 US2005155763 A1 US 2005155763A1
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Prior art keywords
cement
composition
fluid
particle
size distribution
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US10/759,678
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B. Reddy
Anthony Palmer
Ashok Santra
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Halliburton Energy Services Inc
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Halliburton Energy Services Inc
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Assigned to HALLIBURTON ENERGY SERVICES, INC. reassignment HALLIBURTON ENERGY SERVICES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: REDDY, B. RAGHAVA, PALMER, ANTHONY V., SANTRA, ASHOK K.
Priority to US10/759,678 priority Critical patent/US20050155763A1/en
Application filed by Halliburton Energy Services Inc filed Critical Halliburton Energy Services Inc
Priority to US10/946,671 priority patent/US7328756B2/en
Priority to CA 2552575 priority patent/CA2552575C/en
Priority to GB0720363A priority patent/GB2442880B/en
Priority to AU2004313746A priority patent/AU2004313746B2/en
Priority to PCT/GB2004/005311 priority patent/WO2005068776A2/en
Priority to GB0611771A priority patent/GB2423985B/en
Priority to ARP050100119 priority patent/AR047636A1/en
Publication of US20050155763A1 publication Critical patent/US20050155763A1/en
Priority to NO20062851A priority patent/NO20062851L/en
Priority to US11/503,634 priority patent/US20060272819A1/en
Priority to US11/867,952 priority patent/US20080023200A1/en
Priority to NO20141321A priority patent/NO20141321A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/06Oxides, Hydroxides
    • C04B22/062Oxides, Hydroxides of the alkali or alkaline-earth metals
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/12Nitrogen containing compounds organic derivatives of hydrazine
    • C04B24/122Hydroxy amines
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/38Polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00Sealing or packing boreholes or wells
    • E21B33/10Sealing or packing boreholes or wells in the borehole
    • E21B33/13Methods or devices for cementing, for plugging holes, crevices, or the like
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034Physico-chemical characteristics of the mixtures
    • C04B2111/00146Sprayable or pumpable mixtures
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to subterranean operations, and more particularly, to settable fluids comprising particle-size distribution-adjusting agents, and methods of using such settable fluids.
  • Hydraulic cement compositions are commonly utilized in subterranean operations, particularly subterranean well completion and remedial operations.
  • hydraulic cement compositions are used in primary cementing operations whereby pipe strings, such as casings and liners, are cemented in well bores.
  • primary cementing hydraulic cement compositions are pumped into the annular 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 annular 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.
  • Hydraulic cement compositions also are used in remedial cementing operations such as plugging highly permeable zones or fractures in well bores, plugging cracks and holes in pipe strings, and the like.
  • Set-delayed cement compositions are often utilized in circumstances where an operator finds it desirable to prepare a volume of a cement composition that remains in a pumpable state for a long period of time (e.g., for about two weeks or more), and that can be selectively activated to set into a hard mass at a desired time.
  • a volume of a cement composition that remains in a pumpable state for a long period of time (e.g., for about two weeks or more), and that can be selectively activated to set into a hard mass at a desired time.
  • the equipment required for mixing and pumping the requisite large volumes of cement composition may be very expensive, and may be difficult to assemble at the desired location.
  • the storage of the requisite amount of dry cement prior to use may be another problem.
  • a set-delayed cement composition may also be desirable in circumstances where a relatively small volume of cement composition is used, such as a small construction job, for example, or a plugging and squeezing operation performed in the petroleum industry, for instance.
  • the cost to transport the cement composition to a job site, and to mix and pump it on location may be undesirable relative to the revenue generated from performing the cementing operation.
  • Set-delayed cement compositions may be useful in circumstances such as those described above, as they can be prepared at a convenient location, then transported to and stored at a job site until use.
  • the set-delayed cement composition may be mixed with a set activating agent; the resulting mixture may then be placed into a desired location (e.g., into a subterranean formation) and permitted to set therein.
  • a desired location e.g., into a subterranean formation
  • an excessive amount of set-activating agents have been injected into the set-delayed cement compositions, thereby “overactivating” the cement composition, after which a retarder is then added to the cement composition, in an attempt to fine-tune the eventual set time of the cement composition.
  • cement compositions may thicken or gel with time, increasing the cement composition's viscosity, and thus impairing its pumpability.
  • Another difficulty is that the activation process may be quite complicated, as exemplified by operations wherein the cement composition's set-time is first delayed until shortly before use, after which the cement composition is over-activated and again retarded.
  • Another problem that may occur with conventional set-delayed cement compositions is that the addition of set-activating agents may cause premature localized setting of the cement, e.g., localized regions within the bulk cement slurry wherein the set-activating agent becomes concentrated, thereby causing premature setting of a portion of the bulk cement.
  • premature localized setting of the cement composition may be likely to occur when the cement composition is inadequately mixed.
  • Premature localized setting of the cement composition may lead to pumping problems (e.g., hardened cement particles may damage pump impellers), and may also cause problems such as setting of the bulk cement while in storage tanks.
  • the present invention relates to subterranean operations, and more particularly, to settable fluids comprising particle-size distribution-adjusting agents, and methods of using such settable fluids.
  • An example of a method of the present invention is a method of cementing, comprising the steps of: providing a cement composition comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent; activating the cement composition; placing the cement composition in a desired location; and permitting the cement composition to set therein.
  • Another example of a method of the present invention is a method of drilling in a subterranean formation comprising the step of drilling a well bore in a subterranean formation using a drilling fluid comprising a cement, a set retarder, and a particle-size distribution-adjusting agent.
  • Another example of a method of the present invention is a method of using a fluid in a subterranean formation comprising the steps of: placing a displacement fluid comprising a cement, a set retarder, a particle-size distribution-adjusting agent, and an activator composition in a well bore in a subterranean formation so as to displace a second fluid therefrom.
  • composition of the present invention is a settable fluid comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent.
  • composition of the present invention is an activator composition for activating a settable fluid comprising a mixture of triethanolamine and an alkali metal hydroxide.
  • composition of the present invention is a particle-size distribution-adjusting agent for adjusting the particle-size distribution of a settable fluid to a desired range, the particle-size distribution-adjusting agent comprising a cationic polymer.
  • FIG. 1 depicts a graphical representation of the results of a rheology test performed on an exemplary embodiment of a settable fluid of the present invention.
  • FIG. 2 depicts a graphical representation of the results of a particle-size distribution test performed on a variety of settable fluids, including exemplary embodiments of the settable fluids of the present invention.
  • FIG. 3 depicts a graphical representation of the results of a particle-size distribution test performed on a variety of settable fluids, including exemplary embodiments of the settable fluids of the present invention.
  • FIG. 4 depicts a graphical representation of the results of a particle-size distribution test performed on a variety of settable fluids, including exemplary embodiments of the settable fluids of the present invention.
  • FIG. 5 depicts a graphical representation of the results of a thickening time test performed on exemplary embodiments of the settable fluids of the present invention.
  • FIG. 6 depicts a graphical representation of the results of a compressive strength test performed on exemplary embodiments of settable fluids of the present invention.
  • the present invention relates to subterranean operations, and more particularly, to settable fluids comprising particle-size distribution-adjusting agents, and methods of using such settable fluids.
  • the settable fluids of the present invention generally comprise a cement, water, a set retarder, and a particle-size distribution-adjusting agent.
  • other additives suitable for use in a settable fluid may be added.
  • the settable fluids of the present invention have a density in the range of from about 4 to about 25 pounds per gallon.
  • the settable fluids of the present invention have a density in the range of from about 10 to about 25 pounds per gallon.
  • the improved settable fluids of the present invention comprise a hydraulic cement.
  • hydraulic cements are suitable for use including those comprised of calcium, aluminum, silicon, oxygen, and/or sulfur, which set and harden by reaction with water.
  • hydraulic cements include, but are not limited to, Portland cements, pozzolana cements, gypsum cements, high alumina content cements, silica cements, and high alkalinity cements.
  • the water present in the settable fluids of the present invention may be from any source provided that it does not contain an excess of compounds that adversely affect other compounds in the settable fluids.
  • a settable fluid of the present invention can comprise fresh water, salt water (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated salt water), or seawater.
  • the water may be present in an amount sufficient to produce a pumpable slurry.
  • the water is present in the settable fluids of the present invention in an amount in the range of from about 25% to about 150% by weight of cement (“bwoc”) therein.
  • the water is present in the settable fluids of the present invention in an amount in the range of from about 40% to about 55% bwoc therein.
  • the particle-size distribution-adjusting agent in the settable fluids of the present invention may be any compound that desirably affects the particle-size distribution of the settable fluid such that the settable fluid's rheology remains desirably stable for a chosen period of time.
  • the presence of the particle-size distribution-adjusting agent in the settable fluids may forestall the onset of gelation for a desired period of time. Accordingly, certain embodiments of the settable fluids of the present invention are capable of remaining stable in a slurry state for several weeks or more before being activated by the addition of an activator composition.
  • the presence of the particle-size distribution-adjusting agent in the settable fluid tends to cause smaller particles in the settable fluid to agglomerate, thereby tending to narrow the distribution range of the size of the particles in the settable fluid.
  • a suitable particle-size distribution-adjusting agent is a cationic polymer.
  • cationic polymers suitable for use with the present invention include, but are not limited to, cationic polyacrylamides, cationic hydroxyethyl cellulose, poly(dimethyldiallylammonium chloride), and cationic starches.
  • the cationic polymer used in the settable fluids of the present invention is a cationic starch.
  • the particle-size distribution-adjusting agent may be present in the settable fluid in an amount sufficient to adjust the particle-size distribution of the settable fluid to a desired range. More particularly, the particle-size distribution-adjusting agent may be present in the settable fluid in an amount in the range of from about 0.01% to about 4% bwoc.
  • the settable fluids of the present invention further comprise a set retarder.
