WO2006117524A1 - Set-delayed cement compositions comprising hydrated lime and silica and methods of cementing in subterranean formations - Google Patents
Set-delayed cement compositions comprising hydrated lime and silica and methods of cementing in subterranean formations Download PDFInfo
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- WO2006117524A1 WO2006117524A1 PCT/GB2006/001563 GB2006001563W WO2006117524A1 WO 2006117524 A1 WO2006117524 A1 WO 2006117524A1 GB 2006001563 W GB2006001563 W GB 2006001563W WO 2006117524 A1 WO2006117524 A1 WO 2006117524A1
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- Prior art keywords
- cement composition
- present
- silica
- weight
- cementitious component
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 141
- 239000004568 cement Substances 0.000 title claims abstract description 111
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 37
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 229910001861 calcium hydroxide Inorganic materials 0.000 title claims abstract description 30
- 239000000920 calcium hydroxide Substances 0.000 title claims abstract description 30
- 235000011116 calcium hydroxide Nutrition 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- 238000005755 formation reaction Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- YIBPLYRWHCQZEB-UHFFFAOYSA-N formaldehyde;propan-2-one Chemical class O=C.CC(C)=O YIBPLYRWHCQZEB-UHFFFAOYSA-N 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 22
- 235000011941 Tilia x europaea Nutrition 0.000 description 22
- 239000004571 lime Substances 0.000 description 22
- 239000011398 Portland cement Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000008719 thickening Effects 0.000 description 8
- 239000010881 fly ash Substances 0.000 description 7
- 230000003111 delayed effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000011396 hydraulic cement Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 230000000246 remedial effect Effects 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- -1 defoamers Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions 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
Definitions
- the present invention relates to subterranean operations, and more particularly, to set- delayed cement compositions and methods of using such cement compositions in subterranean applications.
- 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 surfaces 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.
- cement compositions have been used in conventional subterranean cementing operations, including, inter alia, cement compositions comprising Portland cement, and cement compositions comprising water, fly ash, and lime.
- cement compositions comprising Portland cement
- cement compositions comprising water, fly ash, and lime.
- the composition and quality of both Portland cement and fly ash vary widely. Accordingly, the set times of conventional cement compositions employing Portland cement and/or fly ash may be unpredictable. This may be problematic because, inter alia, it may cause such conventional cement compositions to set prematurely, before they have been properly placed in a desired location in a subterranean formation.
- the present invention relates to subterranean operations, and more particularly, to set- delayed cement compositions and methods of using such cement compositions in subterranean applications.
- An example of a cement composition of the present invention is a cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a dispersant.
- a cement composition of the present invention is a cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a set retarder.
- a cement composition of the present invention is a cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a fluid loss control additive.
- the present invention relates to subterranean operations, and more particularly, to set- delayed cement compositions and methods of using such cement compositions in subterranean applications.
- the set-delayed cement compositions of the present invention generally comprise water and a cementitious component consisting essentially of: hydrated lime and silica.
- the set-delayed cement compositions of the present invention may demonstrate better repeatability and reproducibility than conventional cement compositions that may comprise, inter alia, cementitious components comprising Portland cements and/or fly ash.
- Portland cements and fly ashes often vary significantly in their chemical composition, due in part to the process by which Portland cements and fly ashes are made. Accordingly, conventional cement compositions comprising cementitious components that comprise Portland cements and/or fly ashes often will demonstrate undesirable variability in their performance.
- the chemical composition of hydrated lime and silica demonstrates far less variability, and in certain embodiments, may approach a degree of repeatability comparable to that of chemical-grade reagents.
- the set-delayed cement compositions of the present invention comprising a cementitious component that consists essentially of hydrated lime and silica, may demonstrate desirable repeatability and reproducibility, particularly as compared to conventional cement compositions.
- cementitious components consisting essentially of hydrated lime and silica may be less reactive than cementitious components comprising Portland cements.
- certain embodiments of the set-delayed cement compositions of the present invention comprising cementitious components consisting essentially of hydrated lime and silica, may be particularly suitable for use, inter alia, in subterranean formations having relatively high bottom-hole-circulating temperatures, e.g., temperatures in the range of from about 400°F to about 500°F.
- the set-delayed cement compositions of the present invention optionally may comprise other additives suitable for use in the set-delayed cement compositions may be added, such as set retarders, fluid loss control agents, dispersants, and the like.
