WO2005052309A1 - Methods, cement compositions and oil suspensions of powder - Google Patents
Methods, cement compositions and oil suspensions of powder Download PDFInfo
- Publication number
- WO2005052309A1 WO2005052309A1 PCT/GB2004/004348 GB2004004348W WO2005052309A1 WO 2005052309 A1 WO2005052309 A1 WO 2005052309A1 GB 2004004348 W GB2004004348 W GB 2004004348W WO 2005052309 A1 WO2005052309 A1 WO 2005052309A1
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- oil suspension
- suspension
- cement
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Classifications
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- 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
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- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to methods of cementing subterranean zones, cement compositions and oil suspensions of powder useful in cement compositions.
- Hydraulic cement compositions are utilized in cementing subterranean zones penetrated by well bores.
- hydraulic cement compositions are used in primary well cementing operations whereby strings of pipe such as casings and liners are cemented in well bores.
- strings of pipe such as casings and liners are cemented in well bores.
- a cement composition is pumped into the annular space between the walls of a well bore and the exterior surfaces of a 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.
- the cement sheath physically 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 whereby the undesirable migration of fluids between zones or formations penetrated by the well bore is prevented.
- large quantities of crystalline and amorphous silica powder are often included in the cement compositions utilized.
- Crystalline silica powder is included in cement compositions to prevent cement compressive strength retrogression, i.e., the loss of compressive strength and increased permeability.
- Amorphous silica powder is also commonly utilized as a light weight filler and to increase the cement compressive strength by reacting with lime to form calcium- silicate-hydrate gel.
- the crystalline and amorphous silica powder utilized have been combined with cement in mechanical blending equipment.
- significant amounts of the silica powder and dust are released into the atmosphere.
- Personnel in the area are often exposed to the powder and dust which can cause silicosis, a chronic disease of the lungs caused by the inhalation of silica powder and dust.
- the present invention provides methods, cement compositions and oil suspensions of silica powder which are combined with the cement compositions without the production of significant silica powder or dust which meet the needs described above and overcome the deficiencies of the prior art.
- the oil suspensions of silica powder of this invention are combined with cement and water in liquid form. Upon contacting the water, the oil suspension releases the suspended silica powder whereby it mixes with the cement and water without losses to the atmosphere.
- the oil suspensions of silica powder of this invention are basically comprised of silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant.
- the cement compositions of this invention are basically comprised of a hydraulic cement, water present in an amount sufficient to form a slurry and an oil suspension of silica powder that comprises silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant.
- the methods of this invention for cementing a subterranean zone penetrated by a well bore are comprised of the following steps.
- a cement composition is prepared or provided comprising a hydraulic cement, sufficient water to form a slurry and an oil suspension of silica powder that comprises silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant.
- this invention provides oil suspensions of silica powder that can be quickly and easily added to a cement composition without the release of silica powder and dust.
- the oil suspensions can contain fine or coarse crystalline silica powder or amorphous silica powder, or both.
- the oil suspensions of silica powder of this invention are comprised of silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant.
- the silica powder in the oil suspension can be crystalline silica powder or amorphous silica powder, or both. Crystalline silica powder is utilized in cement compositions to prevent cement compressive strength retrogression at high temperatures. In addition to preventing the loss of compressive strength, the undesirable increase in cement permeability that also takes place is prevented.
- the presence of amorphous silica powder in the cement composition functions as a light weight filler and increases the compressive strength by reacting with lime to form calcium-silicate-hydrate gel.
- the crystalline silica powder utilized in cement compositions can have a particle size in the general range of from about 15 microns to about 350 microns.
- the crystalline silica powder is generally present in the oil suspension in an amount in the range of from about 45% to about 52% by weight of the suspension.
- Amorphous silica powder has a particle size in the general range of from about 5 microns to about 25 microns.
- the amorphous silica powder is generally present in the oil suspension in an amount in the range of from about 43 % to about 47% by weight of the suspension.