  • any set retarder may be used with the settable fluids of the present invention.
  • the set retarders used in the present invention comprise phosphonic acid derivatives, such as those that are described in U.S. Pat. No. 4,676,832, the relevant disclosure of which is hereby incorporated herein.
  • Commercially available examples of a suitable set retarder include those available from Monsanto Corporation of St. Louis, Mo. under the tradename “DEQUEST.”
  • a sodium salt of a phosphonic acid commercially available from Monsanto Corporation of St. Louis, Mo. under the tradename “DEQUEST 2006” is used.
  • the set retarder is present in the settable fluids of the present invention in an amount in the range of from about 0.1% to about 5% bwoc.
  • the settable fluids of the present invention may further comprise a yield stress reducing agent.
  • a yield stress reducing agent may be particularly beneficial in certain exemplary embodiments where a densified settable fluid is used.
  • the use of a yield stress reducing agent may facilitate pumping of the densified settable fluid, inter alia, by reducing the force required to move the densified settable fluid from a static position. While the present invention is not limited by any particular theory, it is believed that the yield stress reducing agent, inter alia, increases the repulsive force between cement particles, thereby preventing them from approaching each other.
  • a suitable yield stress reducing agent is a sulfonated melamine formaldehyde condensate that is commercially available under the tradename “MELADYNE” from Handy Chemicals, Ltd., of Beachwood, Ohio.
  • Another example of a suitable yield stress reducing agent is a sulfite adduct of an acetone formaldehyde condensate, commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the tradename “CFR-3.”
  • Another example of a suitable yield stress reducing agent is a sulfonated naphthalene condensate, commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the tradename “CFR-6.”
  • the settable fluids of the present invention may further comprise an expanding additive.
  • the expanding additive may be any component suitable for incorporating gas into the settable fluid. Where the expanding additive is a gas, gasification of the settable fluid may be achieved at the surface in one preferred embodiment, and the gasified settable fluid may be then introduced into the subterranean formation and permitted to set therein into a resilient, ductile, and tough gasified cement mass.
  • the settable fluid may be gasified during, or after, its placement in the subterranean formation, by the inclusion of a particular expanding additive within the settable fluid. Where an expanding additive in particulate form is used, aluminum powder, gypsum blends, and deadburned magnesium oxide are preferred.
  • Preferred expanding additives comprising aluminum powder are commercially available under the tradenames “GAS-CHEK®” and “SUPER CBL” from Halliburton Energy Services, Inc., of Duncan, Okla.; a preferred expanding additive comprising a blend containing gypsum is commercially available under the tradename “MICROBOND” from Halliburton Energy Services, Inc., of Duncan, Okla.; and preferred expanding additives comprising deadburned magnesium oxide are commercially available under the tradenames “MICROBOND M” and “MICROBOND HT” from Halliburton Energy Services, Inc., of Duncan, Okla. Such preferred expanding additives are described in commonly-owned U.S. Pat. Nos.
  • the settable fluids of the present invention are to be foamed (e.g., to reduce the density of the settable fluid, or to improve its mechanical properties)
  • the settable fluid is foamed in one exemplary embodiment by direct addition of the expanding additive into the settable fluid.
  • the gas utilized can be air or any suitable inert gas, such as nitrogen, or even a mixture of such gases. In certain exemplary embodiments, nitrogen is used.
  • the gas may be present in the composition in an amount sufficient to foam the composition, generally in an amount in the range of from about 0.01% to about 60% by volume of the composition.
  • the settable fluid is foamed by gas generated by a reaction between the cement slurry and an expanding additive present in the settable fluid in particulate form.
  • the composition may be foamed by hydrogen gas generated in situ as the product of a reaction between the slurry and fine aluminum powder present in the settable fluid.
  • surfactants optionally may be added to the settable fluid.
  • Surfactant compositions suitable for use in the present invention are described in U.S. Pat. Nos. 6,063,738 and 6,367,550, the relevant disclosures of which are hereby incorporated herein by reference.
  • Additional additives may be added to the settable fluids of the present invention as deemed appropriate by one skilled in the art with the benefit of this disclosure.
  • additives include, inter alia, fluid loss control additives, salts, vitrified shale, fly ash, fumed silica, bentonite, fixed-density weighting agents, and the like.
  • An example of a suitable fluid loss control additive is commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the tradename “HALAD® 9.”
  • an activator composition of the present invention may be added.
  • the activator compositions of the present invention generally comprise a mixture of at least one alkali or alkaline earth metal hydroxide, and a trialkanolamine.
  • alkali or alkaline earth metal hydroxides are suitable for use in the present invention.
  • the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide and potassium hydroxide.
  • trialkanolamines are suitable for use in the present invention.
  • the trialkanolamine is selected from the group consisting of: triethanolamine (“TEA”), tripropanolamine, and triisopropanolamine.
  • the trialkanolamine is TEA.
  • TEA triethanolamine
  • the alkali metal hydroxide is sodium hydroxide.
  • the activator composition may be added to a settable fluid of the present invention in an amount sufficient to enable the settable fluid to achieve a desired compressive strength and a desired thickening time.
  • the activator composition may be added to the settable fluid in an amount in the range of from about 0.1% to 5% bwoc.
  • the alkali or alkaline earth metal hydroxide may be present in the activator composition in an amount in the range of from about 50% to about 99.9% by weight.
  • the trialkanolamine may be present in the activator composition in an amount in the range of from about 0.1% to about 50% by weight.
  • the activator composition may be added in a variety of ways.
  • the activator composition may be added to the settable fluid while the latter is still in storage.
  • the activator composition may be injected into the settable fluid at the same time that the settable fluid is injected into the subterranean formation.
  • the injection of the activator composition while the settable fluid is injected into the formation may assist in minimizing the development within the settable fluid of localized regions having a high activator concentration.
  • the settable fluid may be formulated as a “densified” settable fluid (e.g., formulated with a significantly higher density than that which is calculated to be necessary for its intended use) before the addition of the activator composition.
  • a densified settable fluid may be provided in a variety of ways, such as through the addition of high-density particles, or by formulating the settable fluid with less water than necessary for its intended use.
  • the employment of a densified settable fluid will facilitate the addition of an activator composition in the form of a dilute solution.
  • a densified settable fluid having a density of, say, 17.0 lb/gallon or higher may be provided and activated with an activator composition diluted with sufficient water to ultimately provide the desired 16.4 lb/gallon slurry.
  • the addition of the activator composition in a dilute solution to a densified settable fluid may minimize the possibility of developing localized zones having excessive activator concentration due to inadequate mixing.
  • the settable fluids of the present invention may be used as a drilling fluid.
  • a drilling fluid of the present invention comprising a cement, a set retarder, and a particle-size distribution-adjusting agent may be used to drill a subterranean formation, e.g., by circulating the drilling fluid while drilling a well in contact with a drill bit and a subterranean formation.
  • the drilling fluid is used to drill a well bore in a subterranean formation, after which casing is placed within the well bore.
  • an activator composition of the present invention is then mixed with the drilling fluid, and the drilling fluid is permitted to set behind the casing.
  • an exemplary method of the present invention comprises the step of drilling a well bore in a subterranean formation using a drilling fluid comprising a cement, a set retarder, and a particle-size distribution-adjusting agent. Additional steps include, but are not limited to, placing a casing string within the well bore; mixing an activator composition of the present invention with the drilling fluid; and permitting the drilling fluid to set behind the casing string.
  • the settable fluids of the present invention may be used as a displacement fluid.
  • a displacement fluid of the present invention comprising a cement, a set retarder, a particle-size distribution-adjusting agent, and an activator composition of the present invention may be placed in a well bore that has been drilled (with a drilling fluid) in a subterranean formation so as to partially or completely displace the drilling fluid from the well bore.
  • a cement composition is subsequently placed in the well bore so as to partially or completely displace the displacement fluid therefrom.
  • an exemplary method of the present invention comprises the steps of: placing a displacement fluid comprising a cement, a set retarder, a particle-size distribution-adjusting agent, and an activator composition in a well bore in a subterranean formation so as to displace a second fluid therefrom.
  • Additional steps include, but are not limited to, placing a casing string within the well bore; placing a cement composition within the well bore so as to displace at least a portion of the displacement fluid therefrom; permitting the cement composition to set therein; and permitting any undisplaced displacement fluid to set therein.
  • Another example of a method of the present invention is a method of cementing, comprising the steps of: providing a cement composition comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent; activating the cement composition; placing the cement composition in a desired location; and permitting the cement composition to set therein. Additional steps include, but are not limited to, permitting the cement composition to remain in a slurry state for at least twenty four hours before being activated; permitting the cement composition to remain in a slurry state for at least two weeks before being activated; and permitting the cement composition to remain in a slurry state for more than two weeks before being activated.
  • Sample Composition No. 1 comprised Class H cement, to which 34.52% water bwoc and 0.933% DEQUEST 2006 bwoc were added. Within four days, the viscosity of Sample Composition No. 1 had increased to such an extent that Sample Composition No. 1 could not be pumped. TABLE 1 Fann 35 Rheometer Settings (rpm) Day 600 300 200 100 6 3 0 234 128 92 51 8 6 1 245 150 110 68 25 20 3 275 182 145 103 55 47 4 Too thick for rheology measurements
  • Sample Composition No. 2 comprised Class H cement, to which 34.52% water bwoc was added. Next, 0.267% HALAD® 9 bwoc was added, along with 0.098% CFR-6 bwoc, 0.233% REDIBOND 5330 A bwoc, and 0.933% DEQUEST 2006 bwoc. The density of Sample Composition No. 2 was measured to be 17.0 lb/gallon.
  • the settable fluids of the present invention comprising particle-size distribution-adjusting agents may maintain their original Theological properties during a storage period of at least about two weeks.