- the water present in the set-delayed cement compositions 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 set-delayed cement compositions.
- a set-delayed cement composition 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 set-delayed cement compositions of the present invention in an amount in the range of from about 20% to about 80% by weight of the cementitious component.
- the water is present in the set- delayed cement compositions in an amount in the range of from about 35% to about 45% by weight of the cementitious component.
- the set-delayed cement compositions of the present invention comprise hydrated lime.
- hydrated lime will be understood to mean calcium hydroxide.
- the hydrated lime may be present in the set-delayed cement compositions in an amount in the range of from about 1% to about 40% by weight of the cementitious component. In certain embodiments, the hydrated lime may be present in the set-delayed cement compositions in an amount in the range of from about 5% to about 20% by weight of the cementitious component.
- An example of a suitable hydrated lime is commercially available from Continental Lime, Inc., of Salt Lake City, Utah.
- the silica present in the set-delayed cement compositions of the present invention comprises ground quartz.
- suitable silicas include those that are commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade names "SSA-I” and "SSA-2.”
- the silica may be present in the set-delayed cement compositions in an amount in the range of from about 60% to about 99% by weight of the cementitious component. In certain embodiments, the silica is present in the set-delayed cement compositions in an amount in the range of from about 80% to about 95% by weight of the cementitious component.
- the set-delayed cement compositions of the present invention further may comprise a set retarder.
- a set retarder may be used with the set-delayed cement compositions of the present invention. Examples of suitable set retarders include those that are commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade names SCR-100, HR ® -5, and HR ® -25.
- the optional set retarder may be present in the set-delayed cement compositions in an amount in the range of from about 0.05% to about 2.5% by weight of the cementitious component. In higher-temperature applications, the optional set retarder may be present in the set-delayed cement compositions in an amount in the range of from about 1.5% to about 2.5% by weight of the cementitious component.
- the set-delayed cement compositions of the present invention may further comprise a weighting agent.
- any weighting agent may be used with the set- delayed cement compositions of the present invention.
- the weighting agents used in the present invention comprise hematites.
- An example of a suitable hematite is commercially available under the trade name "Hi-Dense ® No. 4" from Halliburton Energy Services, Inc., of Duncan, Oklahoma.
- the weighting agent may be present in an amount in the range of from about 5% to about 45% by weight of the cementitious component.
- the weighting agent may be present in an amount in the range of from about 35% to about 45% by weight of the cementitious component.
- Additional additives optionally may be added to the set-delayed cement compositions of the present invention as deemed appropriate by one skilled in the art with the benefit of this disclosure.
- additives include, among other things, fluid loss control additives, defoamers, microspheres, dispersants, salts, and formation conditioning agents, and the like.
- a dispersant may be present in the set-delayed cement compositions of the present invention in an amount in the range of from about 0.1% to about 1.0% by weight of the cementitious component.
- An example of a suitable dispersant is a sulfonated acetone formaldehyde condensate that is commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade name CFR-3.
- a fluid loss control additive may be present in the set-delayed cement compositions of the present invention in an amount in the range of from about 0.1% to about 1.0% by weight of the cementitious component.
- suitable fluid loss control additives are commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade names HALAD ® 344 and HALAD ® 413.
- a set-delayed cement composition of the present invention may be provided that comprises water and a cementitious component consisting essentially of silica and hydrated lime.
- the set-delayed cement composition may be placed in a subterranean formation and permitted to set therein.
- a set-delayed cement composition of the present invention may be provided that comprises water, and a cementitious component consisting essentially of: silica, and hydrated lime.
- the set-delayed cement composition further may comprise a dispersant.
- the set-delayed cement composition may be permitted to remain in storage for a desired time period (e.g., a time period in the range of from about 12 hours to about seven days after the date on which the set-delayed cement composition was provided), after which a set-retarder may be added to the set- delayed cement composition, and the mixture of the set-delayed cement composition plus retarder may be placed in a subterranean formation and permitted to set therein.
- a set-delayed cement composition of the present invention may be provided that comprises water, a set retarder, and a cementitious component consisting essentially of: silica and hydrated lime.
- the set-delayed cement composition may be permitted to remain in storage for a time period in the range of from about 5 minutes to about 24 hours, after which the set-delayed cement composition may be placed in a subterranean formation and permitted to set therein.