- coarse crystalline silica powder is included in a cement composition, it usually has a particle size in the range of from about 175 microns to about 350 microns.
- Such coarse crystalline silica is commercially available under the trade designation "SSA-1TM” from Halliburton Energy Services of Duncan, Oklahoma.
- SSA-1TM coarse crystalline silica
- fine crystalline silica powder When fine crystalline silica powder is utilized in a cement composition, it usually has a particle size in the range of from about 16 microns to about 20 microns. Such a fine crystalline silica is commercially available from Halliburton Energy Services of Duncan, Oklahoma under the trade designation “SSA-2TM”.
- SSA-2TM trade designation
- amorphous silica powder When amorphous silica powder is utilized, it usually has a particle size in the range of from about 5 microns to about 20 microns.
- SILICALITETM Such amorphous silica is commercially available from Halliburton Energy Services of Duncan, Oklahoma under the trade designation "SILICALITETM”.
- coarse crystalline silica powder is included in the oil suspension of this invention in an amount in the range of from about 47% to about 52% by weight of the suspension and fine crystalline silica is included in the oil suspension in an amount in the range of from about 47% to about 52% by weight of the suspension.
- fine crystalline silica is included in the oil suspension in an amount in the range of from about 47% to about 52% by weight of the suspension.
- amorphous silica it is generally present in the oil suspension in an amount in the range of from about 43%o to about 47% by weight of the suspension.
- the suspensions and methods of the present invention may be suitable for or used with any component of a cement composition that may be provided in powder form.
- Particularly suitable powders have a particle size in the range of from about 5 microns to about 350 microns.
- examples of such components that may be provided in powder form include, but are not limited to, micro-silica, silica flour, fine silica flour, silica sand, fine particle size cement, ultra-fine particle size cement, fly ash, slag, vitrified shale and zeolite.
- the powder is present in the suspension in an amount in the range of from about 43% to about 52% by weight of said suspension.
- Methods of using the suspensions include preparing or providing a cement composition comprising a hydraulic cement, sufficient water to form a slurry and an oil suspension of the powder that comprises mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant; placing said cement composition in a subterranean zone; and allowing said cement composition to set therein.
- the water is present in said cement composition in an amount in the range of from about 35% to about 65% by weight of hydraulic cement therein and the oil suspension is present in said cement composition in an amount in the range of from about 10% to about 70% by weight of hydraulic cement therein.
- the mineral oil utilized in the oil suspension of this invention preferably has a viscosity at 100°F in the range of from about 60 saybolt seconds to about 100 saybolt seconds, more preferably 70 saybolt seconds.
- the mineral oil is generally included in the oil suspension in an amount in the range of from about 40% to about 55% by weight of the oil suspension.
- the oleophilic clay is included in the oil suspension to provide viscosity and texture to the mineral oil and to maintain the silica powder in suspension. The amount of oleophilic clay included in the oil suspension depends on the amount of silica to be suspended as well as the particle size of the silica powder.
- the oleophilic clay is present in the oil suspension in an amount in the range of from about 0.75% to about 5.5% by weight of the suspension.
- a particularly suitable oleophilic clay is commercially available from the Southern Clay Company of Gonzales, Texas.
- the oleophilic surfactant included in the oil suspension functions to cause the clay particles to be coated with mineral oil and to readily become suspended therein.
- examples of oleophilic surfactants that can be utilized include, but are not limited to, sorbitantrioleate, sorbitantrilaurate, sorbitantripalmitate, sorbitantristearate and sorbitantrisesquioleate. Of these, sorbitantrioleate is preferred.
- the oleophilic surfactant utilized is generally included in the oil suspension in an amount of the range of from about 0.1 % to about 0.2% by weight of the oil suspension.
- the hydrophilic surfactant in the oil suspension functions to release the suspended silica from the oil suspension when the oil suspension is combined with a cement composition containing water. When released, the silica powder is dispersed in the cement composition by stirring or blending.