  • sample settable fluids Two sample settable fluids were prepared comprising Class H cement and water, such that the density of each settable fluid was 16.5 pounds per gallon.
  • a particle-size distribution-adjusting agent was then added to one sample settable fluid (Sample Composition No. 4).
  • the particle size distribution of each sample composition was measured according to the following procedure. First, cement was added to a circulating stream of water, at which point the particle-size distribution of the mixture was measured. For Sample Composition No. 4, a known amount of the particle-size distribution-adjusting agent was then added to the circulating stream, and the particle-size distribution was again measured; additional amounts of the particle-size distribution-adjusting agent were added, and additional particle-size distribution measurements were taken, until no further change in particle size was observed.
  • the particle sizes in the sample settable fluids were measured on a Malvern Particle Size Analyzer, available from Malvern Instruments Ltd., of Worcestershire, UK. For a given particle size, the Particle Size Analyzer identifies the volume percentage of particles in the sample that are beneath that particle size. The Particle Size Analyzer also provides a median particle size. Another parameter reported by the Particle Size Analyzer is the “Span,” which describes the width of the distribution independent of the median particle size. The Particle Size Analyzer also reports the “Uniformity” of the particle-size distribution, which is a measure of the absolute deviation from the median particle size, and which is also independent of the median particle size. The lower the value reported for the “Uniformity,” the smaller the absolute deviation from the median particle size, and thus the more uniform the settable fluid.
  • Sample Composition No. 3 did not further comprise a particle-size distribution-adjusting agent.
  • Sample Composition No. 4 a settable fluid of the present invention, further comprised 0.233% bwoc of REDIBOND 5330 A.
  • Sample Composition No. 5 comprised Class G cement, to which 40.00% water bwoc was added. Next, 0.267% HALAD-9 bwoc was added, along with 0.098% CFR-6 bwoc, 0.233% bwoc REDIBOND 5330 A, and 0.933% DEQUEST 2006 bwoc. The density of Sample Composition No. 5 was measured to be 16.32 ppg.
  • settable fluids of the present invention comprising Class G cement substantially maintain their original rheological properties for at least about two weeks.
  • Sample Composition No. 6 comprised Class A cement, to which 42.00% water bwoc was added. Next, 0.534% HALAD-9 bwoc was added, along with 0.098% CFR-6 bwoc, 0.233% bwoc REDIBOND 5330 A, and 0.933% DEQUEST 2006 bwoc. The density of Sample Composition No. 6 was measured to be 16.03 ppg.
  • settable fluids of the present invention comprising Class A cement may maintain their original rheological properties for at least about two weeks.
  • Sample Composition No. 7 had a composition identical to that in Sample Composition No. 2, except that DEQUEST 2006 was replaced by a molar equivalent of DEQUEST 2000.
  • settable fluids of the present invention comprising DEQUEST 2000 may maintain their original rheological properties for at least about two weeks.
  • the rheology and the free water content of the slurry were measured at the indicated time intervals in Table 10. Additionally, a composite of the slurry was activated at the time intervals reported in Table 10, and the set times were measured.
  • the activator composition comprised 3.78% water bwoc, 0.07% TEA bwoc, and 0.75% sodium hydroxide bwoc.
  • the settable fluids of the present composition may be taken from storage at any time within about two weeks or more after their initial preparation, activated with an activator composition of the present invention, to be utilized in a desired application.
  • the storage time did not appear to significantly affect the set characteristics or other properties of the cement.
  • the density of a set composite of Sample Composition No. 8 was measured at the top, middle, and bottom, by mechanically separating the Sample Composition into top, middle, and bottom portions, and measuring the density of each portion.
  • the top set density was measured to be 16.96 lb/gallon.
  • the middle set density was measured to be 17.12 lb/gallon.
  • the bottom set density was measured to be 17.24 lb/gallon.
  • Sample settable fluids were prepared, each having a composition identical to that of Sample Composition No. 2, except that each comprised a different combination of various activators.
  • Sample Composition No. 9 did not comprise an activator.
  • Sample Composition No. 10 comprised 0.5% TEA bwoc.
  • Sample Composition No. 11 comprised 0.75% sodium hydroxide bwoc.
  • Sample Composition No. 12 comprised 0.75% sodium hydroxide bwoc and 2% calcium chloride bwoc.
  • Sample Composition No. 13 comprised 0.5% TEA bwoc and 0.75% sodium hydroxide bwoc, an activator composition of the present invention.
  • Sample settable fluids were prepared having a composition identical to that of Sample Composition No. 2, further comprising 0.07% TEA bwoc, and various amounts of sodium hydroxide, to determine the effect of sodium hydroxide on thickening time and compressive strength development.
  • Sample Composition No. 14 comprised 0.11% sodium hydroxide bwoc.
  • Sample Composition No. 15 comprised 0.75% sodium hydroxide bwoc.
  • Sample Composition No. 16 comprised 1.0% sodium hydroxide bwoc.
  • the presence of sodium hydroxide in the activator compositions of the present invention may impart a substantially linear effect on thickening time and compressive strength development.

Abstract

The present invention relates to subterranean operations, and more particularly, to settable fluids comprising particle-size distribution-adjusting agents, and methods of using such settable fluids in subterranean and surface applications. In certain exemplary embodiments of the present invention, the settable fluid comprises a cement, a set retarder, and a particle-size distribution-adjusting agent. Exemplary methods of the present invention include, but are not limited to, methods of drilling with the settable fluids of the present invention, methods of cementing with the settable fluids of the present invention, and methods of using a settable fluid of the present invention to displace another fluid from a well bore in a subterranean formation.

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to subterranean operations, and more particularly, to settable fluids comprising particle-size distribution-adjusting agents, and methods of using such settable fluids.
  • Hydraulic cement compositions are commonly utilized in subterranean operations, particularly subterranean well completion and remedial operations. For example, hydraulic cement compositions are used in primary cementing operations whereby pipe strings, such as casings and liners, are cemented in well bores. In performing primary cementing, hydraulic cement compositions are pumped into the annular 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 annular 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. Hydraulic cement compositions also are used in remedial cementing operations such as plugging highly permeable zones or fractures in well bores, plugging cracks and holes in pipe strings, and the like.
  • Set-delayed cement compositions are often utilized in circumstances where an operator finds it desirable to prepare a volume of a cement composition that remains in a pumpable state for a long period of time (e.g., for about two weeks or more), and that can be selectively activated to set into a hard mass at a desired time. For example, in circumstances where very large volumes of cement are utilized (such as in offshore platform grouting), the equipment required for mixing and pumping the requisite large volumes of cement composition may be very expensive, and may be difficult to assemble at the desired location. The storage of the requisite amount of dry cement prior to use may be another problem. As another example, the use of a set-delayed cement composition may also be desirable in circumstances where a relatively small volume of cement composition is used, such as a small construction job, for example, or a plugging and squeezing operation performed in the petroleum industry, for instance. In such circumstances, the cost to transport the cement composition to a job site, and to mix and pump it on location may be undesirable relative to the revenue generated from performing the cementing operation. Set-delayed cement compositions may be useful in circumstances such as those described above, as they can be prepared at a convenient location, then transported to and stored at a job site until use. At a desired time, the set-delayed cement composition may be mixed with a set activating agent; the resulting mixture may then be placed into a desired location (e.g., into a subterranean formation) and permitted to set therein. In some formulations, an excessive amount of set-activating agents have been injected into the set-delayed cement compositions, thereby “overactivating” the cement composition, after which a retarder is then added to the cement composition, in an attempt to fine-tune the eventual set time of the cement composition.
  • Operations involving conventional set-delayed cement compositions may encounter a number of difficulties. For example, the cement composition may thicken or gel with time, increasing the cement composition's viscosity, and thus impairing its pumpability. Another difficulty is that the activation process may be quite complicated, as exemplified by operations wherein the cement composition's set-time is first delayed until shortly before use, after which the cement composition is over-activated and again retarded.
  • Another problem that may occur with conventional set-delayed cement compositions is that the addition of set-activating agents may cause premature localized setting of the cement, e.g., localized regions within the bulk cement slurry wherein the set-activating agent becomes concentrated, thereby causing premature setting of a portion of the bulk cement. Such premature localized setting of the cement composition may be likely to occur when the cement composition is inadequately mixed. Premature localized setting of the cement composition may lead to pumping problems (e.g., hardened cement particles may damage pump impellers), and may also cause problems such as setting of the bulk cement while in storage tanks.
  • An additional difficulty posed by conventional set-delayed cement compositions is that the performance of the set-activating agents commonly used to selectively activate the cement compositions may be unpredictable. This may cause problems such as premature setting of the cement before placement (where the activating agent imparts an unexpectedly strong activating effect), or delayed setting of the cement after placement (where the activating agent imparts an unexpectedly weak activating effect). Both are undesirable.
  • SUMMARY OF THE INVENTION
  • The present invention relates to subterranean operations, and more particularly, to settable fluids comprising particle-size distribution-adjusting agents, and methods of using such settable fluids.
  • An example of a method of the present invention is a method of cementing, comprising the steps of: providing a cement composition comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent; activating the cement composition; placing the cement composition in a desired location; and permitting the cement composition to set therein.
  • Another example of a method of the present invention is a method of drilling in a subterranean formation comprising the step of drilling a well bore in a subterranean formation using a drilling fluid comprising a cement, a set retarder, and a particle-size distribution-adjusting agent.
  • Another example of a method of the present invention is a method of using a fluid in a subterranean formation comprising the steps of: placing a displacement fluid comprising a cement, a set retarder, a particle-size distribution-adjusting agent, and an activator composition in a well bore in a subterranean formation so as to displace a second fluid therefrom.
  • An example of a composition of the present invention is a settable fluid comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent.
  • Another example of a composition of the present invention is an activator composition for activating a settable fluid comprising a mixture of triethanolamine and an alkali metal hydroxide.