- a set-delayed cement composition of the present invention may comprise about 25% by weight water, 12% by weight hydrated lime, 20% by weight micro silica, 20% by weight silica flour, 20% by weight SSA-2, 2% by weight bentonite, 0.7% by weight SCR-100.
- Sample set-delayed cement compositions of the present invention were prepared comprising 250 grams of water, 120 grams of hydrated lime, 200 grams of micro silica, 200 grams of silica flour, 200 grams of SSA-2, 21.6 grams of bentonite, and 7.2 grams of SCR- 100.
- the sample compositions (referred to herein as Sample Composition No. 1 and Sample Composition No. 2) were prepared at room temperature and subjected to a thickening time test at 250°F, either immediately after mixing or after standing at room temperature for 24 hours after mixing. The thickening test was performed in accordance with API Spec 10.
- a conventional cement composition was prepared comprising class H cement blended with 1% SCR-100 and 38% water. After mixing, the conventional cement composition was left standing overnight and then subjected to the same thickening time test described above.
- Sample Composition No. 1 was tested immediately after mixing and had a thickening time of 2:48.
- Sample Composition No. 2 was tested after standing for 24 hours, and had a thickening time of 2:32.
- the conventional cement composition was semi-set and could not be re-blended after 24 hours.
- Additional sample cement compositions were prepared as follows. About 600 grams of SSA-I were added to 60 grams of lime and 231 grams of water. Varying amounts of set retarder were added, and thickening tests were conducted on the sample cement compositions at varying test temperatures. The thickening tests were conducted according to API Spec 1OB.
- Sample Composition No. 3 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.5% HR ® -5 by weight of the mixture of lime and silica.
- Sample Composition No. 4 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.6% HR ® -5 by weight of the mixture of lime and silica.
- Sample Composition No. 5 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 1.0% HR ® -5 by weight of the mixture of lime and silica.
- Sample Composition No. 6 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.6% HR ® -5 by weight of the mixture of lime and silica.
- Sample Composition No. 7 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.7% HR ® -5 by weight of the mixture of lime and silica.
- Sample Composition No. 8 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, 1.0% HR ® -5 by weight of the mixture of lime and silica, and 0.5% HR ® -25 by weight of the mixture of lime and silica.
- Sample Composition No. 9 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, 2.0% HR ® -5 by weight of the mixture of lime and silica, and 1.0% HR ® -25 by weight of the mixture of lime and silica.
- Sample Composition No. 10 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, 2.0% HR ® -5 by weight of the mixture of lime and silica, and 1.0% HR ® -25 by weight of the mixture of lime and silica.
Abstract
Cement compositions for use in subterranean formations are provided. An example of a cement composition is a cement composition comprising: water, a cementitious component consisting essentially of: hydrated lime, and silica; and a dispersant. Another example of a cement composition is a cement composition comprising: water, a cementitious component consisting essentially of: hydrated lime, and silica; and a set retarder. Another example of a cement composition is a cement composition comprising: water, a cementitious component consisting essentially of: hydrated lime, and silica; and a fluid loss control additive.
Description
SET-DELAYED CEMENT COMPOSITIONS COMPRISING HYDRATED LIME AND SDLICA AND METHODS OF CEMENTING IN SUBTERRANEAN
FORMATIONS
BACKGROUND
The present invention relates to subterranean operations, and more particularly, to set- delayed cement compositions and methods of using such cement compositions in subterranean applications.
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 surfaces 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.
A broad variety of cement compositions have been used in conventional subterranean cementing operations, including, inter alia, cement compositions comprising Portland cement, and cement compositions comprising water, fly ash, and lime. However, the composition and quality of both Portland cement and fly ash vary widely. Accordingly, the set times of conventional cement compositions employing Portland cement and/or fly ash may be unpredictable. This may be problematic because, inter alia, it may cause such conventional cement compositions to set prematurely, before they have been properly placed in a desired location in a subterranean formation.
SUMMARY
The present invention relates to subterranean operations, and more particularly, to set- delayed cement compositions and methods of using such cement compositions in subterranean applications.
An example of a cement composition of the present invention is a cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a dispersant.
Another example of a cement composition of the present invention is a cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a set retarder.
Another example of a cement composition of the present invention is a cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a fluid loss control additive.
The features and advantages of the present invention will be readily apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention relates to subterranean operations, and more particularly, to set- delayed cement compositions and methods of using such cement compositions in subterranean applications.