- hydrophilic surfactants which can be utilized include, but are not limited to, polyethoxylated sorbitantrioleate, polyethoxylated sorbitantrilaurate, polyethoxylated sorbitantripalmitate, polyethoxylated sorbitantristearate and polyethoxylated sorbitantrisesquioleate. Of these, polyethoxylated sorbitantrioleate is preferred.
- polyethoxylated is used herein to mean that the surfactant is substituted with at least 20 moles of ethylene of oxide.
- the hydrophilic surfactant utilized is generally present in the oil suspension in an amount in the range of from about from about 2.5% to about 3.5% by weight of the suspension.
- a particularly suitable oil suspension of this invention containing coarse crystalline silica having a particle size in the range of from about 175 microns to about 350 microns is comprised of the following components: coarse crystalline silica present in an amount of about 50% by weight of the oil suspension; mineral oil having a viscosity at 100°F of 70 saybolt seconds present in an amount of about 42.9%) by weight of the suspension; oleophilic clay present in an amount of about 4% by weight of the suspension; a sorbitantrioleate oleophilic surfactant present in an amount of about 0.1 % by weight of the suspension; and a polyethoxylated sorbitantrioleate hydrophilic surfactant present in an amount of about 3% by weight of the suspension.
- a particularly suitable oil suspension of fine crystalline silica having a particle size in the range of from about 16 microns to about 20 microns is comprised of the following components: fine crystalline silica present in an amount of about 50% by weight of the oil suspension; mineral oil having a viscosity at 100°F of 70 saybolt seconds present in an amount of about 43.9% by weight of the suspension; oleophilic clay present in an amount of about 3% by weight of the suspension; a sorbitantrioleate oleophilic surfactant present in an amount of about 0.1 %> by weight of the suspension; and a polyethoxylated sorbitantrioleate hydrophilic surfactant present in an amount of about 3% by weight of the suspension.
- a particularly suitable oil suspension of amorphous silica having a particle size in the range of from about 5 to about 20 microns is comprised of the following components: amorphous silica present in an amount of about 45% by weight of the suspension; mineral oil having a viscosity at 100°F of 70 saybolt seconds present in an amount 50.9%) by weight of the suspension; oleophilic clay present in an amount of about 1%> by weight of the suspension; a sorbitantrioleate oleophilic surfactant present in an amount of about 0.1 %> by weight of the suspension; and a polyethoxylated sorbitantrioleate hydrophilic surfactant present in an amount of about 3%> by weight of the suspension.
- a cement composition of this invention is comprised of the following components: a hydraulic cement, water present in an amount sufficient to form a slurry and an oil suspension of silica powder that comprises silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant.
- the cement compositions of this invention can also include a dispersant, a set retarder, a fluid loss control additive, a light weight or heavy weight additive and other additives depending on the well conditions.
- hydraulic cements which can be utilized in the cement compositions include, but are not limited to, Portland cements, slag cements, pozzolana cements, gypsum cements, aluminous cements, alkaline cements and mixtures thereof. Of these, Portland cement is preferred.
- the water utilized in the cement compositions can be fresh water or salt water.
- salt water is used herein to mean unsaturated salt solutions and saturated salt solutions including brines and seawater.
- the water is present in the cement composition in an amount sufficient to form a slurry which is generally in the range of from about 35% to about 65% water by weight of hydraulic cement in the cement composition.
- the oil suspension containing the crystalline and/or amorphous silica powder is present in the cement composition in an amount in the range of from about 10%> to about 70%> by weight of hydraulic cement therein.
- the components in the oil suspension i.e., silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant are the same as those described above and are present in the amounts set forth above.
- the methods of cementing a subterranean zone penetrated by a well bore of this invention are basically comprised of the following steps.
- a cement composition is prepared or provided comprising a hydraulic cement, sufficient water to form a slurry and an oil suspension of silica powder that comprises silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant.
- the cement composition is placed in the subterranean zone to be cemented and thereafter the cement composition is allowed to set into a solid mass therein.