  • Another example of a composition of the present invention is a particle-size distribution-adjusting agent for adjusting the particle-size distribution of a settable fluid to a desired range, the particle-size distribution-adjusting agent comprising a cationic polymer.
  • The features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of exemplary embodiments, which follows.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • A more complete understanding of the present disclosure and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, wherein:
  • FIG. 1 depicts a graphical representation of the results of a rheology test performed on an exemplary embodiment of a settable fluid of the present invention.
  • FIG. 2 depicts a graphical representation of the results of a particle-size distribution test performed on a variety of settable fluids, including exemplary embodiments of the settable fluids of the present invention.
  • FIG. 3 depicts a graphical representation of the results of a particle-size distribution test performed on a variety of settable fluids, including exemplary embodiments of the settable fluids of the present invention.
  • FIG. 4 depicts a graphical representation of the results of a particle-size distribution test performed on a variety of settable fluids, including exemplary embodiments of the settable fluids of the present invention.
  • FIG. 5 depicts a graphical representation of the results of a thickening time test performed on exemplary embodiments of the settable fluids of the present invention.
  • FIG. 6 depicts a graphical representation of the results of a compressive strength test performed on exemplary embodiments of settable fluids of the present invention.
  • While the present invention is susceptible to various modifications and alternative forms, specific exemplary embodiments thereof have been shown in the drawings and are herein described. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
  • DESCRIPTION OF EXEMPLARY EMBODIMENTS
  • The present invention relates to subterranean operations, and more particularly, to settable fluids comprising particle-size distribution-adjusting agents, and methods of using such settable fluids.
  • The settable fluids of the present invention generally comprise a cement, water, a set retarder, and a particle-size distribution-adjusting agent. Optionally, other additives suitable for use in a settable fluid may be added. Generally, the settable fluids of the present invention have a density in the range of from about 4 to about 25 pounds per gallon. In certain exemplary embodiments, the settable fluids of the present invention have a density in the range of from about 10 to about 25 pounds per gallon.
  • Any cements suitable for use in subterranean applications are suitable for use in the present invention. Furthermore, any cements suitable for use in surface applications, e.g., construction cements, are suitable for use in the present invention. In certain exemplary embodiments, the improved settable fluids of the present invention comprise a hydraulic cement. A variety of hydraulic cements are suitable for use including those comprised of calcium, aluminum, silicon, oxygen, and/or sulfur, which set and harden by reaction with water. Such hydraulic cements include, but are not limited to, Portland cements, pozzolana cements, gypsum cements, high alumina content cements, silica cements, and high alkalinity cements.
  • The water present in the settable fluids of the present invention may be from any source provided that it does not contain an excess of compounds that adversely affect other compounds in the settable fluids. For example, a settable fluid of the present invention can comprise fresh water, salt water (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated salt water), or seawater. The water may be present in an amount sufficient to produce a pumpable slurry. Generally, the water is present in the settable fluids of the present invention in an amount in the range of from about 25% to about 150% by weight of cement (“bwoc”) therein. In certain exemplary embodiments, the water is present in the settable fluids of the present invention in an amount in the range of from about 40% to about 55% bwoc therein.
  • The particle-size distribution-adjusting agent in the settable fluids of the present invention may be any compound that desirably affects the particle-size distribution of the settable fluid such that the settable fluid's rheology remains desirably stable for a chosen period of time. Among other benefits, the presence of the particle-size distribution-adjusting agent in the settable fluids may forestall the onset of gelation for a desired period of time. Accordingly, certain embodiments of the settable fluids of the present invention are capable of remaining stable in a slurry state for several weeks or more before being activated by the addition of an activator composition. Among other benefits, the presence of the particle-size distribution-adjusting agent in the settable fluid tends to cause smaller particles in the settable fluid to agglomerate, thereby tending to narrow the distribution range of the size of the particles in the settable fluid. One example of a suitable particle-size distribution-adjusting agent is a cationic polymer. Examples of cationic polymers suitable for use with the present invention include, but are not limited to, cationic polyacrylamides, cationic hydroxyethyl cellulose, poly(dimethyldiallylammonium chloride), and cationic starches. In an exemplary embodiment, the cationic polymer used in the settable fluids of the present invention is a cationic starch. A commercially available example of a cationic starch is available under the tradename “REDIBOND 5330 A,” from National Starch Co. of Bridgewater, Conn. Generally, the particle-size distribution-adjusting agent may be present in the settable fluid in an amount sufficient to adjust the particle-size distribution of the settable fluid to a desired range. More particularly, the particle-size distribution-adjusting agent may be present in the settable fluid in an amount in the range of from about 0.01% to about 4% bwoc.
  • The settable fluids of the present invention further comprise a set retarder. Generally, any set retarder may be used with the settable fluids of the present invention. In certain exemplary embodiments, the set retarders used in the present invention comprise phosphonic acid derivatives, such as those that are described in U.S. Pat. No. 4,676,832, the relevant disclosure of which is hereby incorporated herein. Commercially available examples of a suitable set retarder include those available from Monsanto Corporation of St. Louis, Mo. under the tradename “DEQUEST.” In certain exemplary embodiments of the present invention, a sodium salt of a phosphonic acid commercially available from Monsanto Corporation of St. Louis, Mo. under the tradename “DEQUEST 2006” is used. Generally, the set retarder is present in the settable fluids of the present invention in an amount in the range of from about 0.1% to about 5% bwoc.
  • Optionally, the settable fluids of the present invention may further comprise a yield stress reducing agent. The use of such yield stress reducing agents may be particularly beneficial in certain exemplary embodiments where a densified settable fluid is used. Among other benefits, the use of a yield stress reducing agent may facilitate pumping of the densified settable fluid, inter alia, by reducing the force required to move the densified settable fluid from a static position. While the present invention is not limited by any particular theory, it is believed that the yield stress reducing agent, inter alia, increases the repulsive force between cement particles, thereby preventing them from approaching each other. An example of a suitable yield stress reducing agent is a sulfonated melamine formaldehyde condensate that is commercially available under the tradename “MELADYNE” from Handy Chemicals, Ltd., of Beachwood, Ohio. Another example of a suitable yield stress reducing agent is a sulfite adduct of an acetone formaldehyde condensate, commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the tradename “CFR-3.” Another example of a suitable yield stress reducing agent is a sulfonated naphthalene condensate, commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the tradename “CFR-6.” One of ordinary skill in the art, with the benefit of this disclosure, will be able to identify a suitable yield stress reducing agent for a particular application.
  • Optionally, the settable fluids of the present invention may further comprise an expanding additive. The expanding additive may be any component suitable for incorporating gas into the settable fluid. Where the expanding additive is a gas, gasification of the settable fluid may be achieved at the surface in one preferred embodiment, and the gasified settable fluid may be then introduced into the subterranean formation and permitted to set therein into a resilient, ductile, and tough gasified cement mass. Alternatively, the settable fluid may be gasified during, or after, its placement in the subterranean formation, by the inclusion of a particular expanding additive within the settable fluid. Where an expanding additive in particulate form is used, aluminum powder, gypsum blends, and deadburned magnesium oxide are preferred. Preferred expanding additives comprising aluminum powder are commercially available under the tradenames “GAS-CHEK®” and “SUPER CBL” from Halliburton Energy Services, Inc., of Duncan, Okla.; a preferred expanding additive comprising a blend containing gypsum is commercially available under the tradename “MICROBOND” from Halliburton Energy Services, Inc., of Duncan, Okla.; and preferred expanding additives comprising deadburned magnesium oxide are commercially available under the tradenames “MICROBOND M” and “MICROBOND HT” from Halliburton Energy Services, Inc., of Duncan, Okla. Such preferred expanding additives are described in commonly-owned U.S. Pat. Nos. 4,304,298; 4,340,427; 4,367,093; 4,450,010; and 4,565,578, the relevant disclosures of which are hereby incorporated herein by reference. One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine the appropriate amount of expanding additive to include in the settable fluids of the present invention for a particular application.
  • Where the settable fluids of the present invention are to be foamed (e.g., to reduce the density of the settable fluid, or to improve its mechanical properties), the settable fluid is foamed in one exemplary embodiment by direct addition of the expanding additive into the settable fluid. For instance, where the settable fluid is foamed by the direct injection of gas into the composition, the gas utilized can be air or any suitable inert gas, such as nitrogen, or even a mixture of such gases. In certain exemplary embodiments, nitrogen is used. Where foaming is achieved by direct injection of gas, the gas may be present in the composition in an amount sufficient to foam the composition, generally in an amount in the range of from about 0.01% to about 60% by volume of the composition. In another preferred embodiment, the settable fluid is foamed by gas generated by a reaction between the cement slurry and an expanding additive present in the settable fluid in particulate form. For example, the composition may be foamed by hydrogen gas generated in situ as the product of a reaction between the slurry and fine aluminum powder present in the settable fluid. To stabilize the foam, surfactants optionally may be added to the settable fluid. Surfactant compositions suitable for use in the present invention are described in U.S. Pat. Nos. 6,063,738 and 6,367,550, the relevant disclosures of which are hereby incorporated herein by reference.
  • Additional additives may be added to the settable fluids of the present invention as deemed appropriate by one skilled in the art with the benefit of this disclosure. Examples of such additives include, inter alia, fluid loss control additives, salts, vitrified shale, fly ash, fumed silica, bentonite, fixed-density weighting agents, and the like. An example of a suitable fluid loss control additive is commercially available from Halliburton Energy Services, Inc., of Duncan, Okla., under the tradename “HALAD® 9.”