The set-delayed cement compositions of the present invention generally comprise water and a cementitious component consisting essentially of: hydrated lime and silica. Among other things, the set-delayed cement compositions of the present invention may demonstrate better repeatability and reproducibility than conventional cement compositions that may comprise, inter alia, cementitious components comprising Portland cements and/or fly ash. Portland cements and fly ashes often vary significantly in their chemical composition, due in part to the process by which Portland cements and fly ashes are made. Accordingly, conventional cement compositions comprising cementitious components that comprise Portland cements and/or fly ashes often will demonstrate undesirable variability in their performance. In contrast, the chemical composition of hydrated lime and silica demonstrates far less variability, and in certain embodiments, may approach a degree of repeatability comparable to that of chemical-grade reagents. Accordingly, the set-delayed cement compositions of the present invention, comprising a cementitious component that consists essentially of hydrated lime and silica, may demonstrate desirable repeatability and reproducibility, particularly as compared to conventional cement compositions. Moreover, cementitious components consisting essentially of hydrated lime and silica may be less
reactive than cementitious components comprising Portland cements. Accordingly, certain embodiments of the set-delayed cement compositions of the present invention, comprising cementitious components consisting essentially of hydrated lime and silica, may be particularly suitable for use, inter alia, in subterranean formations having relatively high bottom-hole-circulating temperatures, e.g., temperatures in the range of from about 400°F to about 500°F. In certain optional embodiments, the set-delayed cement compositions of the present invention optionally may comprise other additives suitable for use in the set-delayed cement compositions may be added, such as set retarders, fluid loss control agents, dispersants, and the like.
The water present in the set-delayed cement compositions 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 set-delayed cement compositions. For example, a set-delayed cement composition 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 set-delayed cement compositions of the present invention in an amount in the range of from about 20% to about 80% by weight of the cementitious component. In certain exemplary embodiments, the water is present in the set- delayed cement compositions in an amount in the range of from about 35% to about 45% by weight of the cementitious component.
The set-delayed cement compositions of the present invention comprise hydrated lime. As referred to herein, hydrated lime will be understood to mean calcium hydroxide. The hydrated lime may be present in the set-delayed cement compositions in an amount in the range of from about 1% to about 40% by weight of the cementitious component. In certain embodiments, the hydrated lime may be present in the set-delayed cement compositions in an amount in the range of from about 5% to about 20% by weight of the cementitious component. An example of a suitable hydrated lime is commercially available from Continental Lime, Inc., of Salt Lake City, Utah.
The silica present in the set-delayed cement compositions of the present invention comprises ground quartz. Examples of suitable silicas include those that are commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade names "SSA-I" and "SSA-2." The silica may be present in the set-delayed cement
compositions in an amount in the range of from about 60% to about 99% by weight of the cementitious component. In certain embodiments, the silica is present in the set-delayed cement compositions in an amount in the range of from about 80% to about 95% by weight of the cementitious component.
Optionally, the set-delayed cement compositions of the present invention further may comprise a set retarder. Whether a particular application will require the inclusion of a set retarder in a particular set-delayed cement composition may depend upon factors including, but not limited to, the bottom hole circulating temperature of the application. One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine whether a set retarder is appropriate for a particular application. Generally, any set retarder may be used with the set-delayed cement compositions of the present invention. Examples of suitable set retarders include those that are commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade names SCR-100, HR®-5, and HR®-25. Where included, the optional set retarder may be present in the set-delayed cement compositions in an amount in the range of from about 0.05% to about 2.5% by weight of the cementitious component. In higher-temperature applications, the optional set retarder may be present in the set-delayed cement compositions in an amount in the range of from about 1.5% to about 2.5% by weight of the cementitious component.
Optionally, the set-delayed cement compositions of the present invention may further comprise a weighting agent. Generally, any weighting agent may be used with the set- delayed cement compositions of the present invention. In certain embodiments, the weighting agents used in the present invention comprise hematites. An example of a suitable hematite is commercially available under the trade name "Hi-Dense® No. 4" from Halliburton Energy Services, Inc., of Duncan, Oklahoma. In certain embodiments of the present invention where a weighting agent may be present in a set-delayed cement composition, the weighting agent may be present in an amount in the range of from about 5% to about 45% by weight of the cementitious component. In certain embodiments, the weighting agent may be present in an amount in the range of from about 35% to about 45% by weight of the cementitious component.
