Classifications

• • 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
  • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
  • C09K8/504—Compositions based on water or polar solvents
  • C09K8/506—Compositions based on water or polar solvents containing organic compounds
• • 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
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/10—Coating or impregnating
  • C04B20/1018—Coating or impregnating with organic materials
• • 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
  • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
  • C04B28/26—Silicates of the alkali metals
• • 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
• • 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
  • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
  • C09K2208/10—Nanoparticle-containing well treatment fluids
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S507/00—Earth boring, well treating, and oil field chemistry
  • Y10S507/902—Controlled release agent
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S507/00—Earth boring, well treating, and oil field chemistry
  • Y10S507/906—Solid inorganic additive in defined physical form

Definitions

• This invention relates to a sealant fluid, in particular a composition comprising an alkali metal silicate solution and a calcium-containing inorganic compound that can be used to seal narrow cracks and pore spaces of subterranean wells.
• voids may be cracks in the cement, or microannuli between the casing and the cement or between the cement and the formation. These voids could also be pore spaces between gravel in gravel-packs in zones that are producing too much water to remain economic.
• a common method of plugging these voids is to inject a cement formulation where the cement is made from micro-fine cement particles (see p 247 Well Cementing, 2 nd Edition, E. Nelson and D. Guillot editors, Schlumberger 2006) where the micro-fine particles have a median size of 3-5 microns.
• squeeze cement pp 521-543 Well Cementing, 2 nd Edition, E.
• U.S. Pat. No. 6,312,515 also discloses a squeeze cementing method using a cement formulation with micro-fine particles.
• U.S. Pat. No. 6,312,515 also discloses a squeeze cementing method using a cement formulation with micro-fine particles.
• this technology there is a lower limit to the size of the voids that can be filled when using micro-fine cementing technology because of the particle size.
• the voids (microannuli, fractures and pores) in subterranean wells that the sealant composition needs to penetrate can be very small and narrow, and therefore the solid particles in sealant compositions need to be small enough to effectively penetrate into these gaps.
• the reaction between the calcium carbonate and sodium metasilicate can occur very quickly. This can cause problems due to the onset of thickening of the composition before it has sufficiently penetrated the pores and fractures of the formation. If the composition becomes too thick to pump properly the sealant composition may not be correctly placed in all the voids before it sets. This may reduce the extent of, or even prevent the formation of, the barrier that is meant to be created throughout the formation.
• the subterranean formations may have temperatures higher than surface conditions which lead to even higher reaction rates between the calcium carbonate and the silicate solution.
• a first aspect of the invention comprises a sealant composition comprising an alkali metal silicate and a calcium-containing inorganic compound wherein the particles of the calcium containing compound have a mean particle size that is submicron.
• the extremely small size of the calcium containing compound allows the fluid to penetrate into the small fractures and pore spaces in the formation.
• Calcium compounds with a solubility in water ⁇ 2 g/Litre at 20° C. are preferred.
• the calcium containing compound is calcium carbonate.
• other low solubility calcium compounds, e.g. calcium hydroxide, may be used.
• the alkali metal silicate is sodium metasilicate.
• other sodium silicates or potassium or lithium silicates can be used.
• the calcium particles have a mean size below 500 nm.
• the particles may have a mean particle size between 350 and 200 nm.
• the mean particle size is below 100 nm.
• the size of the calcium carbonate particles can depend on the application of the sealant composition.
• the particles of the calcium containing compound may comprise a hydrophobic coating.
• a calcium carbonate may be treated with a fatty acid such as stearic acid to form a hydrophobic coating of calcium stearate on the calcium carbonate particles.
• the composition can also comprise an antifoam and/or a surfactant.
• Other additives may also be present in the composition such as, fluid loss control additives, retarders, and viscosity control additives, such as viscosifiers or dispersants.
• a second aspect of the invention comprises a method for sealing voids in a wellbore comprising injecting a composition as described above into a void of the wellbore and letting the composition set.
• the fluid composition sets it provides an impermeable barrier plugging pores, fractures and other voids in the zone of the wellbore the composition has been injected into.
• the voids can be pores and cracks in the formation, cracks in the cement sheath, voids (microannuli) between the casing and the cement or between the cement and the formation, and/or pores in the gravel packs.
• the method comprises pumping a composition described above from the surface down the wellbore before injecting.
• the method can comprise pumping an alkali metal silicate compound and a calcium containing inorganic compound separately from the surface down the borehole; and allowing the alkali metal silicate compound and the calcium containing compound to mix together downhole before injecting the composition into a void.
• Each compound is initially present as separate composition which are each then pumped down the borehole and allowed to mix such that the silicate/calcium containing sealant composition is formed downhole
• the sealant composition can be used in low temperature environments.
• temperatures may be as low as 4° C. at the seabed in deepwater environments and below 0° C. in permafrost zones.
• the sealant composition of the invention comprises a calcium containing inorganic compound, such as calcium carbonate, in a solution of an alkali metal silicate.