- the components of the cement composition and the components of the oil suspension of silica powder are the same as those described above and are present in the amounts set forth above.
- various well known additives can also be included in the cement composition.
- an oil suspension of silica powder comprises: silica powder; mineral oil; an oleophilic clay; an oleophilic surfactant; and a hydrophilic surfactant.
- the cement composition comprises: a hydraulic cement; water present in an amount sufficient to form a slurry; and an oil suspension of silica powder that comprises silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant.
- a method of cementing a subterranean zone penetrated by a well bore comprises: (a) preparing or providing a cement composition comprising a hydraulic cement, sufficient water to form a slurry and an oil suspension of silica powder that comprises silica powder, mineral oil, an oleophilic clay, an oleophilic surfactant and a hydrophilic surfactant; (b) placing the cement composition in the subterranean zone; and (c) allowing the cement composition to set into a solid mass therein.
- EXAMPLE 1 A mineral oil suspension of coarse silica having a particle size in the range of from 175 microns to 350 microns was prepared comprised of 50%> coarse silica, 42.9% mineral oil having a viscosity at 100°F of 70 saybolt seconds, 4% oleophilic clay, 0.1% sorbitantrioleate oleophilic surfactant and 3% polyethoxylated sorbitantrioleate hydrophilic surfactant (ethoxylated with 20 moles of ethylene oxide), all by weight of the oil suspension.
- the mixture was thoroughly stirred and allowed to stand at room temperature until it attained a temperature in the range of from 70 to 75°F.
- a sample of the oil suspension was then placed in a centrifuge tube and subjected to 6 minutes of rotation at 1,000 revolutions per minute. The resulting oil suspension did not exhibit separation, settling or sludging over time.
- EXAMPLE 2 A mineral oil suspension of fine silica having a particle size in the range of from 16 to 20 microns was prepared comprised of 50%> fine silica, 43.9% mineral oil having a viscosity at 100°F of 70 saybolt seconds, 3% oleophilic clay, 0.1% sorbitantrioleate oleophilic surfactant and 3% polyethoxylated sorbitantrioleate hydrophilic surfactant (substituted with 20 moles of ethylene oxide), all by weight of the oil suspension. The mixture was thoroughly stirred and allowed to stand at room temperature until it attained a temperature in the range of from 70 to 75°F.
- a sample of the oil suspension was then placed in a centrifuge tube and subjected to 6 minutes of rotation at 1,000 revolutions per minute. The resulting oil suspension did not exhibit separation, settling or sludging over time.
- EXAMPLE 3 A mineral oil suspension of amorphous silica having a particle size in the range of from 5 to 20 microns was prepared comprised of 45% amorphous silica, 50.9%> mineral oil having a viscosity at 100°F of 70 saybolt seconds, 1% oleophilic clay, 0.1% sorbitantrioleate oleophilic surfactant and 3% polyethoxylated sorbitantrioleate hydrophilic surfactant (ethoxylated with 20 moles of ethylene oxide), all by weight of the oil suspension.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/695,892 US6983800B2 (en) | 2003-10-29 | 2003-10-29 | Methods, cement compositions and oil suspensions of powder |
US10/695,892 | 2003-10-29 |
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WO2005052309A1 true WO2005052309A1 (en) | 2005-06-09 |
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PCT/GB2004/004348 WO2005052309A1 (en) | 2003-10-29 | 2004-10-14 | Methods, cement compositions and oil suspensions of powder |
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US (3) | US6983800B2 (en) |
WO (1) | WO2005052309A1 (en) |
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2006
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Also Published As
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US7393814B2 (en) | 2008-07-01 |
US6983800B2 (en) | 2006-01-10 |
US20060048683A1 (en) | 2006-03-09 |
US20050092491A1 (en) | 2005-05-05 |
US20070022917A1 (en) | 2007-02-01 |
US7147705B2 (en) | 2006-12-12 |
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