Additional additives optionally may be added to the set-delayed cement compositions of the present invention as deemed appropriate by one skilled in the art with the benefit of this disclosure. Examples of such additives include, among other things, fluid loss control
additives, defoamers, microspheres, dispersants, salts, and formation conditioning agents, and the like. Where included, a dispersant may be present in the set-delayed cement compositions of the present invention in an amount in the range of from about 0.1% to about 1.0% by weight of the cementitious component. An example of a suitable dispersant is a sulfonated acetone formaldehyde condensate that is commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade name CFR-3. Where included, a fluid loss control additive may be present in the set-delayed cement compositions of the present invention in an amount in the range of from about 0.1% to about 1.0% by weight of the cementitious component. Examples of suitable fluid loss control additives are commercially available from Halliburton Energy Services, Inc., of Duncan, Oklahoma, under the trade names HALAD® 344 and HALAD® 413.
In one embodiment of the present invention, a set-delayed cement composition of the present invention may be provided that comprises water and a cementitious component consisting essentially of silica and hydrated lime. The set-delayed cement composition may be placed in a subterranean formation and permitted to set therein.
In another embodiment of the present invention, a set-delayed cement composition of the present invention may be provided that comprises water, and a cementitious component consisting essentially of: silica, and hydrated lime. In certain embodiments, the set-delayed cement composition further may comprise a dispersant. The set-delayed cement composition may be permitted to remain in storage for a desired time period (e.g., a time period in the range of from about 12 hours to about seven days after the date on which the set-delayed cement composition was provided), after which a set-retarder may be added to the set- delayed cement composition, and the mixture of the set-delayed cement composition plus retarder may be placed in a subterranean formation and permitted to set therein.
In another embodiment of the present invention, a set-delayed cement composition of the present invention may be provided that comprises water, a set retarder, and a cementitious component consisting essentially of: silica and hydrated lime. The set-delayed cement composition may be permitted to remain in storage for a time period in the range of from about 5 minutes to about 24 hours, after which the set-delayed cement composition may be placed in a subterranean formation and permitted to set therein.
In one embodiment, a set-delayed cement composition of the present invention may comprise about 25% by weight water, 12% by weight hydrated lime, 20% by weight micro
silica, 20% by weight silica flour, 20% by weight SSA-2, 2% by weight bentonite, 0.7% by weight SCR-100.
To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the entire scope of the invention.
EXAMPLE l
Sample set-delayed cement compositions of the present invention were prepared comprising 250 grams of water, 120 grams of hydrated lime, 200 grams of micro silica, 200 grams of silica flour, 200 grams of SSA-2, 21.6 grams of bentonite, and 7.2 grams of SCR- 100. The sample compositions (referred to herein as Sample Composition No. 1 and Sample Composition No. 2) were prepared at room temperature and subjected to a thickening time test at 250°F, either immediately after mixing or after standing at room temperature for 24 hours after mixing. The thickening test was performed in accordance with API Spec 10. As a comparison, a conventional cement composition was prepared comprising class H cement blended with 1% SCR-100 and 38% water. After mixing, the conventional cement composition was left standing overnight and then subjected to the same thickening time test described above.
Sample Composition No. 1 was tested immediately after mixing and had a thickening time of 2:48. Sample Composition No. 2 was tested after standing for 24 hours, and had a thickening time of 2:32. The conventional cement composition was semi-set and could not be re-blended after 24 hours.
The above example demonstrates, among other things, that the set-delayed cement compositions of the present invention are suitable for use in subterranean applications.
EXAMPLE 2
Additional sample cement compositions were prepared as follows. About 600 grams of SSA-I were added to 60 grams of lime and 231 grams of water. Varying amounts of set retarder were added, and thickening tests were conducted on the sample cement compositions at varying test temperatures. The thickening tests were conducted according to API Spec 1OB.
Sample Composition No. 3 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.5% HR®-5 by weight of the mixture of lime and silica.
Sample Composition No. 4 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.6% HR®-5 by weight of the mixture of lime and silica.
Sample Composition No. 5 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 1.0% HR®-5 by weight of the mixture of lime and silica.
Sample Composition No. 6 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.6% HR®-5 by weight of the mixture of lime and silica.
Sample Composition No. 7 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, and 0.7% HR®-5 by weight of the mixture of lime and silica.
Sample Composition No. 8 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, 1.0% HR®-5 by weight of the mixture of lime and silica, and 0.5% HR®-25 by weight of the mixture of lime and silica.