• the solution is sodium silicate with a SiO 2 to Na 2 O ratio ⁇ 1.5, such as a sodium metasilicate which has a SiO 2 to Na 2 O ratio of 1:1, but other sodium silicates with SiO 2 to Na 2 O ratio ⁇ 1.5 may be used.
• potassium or lithium silicates may be used.
• the composition comprises nanosized calcium carbonate particles.
• nanosized it is meant particles that are sub microns size i.e. less than 1000 nm in size, preferably less than 500 nm.
• the nanosized calcium carbonate particles are dispersed in an alkali metal silicate solution. This creates an ultra-fine suspension that can be injected into voids in the near-wellbore region and is capable of penetrating the pores and cracks in this region.
• the fluid composition will set to form a hard impermeable mass in the pores and fractures and plug these gaps to prevent lost circulation.
• calcium carbonate When the calcium carbonate is mixed into the silicate solution calcium ions react with the silica in the solution to create calcium silicate hydrates.
• the calcium carbonate can be prepared from ground marble, limestone, calcite or aragonite.
• the setting time of the sealant fluid can be controlled by adjusting the size of calcium carbonate particles that are dispersed in the sodium metasilicate solution. By increasing the size of the particles the surface area is decreased and therefore the particles are less reactive. The size of the particles still remain in the nanosize range and therefore are small enough to fit in the narrow cracks and pores of the formation, however the composition will have a delayed setting time compared to a similar composition having smaller particles.
• the setting time of the sealant fluid can also be increased by using hydrophobically coated calcium carbonate particles in the solution of the sodium metasilicate.
• a sealant fluid comprising hydrophobically coated calcium carbonate particles will have a longer setting time than a composition with calcium carbonates particles that are the same size but are not coated.
• the setting time can also be adjusted by changing the molar ratio of SiO 2 to Na 2 O. Increasing the molar ratio will increase the setting time.
• sodium metasilicate (anhydrous) (available from Van Eyck Chimie).
• the sodium metasilicate is used as a solution containing 30 g of sodium metasilicate and 70 g of distilled water.
• Socal® 31 (Solvay): a rhombohedral calcite (a precipitated calcium carbonate) with a mean particle size of 70 nm
• Socal® 90A (Solvay): an ortho-rhombic aragonite (a precipitated calcium carbonate) with a mean particle size between 200 nm and 350 nm.
• Socal® 312 (Solvay): a version of Socal® 31 that has a hydrophobic coating.
• the calcium carbonate is formed by precipitation from a lime solution.
• the hydrophobically modified calcium carbonate is reacted with fatty acids in suspension.
• Socal®90A with a mean particle size of 250-300 nm resulted in a sealant fluid with a setting time considerably longer than the setting of the composition using Socal®31 where the particles only have a mean size of 70 nm.
• the larger particles have reduced surface area and therefore are less reactive than the smaller particles.
• Another way to increase the setting time of the system is to increase the SiO 2 to Na 2 O ratio.
• the particles used in the composition are small enough to penetrate the fractures and pores of the formation before the composition set. While the setting time of the composition can be delayed enough to allow the sodium metasilicate and calcium carbonate to be mixed together before pumping down the wellbore and injection into the voids. This simplifies the process as rather then using a two stage process whereby each component is injected separately, the composition can be injected as one composition. If a two stage process system is used the silicate containing composition and a calcium containing composition are mixed together downhole after being pumped separately down the borehole but before injection into the void. A silicate containing solution and a calcium containing solution can be pumped separately down the wellbore, either by pumping the compositions down two separate tubes or down two separate compartments of the same tube. Alternatively one component is pumped down a tube or pipe in the wellbore, such as the drill pipe or coiled tubing, and the other component is pumped down the annulus formed by the tube and the casing/wellbore, before mixing at the place of injection.
• the sealant fluid is also suitable for use in low temperature applications, where conventional sealant systems can take a long time to set, such as at the seabed in deep water environments, which the temperature can be as low as 4° C. or permafrost zones where temperatures can be below 0° C. In this situation it may be sufficient to provide calcium carbonate particles of any size in the nanosize range, without the need to retard the setting time of the composition, i.e. by increasing the particles size or using hydrophobic particles, as the low temperatures will slow the reactions and setting time down.
• the sealant composition When the calcium carbonate/sodium metasilicate composition with nanosized calcium carbonate particles is used in low temperature environments, the sealant composition will have a faster setting time than conventional sealant systems.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Ceramic Engineering (AREA)
• Inorganic Chemistry (AREA)
• Structural Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Sealing Material Composition (AREA)
• Glass Compositions (AREA)
• Soil Conditioners And Soil-Stabilizing Materials (AREA)

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• 2007
  • 2007-10-30 DK DK07119640.6T patent/DK2055683T3/da active
  • 2007-10-30 AT AT07119640T patent/ATE510803T1/de not_active IP Right Cessation
  • 2007-10-30 EP EP07119640A patent/EP2055683B1/fr not_active Not-in-force
• 2008
  • 2008-10-28 US US12/259,532 patent/US20090107677A1/en not_active Abandoned
  • 2008-10-29 WO PCT/EP2008/009126 patent/WO2009056291A1/fr active Application Filing
  • 2008-10-29 CA CA2703729A patent/CA2703729C/fr not_active Expired - Fee Related
• 2010
  • 2010-04-16 NO NO20100547A patent/NO20100547L/no not_active Application Discontinuation
  • 2010-12-06 US US12/961,091 patent/US8158563B2/en not_active Expired - Fee Related

Patent Citations (7)

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