  • To ready the settable fluids of the present invention for use (e.g., surface use, or placement in a subterranean formation, for example), an activator composition of the present invention may be added. The activator compositions of the present invention generally comprise a mixture of at least one alkali or alkaline earth metal hydroxide, and a trialkanolamine. A wide variety of alkali or alkaline earth metal hydroxides are suitable for use in the present invention. In certain exemplary embodiments, the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide and potassium hydroxide. A wide variety of trialkanolamines are suitable for use in the present invention. In certain exemplary embodiments, the trialkanolamine is selected from the group consisting of: triethanolamine (“TEA”), tripropanolamine, and triisopropanolamine. In certain exemplary embodiments, the trialkanolamine is TEA. Such combination has been found to provide a synergistic effect, resulting in settable fluids that achieve desirably high compressive strengths at a faster rate than would be achieved had the TEA or alkali metal hydroxide been added individually. In certain exemplary embodiments, the alkali metal hydroxide is sodium hydroxide. Generally, the activator composition may be added to a settable fluid of the present invention in an amount sufficient to enable the settable fluid to achieve a desired compressive strength and a desired thickening time. More particularly, the activator composition may be added to the settable fluid in an amount in the range of from about 0.1% to 5% bwoc. Generally, the alkali or alkaline earth metal hydroxide may be present in the activator composition in an amount in the range of from about 50% to about 99.9% by weight. Generally, the trialkanolamine may be present in the activator composition in an amount in the range of from about 0.1% to about 50% by weight.
  • The activator composition may be added in a variety of ways. For example, the activator composition may be added to the settable fluid while the latter is still in storage. In certain other exemplary embodiments, the activator composition may be injected into the settable fluid at the same time that the settable fluid is injected into the subterranean formation. Among other benefits, the injection of the activator composition while the settable fluid is injected into the formation may assist in minimizing the development within the settable fluid of localized regions having a high activator concentration.
  • In certain exemplary embodiments of the present invention, the settable fluid may be formulated as a “densified” settable fluid (e.g., formulated with a significantly higher density than that which is calculated to be necessary for its intended use) before the addition of the activator composition. Such a densified settable fluid may be provided in a variety of ways, such as through the addition of high-density particles, or by formulating the settable fluid with less water than necessary for its intended use. Among other benefits, the employment of a densified settable fluid will facilitate the addition of an activator composition in the form of a dilute solution. For example, if a settable fluid having a 16.4 lb/gallon density is required, a densified settable fluid having a density of, say, 17.0 lb/gallon or higher may be provided and activated with an activator composition diluted with sufficient water to ultimately provide the desired 16.4 lb/gallon slurry. Among other benefits, the addition of the activator composition in a dilute solution to a densified settable fluid may minimize the possibility of developing localized zones having excessive activator concentration due to inadequate mixing.
  • In one embodiment of the methods of the present invention, the settable fluids of the present invention may be used as a drilling fluid. A drilling fluid of the present invention comprising a cement, a set retarder, and a particle-size distribution-adjusting agent may be used to drill a subterranean formation, e.g., by circulating the drilling fluid while drilling a well in contact with a drill bit and a subterranean formation. In an exemplary embodiment, the drilling fluid is used to drill a well bore in a subterranean formation, after which casing is placed within the well bore. In this exemplary embodiment, an activator composition of the present invention is then mixed with the drilling fluid, and the drilling fluid is permitted to set behind the casing. Accordingly, an exemplary method of the present invention comprises the step of drilling a well bore in a subterranean formation using a drilling fluid comprising a cement, a set retarder, and a particle-size distribution-adjusting agent. Additional steps include, but are not limited to, placing a casing string within the well bore; mixing an activator composition of the present invention with the drilling fluid; and permitting the drilling fluid to set behind the casing string.
  • In another embodiment, the settable fluids of the present invention may be used as a displacement fluid. For example, a displacement fluid of the present invention comprising a cement, a set retarder, a particle-size distribution-adjusting agent, and an activator composition of the present invention may be placed in a well bore that has been drilled (with a drilling fluid) in a subterranean formation so as to partially or completely displace the drilling fluid from the well bore. Generally, after the displacement fluid has been placed in the well bore, a cement composition is subsequently placed in the well bore so as to partially or completely displace the displacement fluid therefrom. Any portion of the displacement fluid that is not displaced by the cement composition, and that inadvertently remains within the well bore, will develop sufficient compressive strength so as not to adversely affect the integrity of the resultant cement sheath. One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine the appropriate balance of set retarder and activator composition such that the displacement fluid will not set for a desired period of time, and will then develop compressive strength thereafter. Accordingly, an exemplary method of the present invention comprises the steps of: placing a displacement fluid comprising a cement, a set retarder, a particle-size distribution-adjusting agent, and an activator composition in a well bore in a subterranean formation so as to displace a second fluid therefrom. Additional steps include, but are not limited to, placing a casing string within the well bore; placing a cement composition within the well bore so as to displace at least a portion of the displacement fluid therefrom; permitting the cement composition to set therein; and permitting any undisplaced displacement fluid to set therein.
  • Another example of a method of the present invention is a method of cementing, comprising the steps of: providing a cement composition comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent; activating the cement composition; placing the cement composition in a desired location; and permitting the cement composition to set therein. Additional steps include, but are not limited to, permitting the cement composition to remain in a slurry state for at least twenty four hours before being activated; permitting the cement composition to remain in a slurry state for at least two weeks before being activated; and permitting the cement composition to remain in a slurry state for more than two weeks before being activated.
  • To facilitate a better understanding of the present invention, the following examples of some exemplary embodiments are given. In no way should such examples be read to limit the scope of the invention.
  • EXAMPLES
  • The cement slurry preparation, thickening time, free water content, and compressive strengths in the examples were measured according to API Specification 10A, Twenty-Third Edition, April, 2002.
  • Example 1
  • Sample Composition No. 1 comprised Class H cement, to which 34.52% water bwoc and 0.933% DEQUEST 2006 bwoc were added. Within four days, the viscosity of Sample Composition No. 1 had increased to such an extent that Sample Composition No. 1 could not be pumped.
    TABLE 1
    Fann 35 Rheometer Settings (rpm)
    Day 600 300 200 100 6 3
    0 234 128 92 51 8 6
    1 245 150 110 68 25 20
    3 275 182 145 103 55 47
    4 Too thick for rheology measurements
  • Example 2
  • Sample Composition No. 2 comprised Class H cement, to which 34.52% water bwoc was added. Next, 0.267% HALAD® 9 bwoc was added, along with 0.098% CFR-6 bwoc, 0.233% REDIBOND 5330 A bwoc, and 0.933% DEQUEST 2006 bwoc. The density of Sample Composition No. 2 was measured to be 17.0 lb/gallon.
  • The rheology of Sample Composition No. 2 was measured using a Fann 35 Rheometer viscometer. The results are set forth in the table below, as well as in FIG. 1.
    TABLE 2
    Fann 35 Rheometer Settings (rpm)
    Day 600 300 200 100 6 3
    0 346 200 146 80 26 20
    1 440 240 170 96 16 10
    3 430 236 164 94 14 8
    6 414 228 164 92 14 8
    8 410 230 164 94 14 8
    9 430 246 170 100 16 10
    10 444 250 180 116 18 12
    12 450 253 184 116 18 12
  • On Day 13, Sample Composition No. 2 was too thick for its viscosity to be tested.
  • The above example demonstrates, inter alia, that the settable fluids of the present invention comprising particle-size distribution-adjusting agents may maintain their original Theological properties during a storage period of at least about two weeks.
  • Example 3
  • Two sample settable fluids were prepared comprising Class H cement and water, such that the density of each settable fluid was 16.5 pounds per gallon. A particle-size distribution-adjusting agent was then added to one sample settable fluid (Sample Composition No. 4). The particle size distribution of each sample composition was measured according to the following procedure. First, cement was added to a circulating stream of water, at which point the particle-size distribution of the mixture was measured. For Sample Composition No. 4, a known amount of the particle-size distribution-adjusting agent was then added to the circulating stream, and the particle-size distribution was again measured; additional amounts of the particle-size distribution-adjusting agent were added, and additional particle-size distribution measurements were taken, until no further change in particle size was observed.
  • The particle sizes in the sample settable fluids were measured on a Malvern Particle Size Analyzer, available from Malvern Instruments Ltd., of Worcestershire, UK. For a given particle size, the Particle Size Analyzer identifies the volume percentage of particles in the sample that are beneath that particle size. The Particle Size Analyzer also provides a median particle size. Another parameter reported by the Particle Size Analyzer is the “Span,” which describes the width of the distribution independent of the median particle size. The Particle Size Analyzer also reports the “Uniformity” of the particle-size distribution, which is a measure of the absolute deviation from the median particle size, and which is also independent of the median particle size. The lower the value reported for the “Uniformity,” the smaller the absolute deviation from the median particle size, and thus the more uniform the settable fluid.
  • Sample Composition No. 3 did not further comprise a particle-size distribution-adjusting agent.
  • Sample Composition No. 4, a settable fluid of the present invention, further comprised 0.233% bwoc of REDIBOND 5330 A.
  • The results of the particle-size distribution tests are reproduced in Tables 3, 4, 5, and 6, below, and also in FIGS. 2, 3, and 4.