Sample Composition No. 9 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, 2.0% HR®-5 by weight of the mixture of lime and silica, and 1.0% HR®-25 by weight of the mixture of lime and silica.
Sample Composition No. 10 comprised 600 grams SSA-I, 60 grams lime, 231 grams of water, 2.0% HR®-5 by weight of the mixture of lime and silica, and 1.0% HR®-25 by weight of the mixture of lime and silica.
The results of the thickening time are set forth in Table 1 below.
TABLE l
The above example demonstrates, among other things, that the set-delayed cement compositions of the present invention are suitable for use in subterranean applications.
Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims. The terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee.
Claims
1. A cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a dispersant.
2. The cement composition of claim 1 wherein the dispersant is present in the cement composition in an amount in the range of from about 0.1% to about 1.0% by weight of the cementitious component.
3. The cement composition of claim 1 wherein the dispersant comprises a sulfonated acetone formaldehyde condensate.
4. The cement composition of claim 1 wherein the hydrated lime is present in the cement composition in an amount in the range of from about 1% to about 40% by weight of the cementitious component.
5. The cement composition of claim 1 wherein the silica is present in the cement composition in an amount in the range of from about 60% to about 99% by weight of the cementitious component.
6. The cement composition of claim 1 wherein the water is present in the cement composition in an amount in the range of from about 20% to about 80% by weight of the cementitious component.
7. A cement composition comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a set retarder.
8. The cement composition of claim 7 wherein the cement composition comprises a dispersant.
9. The cement composition of claim 7 wherein the hydrated lime is present in the cement composition in an amount in the range of from about 1% to about 40% by weight of the cementitious component.
10. The cement composition of claim 7 wherein the silica is present in the cement composition in an amount in the range of from about 60% to about 99% by weight of the cementitious component.
11. The cement composition of claim 7 wherein the water is present in the cement composition in an amount in the range of from about 20% to about 80% by weight of the cementitious component.
12. The cement composition of claim 7 wherein the set retarder is present in the cement composition in an amount in the range of from about 0.05% to about 2.5% by weight of the cementitious component.
13. A cement composition, comprising: water; a cementitious component consisting essentially of: hydrated lime, and silica; and a fluid loss control additive.
14. The cement composition of claim 13 wherein the hydrated lime is present in the cement composition in an amount in the range of from about 1% to about 40% by weight of the cementitious component.
15. The cement composition of claim 13 wherein the silica is present in the cement composition cement composition in an amount in the range of from about 60% to about 99% by weight of the cementitious component.
16. The cement composition of claim 13 wherein the water is present in the cement composition in an amount in the range of from about 20% to about 80% by weight of the cementitious component.
17. The cement composition of claim 13 wherein the fluid loss control additive is present in the cement composition in an amount in the range of from about 0.1% to about 1.0% by weight of the cementitious component.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10626057B2 (en) | 2012-03-09 | 2020-04-21 | Halliburton Energy Services, Inc. | Set-delayed cement compositions comprising pumice and associated methods |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060249289A1 (en) * | 2005-05-05 | 2006-11-09 | Halliburton Energy Services, Inc. | Set-delayed cement compositions comprising hydrated lime and silica and methods of cementing in subterranean formations |
US8276666B2 (en) * | 2007-08-08 | 2012-10-02 | Halliburton Energy Services Inc. | Sealant compositions and methods of use |
US20090038801A1 (en) * | 2007-08-08 | 2009-02-12 | Ravi Krishna M | Sealant Compositions and Methods of Use |