    TABLE 3
    Indicated Individual Volume Percent of
    Particle Size Particles Having Indicated Particle Size
    (microns) Sample Composition No. 3 Sample Composition No. 4
    0.667 0.37 0.21
    1.04 0.43 0.25
    1.52 0.34 0.19
    2.05 0.31 0.15
    2.98 0.5 0.21
    4.02 0.82 0.37
    5.03 1.1 0.57
    5.84 1.28 0.73
    6.78 1.46 0.92
    7.88 1.63 1.11
    9.86 1.85 1.43
  • TABLE 4
    Indicated Individual Volume Percent of
    Particle Size Particles Having Indicated Particle Size
    (microns) Sample Composition No. 3 Sample Composition No. 4
    10.62 1.92 1.53
    20.84 2.65 2.35
    30.29 2.99 2.91
    40.86 2.98 3.52
    51.15 2.61 3.86
    59.41 2.19 3.68
    69 1.7 3.18
    74.36 1.44 2.82
    86.36 0.96 2.02
    93.07 0.74 1.59
    100.3 0.56 1.25
  • TABLE 5
    Indicated Cumulative Volume % of Particles Having A Particle
    Particle Size Size Less Than The Indicated Particle Size
    (microns) Sample Composition No. 3 Sample Composition No. 4
    0.532 0.17 0.09
    0.667 1.01 0.56
    1.04 3.64 2.05
    1.52 5.53 3.13
    2.05 6.77 3.78
    2.98 8.77 4.64
    4.02 11.55 5.85
    5.03 14.57 7.34
    5.84 17.05 8.71
    6.78 19.89 10.44
    7.88 23.06 12.56
    9.86 28.37 16.52
  • TABLE 6
    Indicated Cumulative Volume % of Particles Having A Particle
    Particle Size Size Less Than The Indicated Particle Size
    (microns) Sample Composition No. 3 Sample Composition No. 4
    10.62 30.29 18.05
    20.84 51.16 35.93
    30.29 65.49 49.29
    40.86 77.65 62.44
    51.15 85.93 73.83
    59.41 90.54 81.32
    69 94.19 87.97
    74.36 95.63 90.79
    86.36 97.78 95.24
    93.07 98.52 96.83
    100.3 99.08 98.08
    Median Particle 26.35 35.79
    Size
    Span 2.72 2.38
    Uniformity 0.855 0.797
  • The above example illustrates, inter alia, that the settable fluids of the present invention, comprising particle-size distribution-adjusting agents, demonstrate improved uniformity and homogeneity of particle-size distribution.
  • Example 4
  • Sample Composition No. 5 comprised Class G cement, to which 40.00% water bwoc was added. Next, 0.267% HALAD-9 bwoc was added, along with 0.098% CFR-6 bwoc, 0.233% bwoc REDIBOND 5330 A, and 0.933% DEQUEST 2006 bwoc. The density of Sample Composition No. 5 was measured to be 16.32 ppg.
  • The rheology of Sample Composition No. 5 was measured using a Fann 35 Rheometer. The results are set forth in the table below.
    TABLE 7
    Fann 35 Rheometer Settings (rpm)
    Day 600 300 200 100 6 3
    0 282 165 121 72 26 21
    3 300 179 132 82 31 27
    7 298 185 135 83 31 26
    9 295 191 142 90 46 34
    11 310 201 151 102 60 54
  • The above example demonstrates, inter alia, and that settable fluids of the present invention comprising Class G cement substantially maintain their original rheological properties for at least about two weeks.
  • Example 5
  • Sample Composition No. 6 comprised Class A cement, to which 42.00% water bwoc was added. Next, 0.534% HALAD-9 bwoc was added, along with 0.098% CFR-6 bwoc, 0.233% bwoc REDIBOND 5330 A, and 0.933% DEQUEST 2006 bwoc. The density of Sample Composition No. 6 was measured to be 16.03 ppg.
  • The rheology of Sample Composition No. 6 was measured using a Fann 35 Rheometer. The results are set forth in the table below.
    TABLE 8
    Fann 35 Rheometer Settings (rpm)
    Day 600 300 200 100 6 3
    0 323 186 134 78 15 12
    3 284 164 119 67 7 4
    5 285 166 119 68 8 5
    7 308 186 134 76 9 7
    11 308 192 140 82 12 9
  • The above example demonstrates, inter alia, that settable fluids of the present invention comprising Class A cement may maintain their original rheological properties for at least about two weeks.
  • Example 6
  • Sample Composition No. 7 had a composition identical to that in Sample Composition No. 2, except that DEQUEST 2006 was replaced by a molar equivalent of DEQUEST 2000.
  • The rheology of Sample Composition No. 7 was measured using a Fann 35 Rheometer. The results are set forth in the table below.
    TABLE 9
    Fann 35 Rheometer Settings (rpm)
    Day 600 300 200 100 6 3
    0 340 194 142 82 18 14
    2 460 280 210 124 24 18
    4 450 270 192 116 26 20
    8 400 256 194 124 56 44
    10 430 264 200 134 82 68
  • On Day 12, Sample Composition No. 7 was too thick for its viscosity to be measured.
  • The above example illustrates, inter alia, that settable fluids of the present invention comprising DEQUEST 2000 may maintain their original rheological properties for at least about two weeks.
  • Example 7
  • Sample Composition No. 8 comprised Class H cement, 34.52% water bwoc, 0.267% HALAD-9 bwoc, 0.098% CFR-6 bwoc, 0.933% DEQUEST 2000 bwoc, and 0.233% REDIBOND 5330 A bwoc. The density of Sample Composition No. 8 was measured to be 16.76 ppg.
  • The rheology and the free water content of the slurry were measured at the indicated time intervals in Table 10. Additionally, a composite of the slurry was activated at the time intervals reported in Table 10, and the set times were measured. The activator composition comprised 3.78% water bwoc, 0.07% TEA bwoc, and 0.75% sodium hydroxide bwoc. The density of Sample Composition No. 8, after the injection of the activator composition, was measured to be 16.5 ppg. The results of the testing are set forth in the table below:
    TABLE 10
    Fann 35 Rheometer Settings (rpm) Set Time Free Water
    Day 600 300 200 100 6 3 (hrs) %
    1 >300 223 159 92 18 16 4:00 0.4%
    4 >300 222 152 80 9 6 3:20 0.8%
    7 >300 229 160 86 11 8 4:00 0.8%
    10 >300 274 193 109 18 16 3:45 0.8%
  • The above example demonstrates, inter alia, that the settable fluids of the present composition may be taken from storage at any time within about two weeks or more after their initial preparation, activated with an activator composition of the present invention, to be utilized in a desired application. The storage time did not appear to significantly affect the set characteristics or other properties of the cement.
  • On Day 4, the density of a set composite of Sample Composition No. 8 was measured at the top, middle, and bottom, by mechanically separating the Sample Composition into top, middle, and bottom portions, and measuring the density of each portion. The top set density was measured to be 16.96 lb/gallon. The middle set density was measured to be 17.12 lb/gallon. The bottom set density was measured to be 17.24 lb/gallon. This demonstrates, inter alia, that the slurry suspension parameters of the settable fluids of the present invention are substantially uniform, with minimum settling.
  • Example 8
  • Sample settable fluids were prepared, each having a composition identical to that of Sample Composition No. 2, except that each comprised a different combination of various activators.
  • Sample Composition No. 9 did not comprise an activator.
  • Sample Composition No. 10 comprised 0.5% TEA bwoc.
  • Sample Composition No. 11 comprised 0.75% sodium hydroxide bwoc.
  • Sample Composition No. 12 comprised 0.75% sodium hydroxide bwoc and 2% calcium chloride bwoc.
  • Sample Composition No. 13 comprised 0.5% TEA bwoc and 0.75% sodium hydroxide bwoc, an activator composition of the present invention.
  • The results of the testing are reproduced in the table below.
    TABLE 11
    24 Hour Thickening
    Compressive Time
    TEA % NaOH % CaCl2 % Strength at (hrs: min) at
    Sample No. bwoc bwoc bwoc 190 F. 190 F.
    Sample
    0 0 0   103 psi 6:00
    Composition No. 9
    Sample 0.5 0 0   50 psi 0:47
    Composition No. 10
    Sample 0 0.75 0 Did not set 6:50
    Composition No. 11
    Sample 0 0.75 2.0   50 psi Not measured
    Composition No. 12
    Sample 0.5 0.75 0 4,750 psi 0:29
    Composition No. 13
  • The above example demonstrates, inter alia, the possible effect of combining an alkali metal hydroxide and TEA in the activator compositions of the present invention.
  • Example 9
  • Sample settable fluids were prepared having a composition identical to that of Sample Composition No. 2, further comprising 0.07% TEA bwoc, and various amounts of sodium hydroxide, to determine the effect of sodium hydroxide on thickening time and compressive strength development.
  • Sample Composition No. 14 comprised 0.11% sodium hydroxide bwoc.
  • Sample Composition No. 15 comprised 0.75% sodium hydroxide bwoc.
  • Sample Composition No. 16 comprised 1.0% sodium hydroxide bwoc.
  • The results of the testing are set forth in the table below, as well as in FIG. 5 and FIG. 6.
    TABLE 12
    Time to 500 psi 24 Hour Thickening
    TEA % NaOH % strength Compressive Time (hrs:min)
    Sample No. bwoc bwoc (hours) Strength at 190 F. at 190 F.
    Sample 0.07 0.11 42   50 psi 10:27
    Composition No. 14
    Sample 0.07 0.75 18 3,537 psi  6:00
    Composition No. 15
    Sample 0.07 1.0  12 3,840 psi  4:06
    Composition No. 16
  • As may be seen particularly with reference to FIGS. 4 and 5, the presence of sodium hydroxide in the activator compositions of the present invention may impart a substantially linear effect on thickening time and compressive strength development.
  • Therefore, the present invention is well adapted to carry out the objects and attain the ends and advantages mentioned as well as those that are inherent therein. While the invention has been depicted, described, and is defined by reference to exemplary embodiments of the invention, such a reference does not imply a limitation on the invention, and no such limitation is to be inferred. The invention is capable of considerable modification, alternation, and equivalents in form and function, as will occur to those ordinarily skilled in the pertinent arts and having the benefit of this disclosure. The depicted and described embodiments of the invention are exemplary only, and are not exhaustive of the scope of the invention. Consequently, the invention is intended to be limited only by the spirit and scope of the appended claims, giving full cognizance to equivalents in all respects.

Claims (122)

1. A method of cementing, comprising the steps of: providing a cement composition comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent; activating the cement composition; placing the cement composition in a desired location; and permitting the cement composition to set therein.
2. The method of claim 1 wherein the cement composition further comprises water, and wherein the water is fresh water, salt water, brine, sea water, or a mixture thereof.
3. The method of claim 2 wherein the water is present in the cement composition in an amount sufficient to form a pumpable slurry.
4. The method of claim 3 wherein the water is present in the cement composition in an amount in the range of from about 25% to about 150% by weight of the cement.
5. The method of claim 1 wherein the hydraulic cement is a Portland cement, pozzolana cement, gypsum cement, high alumina cement, silica cement, or a high alkalinity cement.
6. The method of claim 2 wherein the step of providing a cement composition comprises providing a densified cement composition.
7. The method of claim 6 wherein the step of providing a densified cement composition comprises the step of adding high-density particles to the cement composition.
8. The method of claim 6 wherein the step of providing a densified cement composition comprises the step of reducing the amount of water in the cement composition.
9. The method of claim 6 wherein the cement composition further comprises a yield stress reducing agent.
10. The method of claim 1 wherein the set retarder is phosphonic acid or a phosphonic acid derivative.
11. The method of claim 10 wherein the phosphonic acid derivative is a sodium salt of phosphonic acid.
12. The method of claim 1 wherein the set retarder is present in the cement composition in an amount in the range of from about 0.1% to about 5% by weight of the cement.
13. The method of claim 1 wherein the step of activating the cement composition comprises adding an activator composition to the cement composition.
14. The method of claim 13 wherein the activator composition is added in an amount sufficient to enable the cement composition to achieve a desired compressive strength in a desired thickening time.
15. The method of claim 14 wherein the activator composition is added in an amount in the range of from about 0.1 to about 5% by weight of the cement.
16. The method of claim 15 wherein the activator composition comprises a mixture of a trialkanolamine and an alkali or alkaline earth metal hydroxide.
17. The method of claim 16 wherein the trialkanolamine is selected from the group consisting of: triethanolamine, tripropanolamine, and triisopropanolamine.
18. The method of claim 16 wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide and potassium hydroxide.
19. The method of claim 16 wherein the trialkanolamine is present in an amount in the range of from about 0.1% to about 50% by weight of the activator composition.
20. The method of claim 16 wherein the alkali metal hydroxide is present in an amount in the range of from about 50% to about 99.9% by weight of the activator composition.
21. The method of claim 18 wherein the alkali metal hydroxide is sodium hydroxide.
22. The method of claim 16 wherein the activator composition is added to the cement composition in the form of a solution diluted by water.
23. The method of claim 16 wherein the activator composition is added to the cement composition while the cement composition is in storage.
24. The method of claim 16 wherein the activator composition is added to the cement composition while the cement composition is being placed in the subterranean formation.
25. The method of claim 1 wherein the particle-size distribution-adjusting agent is present in the cement composition in an amount sufficient to adjust the particle-size distribution of the cement composition to a desired range.
26. The method of claim 1 wherein the cement composition comprising the particle-size distribution-adjusting agent has a particle-size distribution that is narrower than that of the cement composition lacking the particle-size distribution-adjusting agent.
27. The method of claim 1 wherein the particle-size distribution-adjusting agent is present in the cement composition in an amount in the range of from about 0.01% to about 4% by weight of the cement.
28. The method of claim 1 wherein the particle-size distribution-adjusting agent is a compound that affects the particle-size distribution of the cement such that the rheology of the cement composition remains substantially stable for a desired period of time.
29. The method of claim 1 wherein the particle-size distribution-adjusting agent is a cationic polymer.
30. The method of claim 29 wherein the cationic polymer is selected from the group consisting of: cationic polyacrylamides; cationic hydroxyethyl cellulose; poly(dimethyldiallylammonium chloride); and cationic starches.
31. The method of claim 1 wherein the cement composition further comprises a surfactant, a dispersant, a salt, mica, a formation conditioning agent, a fixed-density weighting agent, vitrified shale, fumed silica, bentonite, fly ash, a fluid loss control additive, an expanding additive, a defoamer, a viscosifier, or a mixture thereof.
32. The method of claim 1 further comprising the step of permitting the cement composition to remain in a slurry state for at least 24 hours.
33. The method of claim 1 further comprising the step of permitting the cement composition to remain in a slurry state for at least two weeks.
34. The method of claim 1 further comprising the step of permitting the cement composition to remain in a slurry state for more than two weeks.
35. The method of claim 1 wherein the suspension properties of the cement composition are substantially uniform throughout the cement composition.
36. The method of claim 32 wherein the rheological properties of the cement composition remain substantially constant while the cement composition remains in a slurry state.
37. The method of claim 9 wherein the yield stress reducing agent is selected from the group consisting of a sulfonated melamine formaldehyde condensate; a sulfonated napthalene condensate; and a sulfite adduct of an acetone formaldehyde condensate.
38. The method of claim 1 wherein the cement composition has a density in the range of from about 4 pounds per gallon to about 25 pounds per gallon.
39. The method of claim 1 wherein the cement composition further comprises water, and wherein the water is present in the cement composition in an amount in the range of from about 25% to about 150% by weight of the cement; wherein the set retarder is a phosphonic acid or phosphonic acid derivative; wherein the step of activating the cement composition comprises adding an activator composition to the cement composition; wherein the activator composition comprises a mixture of triethanolamine and an alkali metal hydroxide; wherein the particle-size distribution-adjusting agent is present in the cement composition in an amount in the range of from about 0.01% to about 4% by weight of the cement; wherein the particle-size distribution-adjusting agent is a cationic polymer.
40. A method of drilling in a subterranean formation comprising the step of drilling a well bore in a subterranean formation using a drilling fluid comprising a cement, a set retarder, and a particle-size distribution-adjusting agent.
41. The method of claim 40 further comprising the step of placing a casing string within the well bore.
42. The method of claim 40 further comprising the step of mixing an activator composition with the drilling fluid.
43. The method of claim 40 further comprising the step of permitting the drilling fluid to set behind the casing string.
44. The method of claim 40 wherein the drilling fluid further comprises water, and wherein the water is fresh water, salt water, brine, sea water, or a mixture thereof.
45. The method of claim 44 wherein the water is present in the drilling fluid in an amount in the range of from about 25% to about 150% by weight of the cement.
46. The method of claim 40 wherein the hydraulic cement is a Portland cement, pozzolana cement, gypsum cement, high alumina cement, silica cement, or a high-alkalinity cement.
47. The method of claim 40 wherein the drilling fluid further comprises a yield stress reducing agent.
48. The method of claim 40 wherein the set retarder is phosphonic acid or a phosphonic acid derivative.
49. The method of claim 48 wherein the phosphonic acid derivative is a sodium salt of phosphonic acid.
50. The method of claim 40 wherein the set retarder is present in the drilling fluid in an amount in the range of from about 0.1% to about 5% by weight of the cement.
51. The method of claim 42 wherein the activator composition is added in an amount sufficient to enable the drilling fluid to achieve a desired compressive strength in a desired thickening time.
52. The method of claim 51 wherein the activator composition is added in an amount in the range of from about 0.1 to about 5% by weight of the cement.
53. The method of claim 52 wherein the activator composition comprises a mixture of a trialkanolamine and an alkali or alkaline earth metal hydroxide.
54. The method of claim 53 wherein the trialkanolamine is selected from the group consisting of: triethanolamine, tripropanolamine, and triisopropanolamine.
55. The method of claim 53 wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide and potassium hydroxide.
56. The method of claim 53 wherein the trialkanolamine is present in an amount in the range of from about 0.1% to about 50% by weight of the activator composition.
57. The method of claim 53 wherein the alkali metal hydroxide is present in an amount in the range of from about 50% to about 99.9% by weight of the activator composition.
58. The method of claim 55 wherein the alkali metal hydroxide is sodium hydroxide.
59. The method of claim 40 wherein the particle-size distribution-adjusting agent is present in the drilling fluid in an amount in the range of from about 0.01% to about 4% by weight of the cement.
60. The method of claim 40 wherein the particle-size distribution-adjusting agent is a cationic polymer.
61. The method of claim 60 wherein the cationic polymer is selected from the group consisting of: cationic polyacrylamides; cationic hydroxyethyl cellulose; poly(dimethyldiallylammonium chloride); and cationic starches.
62. The method of claim 47 wherein the yield stress reducing agent is selected from the group consisting of: a sulfonated melamine formaldehyde condensate; a sulfonated napthalene condensate; and a sulfite adduct of an acetone formaldehyde condensate.
63. A method of using a fluid in a subterranean formation comprising the step of: placing a displacement fluid comprising a cement, a set retarder, a particle-size distribution-adjusting agent, and an activator composition in a well bore in a subterranean formation so as to displace a second fluid therefrom.
64. The method of claim 63 wherein the second fluid is a drilling fluid.
65. The method of claim 63 further comprising the step of placing a casing string within the well bore.
66. The method of claim 63 further comprising the step of placing a cement composition within the well bore so as to displace at least a portion of the displacement fluid therefrom.
67. The method of claim 63 further comprising the step of permitting the cement composition to set in the well bore.
68. The method of claim 63 further comprising the step of permitting any undisplaced displacement fluid to set in the well bore.
69. The method of claim 63 wherein the displacement fluid further comprises water, and wherein the water is fresh water, salt water, brine, sea water, or a mixture thereof.
70. The method of claim 69 wherein the water is present in the displacement fluid in an amount in the range of from about 25% to about 150% by weight of the cement.
71. The method of claim 63 wherein the hydraulic cement is a Portland cement, pozzolana cement, gypsum cement, high alumina cement, silica cement, or a high alkalinity cement.