ES2623159T3 (en) * | 2011-12-01 | 2017-07-10 | Gcp Applied Technologies Inc. | Composition and procedure for obtaining exposed aggregates on molded concrete surfaces and other cementitious materials |
US9371712B2 (en) | 2012-03-09 | 2016-06-21 | Halliburton Energy Services, Inc. | Cement set activators for set-delayed cement compositions and associated methods |
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US9580638B2 (en) | 2012-03-09 | 2017-02-28 | Halliburton Energy Services, Inc. | Use of synthetic smectite in set-delayed cement compositions |
US9255031B2 (en) | 2012-03-09 | 2016-02-09 | Halliburton Energy Services, Inc. | Two-part set-delayed cement compositions |
US10195764B2 (en) | 2012-03-09 | 2019-02-05 | Halliburton Energy Services, Inc. | Set-delayed cement compositions comprising pumice and associated methods |
US9328281B2 (en) | 2012-03-09 | 2016-05-03 | Halliburton Energy Services, Inc. | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
US10082001B2 (en) | 2012-03-09 | 2018-09-25 | Halliburton Energy Services, Inc. | Cement set activators for cement compositions and associated methods |
US9856167B2 (en) | 2012-03-09 | 2018-01-02 | Halliburton Energy Services, Inc. | Mitigation of contamination effects in set-delayed cement compositions comprising pumice and hydrated lime |
US9227872B2 (en) | 2012-03-09 | 2016-01-05 | Halliburton Energy Services, Inc. | Cement set activators for set-delayed cement compositions and associated methods |
US9212534B2 (en) | 2012-03-09 | 2015-12-15 | Halliburton Energy Services, Inc. | Plugging and abandoning a well using a set-delayed cement composition comprising pumice |
CA2815589C (en) * | 2013-04-30 | 2016-01-05 | Baker Hughes Incorporated | Method of real time monitoring of well operations using self-sensing treatment fluids |
WO2015035227A1 (en) * | 2013-09-06 | 2015-03-12 | Halliburton Energy Services, Inc. | Set-delayed cement compositions comprising pumice and associated methods |
RU2635413C2 (en) * | 2013-09-09 | 2017-11-13 | Халлибертон Энерджи Сервисез, Инк. | Cement setting activators for cement compositions and corresponding methods |
GB2530459B (en) | 2013-09-09 | 2021-02-10 | Halliburton Energy Services Inc | Activation of set-delayed cement compositions by retarder exchange |
AU2015223141B2 (en) * | 2014-02-28 | 2017-03-16 | Halliburton Energy Services, Inc. | Settable compositions and methods of use |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0177308A2 (en) * | 1984-09-27 | 1986-04-09 | Halliburton Company | Well cementing methods and compositions |
US5332041A (en) * | 1992-12-30 | 1994-07-26 | Halliburton Company | Set-activated cementitious compositions and methods |
Family Cites Families (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698256A (en) | 1950-01-12 | 1954-12-28 | Great Lakes Carbon Corp | Siliceous composition and method for manufacturing the same |
US2805719A (en) | 1955-09-15 | 1957-09-10 | Halliburton Oil Well Cementing | High temperature well cementing |
US3679446A (en) | 1968-06-04 | 1972-07-25 | Osaka Packing | Molding materials of calcium silicate hydrate and shaped products thereof |
US4238536A (en) | 1978-09-14 | 1980-12-09 | Halliburton Company | Preventing water incursion into commodity piles |
US4234344A (en) | 1979-05-18 | 1980-11-18 | Halliburton Company | Lightweight cement and method of cementing therewith |
SU1080911A1 (en) * | 1982-07-26 | 1984-03-23 | Ленинградский Ордена Октябрьской Революции И Ордена Трудового Красного Знамени Технологический Институт Им.Ленсовета | Mixture for producing moulds and cores by co@ process |
DE3344291A1 (en) | 1983-12-07 | 1985-06-13 | Skw Trostberg Ag, 8223 Trostberg | DISPERSING AGENT FOR SALTY SYSTEMS |
US4515635A (en) | 1984-03-23 | 1985-05-07 | Halliburton Company | Hydrolytically stable polymers for use in oil field cementing methods and compositions |
US4555269A (en) | 1984-03-23 | 1985-11-26 | Halliburton Company | Hydrolytically stable polymers for use in oil field cementing methods and compositions |
US4676317A (en) | 1986-05-13 | 1987-06-30 | Halliburton Company | Method of reducing fluid loss in cement compositions which may contain substantial salt concentrations |
NO165673C (en) | 1987-11-16 | 1991-03-20 | Elkem As | HYDRAULIC CEMENT SUSPENSION. |
US4880468A (en) | 1988-09-29 | 1989-11-14 | Halliburton Services | Waste solidification composition and methods |
JPH0342096A (en) * | 1989-04-21 | 1991-02-22 | Shigenobu Kasamatsu | Method for removing phosphate ion and sulfate ion in water |