72. The method of claim 63 wherein the displacement fluid further comprises a yield stress reducing agent.
73. The method of claim 63 wherein the set retarder is phosphonic acid or a phosphonic acid derivative.
74. The method of claim 73 wherein the phosphonic acid derivative is a sodium salt of phosphonic acid.
75. The method of claim 63 wherein the set retarder is present in the displacement fluid in an amount in the range of from about 0.1% to about 5% by weight of the cement.
76. The method of claim 63 wherein the activator composition is present in an amount in the range of from about 0.1 to about 5% by weight of the cement.
77. The method of claim 63 wherein the activator composition comprises a mixture of a trialkanolamine and an alkali or alkaline earth metal hydroxide.
78. The method of claim 77 wherein the trialkanolamine is selected from the group consisting of: triethanolamine, tripropanolamine, and triisopropanolamine.
79. The method of claim 77 wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide and potassium hydroxide.
80. The method of claim 77 wherein the trialkanolamine is present in an amount in the range of from about 0.1% to about 50% by weight of the activator composition.
81. The method of claim 77 wherein the alkali metal hydroxide is present in an amount in the range of from about 50% to about 99.9% by weight of the activator composition.
82. The method of claim 79 wherein the alkali metal hydroxide is sodium hydroxide.
83. The method of claim 63 wherein the particle-size distribution-adjusting agent is present in the displacement fluid in an amount in the range of from about 0.01% to about 4% by weight of the cement.
84. The method of claim 63 wherein the particle-size distribution-adjusting agent is a cationic polymer.
85. The method of claim 84 wherein the cationic polymer is selected from the group consisting of: cationic polyacrylamides; cationic hydroxyethyl cellulose; poly(dimethyldiallylammonium chloride); and cationic starches.
86. The method of claim 72 wherein the yield stress reducing agent is selected from the group consisting of: a sulfonated melamine formaldehyde condensate; a sulfonated napthalene condensate; and a sulfite adduct of an acetone formaldehyde condensate.
87. A settable fluid comprising a hydraulic cement, a set retarder, and a particle-size distribution-adjusting agent.
88. The settable fluid of claim 87 further comprising water, wherein the water comprises fresh water, salt water, brine, seawater, or a mixture thereof.
89. The settable fluid of claim 88 wherein the water is present in an amount sufficient to form a pumpable slurry.
90. The settable fluid of claim 89 wherein the water is present in an amount in the range of from about 25% to about 150% by weight of the cement.
91. The settable fluid of claim 87 wherein the hydraulic cement is a Portland cement, pozzolana cement, gypsum cement, high alumina cement, silica cement, or a high alkalinity cement.
92. The settable fluid of claim 87 further comprising a yield stress reducing agent.
93. The settable fluid of claim 92 wherein the yield stress reducing agent is selected from the group consisting of: a sulfonated melamine formaldehyde condensate, and a sulfite adduct of an acetone formaldehyde condensate.
94. The settable fluid of claim 87 wherein the set retarder is phosphonic acid or a phosphonic acid derivative.
95. The settable fluid of claim 94 wherein the phosphonic acid derivative is a sodium salt of phosphonic acid.
96. The settable fluid of claim 87 wherein the set retarder is present in an amount in the range of from about 0.1% to about 5% by weight of the cement.
97. The settable fluid of claim 87 further comprising an activator composition.
98. The settable fluid of claim 97 wherein the activator composition is present in an amount in the range of from about 0.1% to about 5% by weight of the cement.
99. The settable fluid of claim 97 wherein the activator composition comprises a mixture of a trialkanolamine and an alkali or alkaline earth metal hydroxide.
100. The settable fluid of claim 99 wherein the trialkanolamine is selected from the group consisting of: triethanolamine, tripropanolamine, and triisopropanolamine.
101. The settable fluid of claim 99 wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of sodium hydroxide and potassium hydroxide.
102. The settable fluid of claim 101 wherein the alkali metal hydroxide is sodium hydroxide.
103. The settable fluid of claim 99 wherein the trialkanolamine is present in an amount in the range of from about 0.1% to about 50% by weight of the activator composition.
104. The settable fluid of claim 99 wherein the alkali metal hydroxide is present in an amount in the range of from about 50% to about 99.9% by weight of the activator composition.
105. The settable fluid of claim 87 wherein the particle-size distribution-adjusting agent is present in an amount sufficient to adjust the particle-size distribution of the settable fluid to a desired range.
106. The settable fluid of claim 105 wherein the particle-size distribution-adjusting agent is present in an amount in the range of from about 0.01% to about 4% by weight of the cement.
107. The settable fluid of claim 87 wherein the particle-size distribution-adjusting agent is a compound that affects the particle size distribution of the settable fluid such that the rheology of the settable fluid remains substantially stable for a desired period of time.
108. The settable fluid of claim 87 wherein the particle-size distribution-adjusting agent is a cationic polymer.
109. The settable fluid of claim 108 wherein the cationic polymer is selected from the group consisting of cationic polyacrylamides; cationic hydroxyethyl cellulose; poly(dimethyldiallylammonium chloride); and cationic starches.
110. The settable fluid of claim 87 further comprising a surfactant, a dispersant, a salt, mica, a formation conditioning agent, a fixed-density weighting agent, vitrified shale, fumed silica, bentonite, fly ash, a fluid loss control additive, an expanding additive, a defoamer, a viscosifier, or a mixture thereof.
111. The settable fluid of claim 87 wherein the suspension properties of the settable fluid are substantially uniform throughout the settable fluid.
112. The settable fluid of claim 87 having a density in the range of from about 4 pounds per gallon to about 25 pounds per gallon.
113. The settable fluid of claim 87 further comprising water, wherein the water is present in an amount in the range of from about 25% to about 150% by weight of the cement; wherein the set retarder is a phosphonic acid or phosphonic acid derivative; wherein the settable fluid further comprises an activator composition; wherein the activator composition comprises a mixture of triethanolamine and an alkali metal hydroxide; wherein the particle-size distribution-adjusting agent is present in the settable fluid in an amount in the range of from about 0.01% to about 4% by weight of the cement; wherein the particle-size distribution-adjusting agent is a cationic polymer.
114. An activator composition for activating a settable fluid comprising a mixture of a trialkanolamine and an alkali or alkaline earth metal hydroxide.
115. The activator composition of claim 114 wherein the trialkanolamine is selected from the group consisting of: triethanolamine, tripropanolamine, and triisopropanolamine.
116. The activator composition of claim 114 wherein the alkali or alkaline earth metal hydroxide is selected from the group consisting of: sodium hydroxide and potassium hydroxide.
117. The activator composition of claim 114 wherein the trialkanolamine is present in an amount in the range of from about 0.1% to about 50% by weight.
118. The activator composition of claim 114 wherein the alkali metal hydroxide is present in an amount in the range of from about 50% to about 99.9% by weight.
119. The activator composition of claim 116 wherein the alkali metal hydroxide is sodium hydroxide.
120. A particle-size distribution-adjusting agent for adjusting the particle size distribution of a settable fluid to a desired range, the particle-size distribution-adjusting agent comprising a cationic polymer.
121. The particle-size distribution-adjusting agent of claim 120 wherein the cationic polymer is selected from the group consisting of: cationic polyacrylamides; cationic hydroxyethyl cellulose; poly(dimethyldiallylammonium chloride); and cationic starches.
122. The particle-size distribution-adjusting agent of claim 120 wherein the cationic polymer is a cationic starch.
US10/759,678 2004-01-16 2004-01-16 Settable fluids comprising particle-size distribution-adjusting agents and methods of use Abandoned US20050155763A1 (en)

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US10/759,678 US20050155763A1 (en) 2004-01-16 2004-01-16 Settable fluids comprising particle-size distribution-adjusting agents and methods of use
US10/946,671 US7328756B2 (en) 2004-01-16 2004-09-22 Settable fluids comprising particle-size distribution-adjusting agents and methods of use
CA 2552575 CA2552575C (en) 2004-01-16 2004-12-17 Settable fluids comprising particle-size distribution-adjusting agents and methods of use
GB0720363A GB2442880B (en) 2004-01-16 2004-12-17 Composition for activating a settable fluid
AU2004313746A AU2004313746B2 (en) 2004-01-16 2004-12-17 Settable fluids comprising particle-size distribution-adjusting agents and methods of use
PCT/GB2004/005311 WO2005068776A2 (en) 2004-01-16 2004-12-17 Settable fluids comprising particle-size distribution-adjusting agents and methods of use
GB0611771A GB2423985B (en) 2004-01-16 2004-12-17 Settable fluids comprising particle-size distribution-adjusting agents and methods of use
ARP050100119 AR047636A1 (en) 2004-01-16 2005-01-13 FRAGUABLE FLUIDS THAT INCLUDE AGENTS TO ADJUST THE SIZE DISTRIBUTION OF THE PARTICLES AND USE METHOD
NO20062851A NO20062851L (en) 2004-01-16 2006-06-19 Sustainable liquids comprising means for controlling particle size distribution, as well as methods for using such liquids
US11/503,634 US20060272819A1 (en) 2004-01-16 2006-08-14 Methods of preparing settable fluids comprising particle-size distribution-adjusting agents, and associated methods
US11/867,952 US20080023200A1 (en) 2004-01-16 2007-10-05 Settable Fluids Comprising Particle-Size Distribution-Adjusting Agents and Methods of Use
NO20141321A NO20141321A1 (en) 2004-01-16 2014-11-06 Activator mixture for activating a solidified liquid

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US20080023200A1 (en) 2008-01-31
CA2552575A1 (en) 2005-07-28
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GB2442880B (en) 2008-07-30
US7328756B2 (en) 2008-02-12
NO20062851L (en) 2006-10-16
WO2005068776A3 (en) 2005-11-24
AU2004313746B2 (en) 2010-06-03
CA2552575C (en) 2009-10-27
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AR047636A1 (en) 2006-02-01
GB2423985B (en) 2008-06-18

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