US4941536A (en) | 1989-06-27 | 1990-07-17 | Halliburton Company | Set retarded cement compositions and methods for well cementing |
US5049288A (en) | 1989-06-27 | 1991-09-17 | Halliburton Company | Set retarded cement compositions and methods for well cementing |
US5336022A (en) | 1991-11-27 | 1994-08-09 | Chemical Lime Company | Method for producing enhanced soil stabilization reactions between lime and clay soils due to the effect of silica addition |
US5346550A (en) | 1992-02-05 | 1994-09-13 | Halliburton Company | Low temperature well cementing compositions and methods |
US5327968A (en) | 1992-12-30 | 1994-07-12 | Halliburton Company | Utilizing drilling fluid in well cementing operations |
US5383521A (en) | 1993-04-01 | 1995-01-24 | Halliburton Company | Fly ash cementing compositions and methods |
JP3569306B2 (en) * | 1993-12-28 | 2004-09-22 | 富士川建材工業株式会社 | Inorganic finishing material composition and method using the same |
US5458195A (en) | 1994-09-28 | 1995-10-17 | Halliburton Company | Cementitious compositions and methods |
US5472051A (en) | 1994-11-18 | 1995-12-05 | Halliburton Company | Low temperature set retarded well cement compositions and methods |
US5577865A (en) | 1995-07-28 | 1996-11-26 | Halliburton Company | Placement of a substantially non-flowable cementitious material in an underground space |
US5711383A (en) | 1996-04-19 | 1998-01-27 | Halliburton Company | Cementitious well drilling fluids and methods |
AUPO612097A0 (en) * | 1997-04-10 | 1997-05-08 | James Hardie Research Pty Limited | Building products |
US6796378B2 (en) | 1997-08-15 | 2004-09-28 | Halliburton Energy Services, Inc. | Methods of cementing high temperature wells and cement compositions therefor |
US5900053A (en) | 1997-08-15 | 1999-05-04 | Halliburton Energy Services, Inc. | Light weight high temperature well cement compositions and methods |
AU738096B2 (en) | 1997-08-15 | 2001-09-06 | Halliburton Energy Services, Inc. | Light weight high temperature well cement compositions and methods |
US6068055A (en) | 1998-06-30 | 2000-05-30 | Halliburton Energy Services, Inc. | Well sealing compositions and methods |
DE19918598A1 (en) * | 1999-04-23 | 2000-10-26 | Hasit Trockenmoertel Gmbh | Joint-less terrazzo floor is produced by pouring a fluid aggregate, binder, additive and water mixture to form a flat layer which is surface polished after gravity compaction and solidification |
US6258160B1 (en) | 1999-09-07 | 2001-07-10 | Halliburton Energy Services, Inc. | Methods and compositions for grouting heat exchange pipe |
US6138759A (en) | 1999-12-16 | 2000-10-31 | Halliburton Energy Services, Inc. | Settable spotting fluid compositions and methods |
US6315042B1 (en) | 2000-07-26 | 2001-11-13 | Halliburton Energy Services, Inc. | Oil-based settable spotting fluid |
US6668929B2 (en) | 2000-07-26 | 2003-12-30 | Halliburton Energy Services, Inc. | Methods and oil-based settable spotting fluid compositions for cementing wells |
US6666268B2 (en) | 2000-07-26 | 2003-12-23 | Halliburton Energy Services, Inc. | Methods and oil-based settable drilling fluid compositions for drilling and cementing wells |
US6716282B2 (en) | 2000-07-26 | 2004-04-06 | Halliburton Energy Services, Inc. | Methods and oil-based settable spotting fluid compositions for cementing wells |
US6562122B2 (en) | 2000-09-18 | 2003-05-13 | Halliburton Energy Services, Inc. | Lightweight well cement compositions and methods |
US6908508B2 (en) * | 2003-06-04 | 2005-06-21 | Halliburton Energy Services, Inc. | Settable fluids and methods for use in subterranean formations |
US6689208B1 (en) | 2003-06-04 | 2004-02-10 | Halliburton Energy Services, Inc. | Lightweight cement compositions and methods of cementing in subterranean formations |
-
2005
- 2005-05-05 US US11/122,438 patent/US7201798B2/en active Active
-
2006
- 2006-04-27 WO PCT/GB2006/001563 patent/WO2006117524A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0177308A2 (en) * | 1984-09-27 | 1986-04-09 | Halliburton Company | Well cementing methods and compositions |
US5332041A (en) * | 1992-12-30 | 1994-07-26 | Halliburton Company | Set-activated cementitious compositions and methods |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10626057B2 (en) | 2012-03-09 | 2020-04-21 | Halliburton Energy Services, Inc. | Set-delayed cement compositions comprising pumice and associated methods |
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