Classifications

• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B33/00—Sealing or packing boreholes or wells
  • E21B33/10—Sealing or packing boreholes or wells in the borehole
  • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
• • 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
  • 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
• • 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
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B33/00—Sealing or packing boreholes or wells
  • E21B33/10—Sealing or packing boreholes or wells in the borehole
  • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
  • E21B33/14—Methods or devices for cementing, for plugging holes, crevices or the like for cementing casings into boreholes
• • 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

• Embodiments relate to subterranean cementing operations and, in certain embodiments, to set-delayed cement compositions and methods of using set-delayed cement compositions in subterranean formations.
• cement compositions may be used in a variety of subterranean operations.
• a pipe string e.g., casing, liners, expandable tubulars, etc.
• the process of cementing the pipe string in place is commonly referred to as "primary cementing.”
• primary cementing In a typical primary cementing method, a cement composition may be pumped into an annulus between the walls of the wellbore and the exterior surface of the pipe string disposed therein.
• the cement composition may set in the annular space, thereby forming an annular sheath of hardened, substantially impermeable cement (i.e., a cement sheath) that may support and position the pipe string in the wellbore and may bond the exterior surface of the pipe string to the subterranean formation.
• a cement sheath the cement sheath surrounding the pipe string functions to prevent the migration of fluids in the annulus, as well as protecting the pipe string from corrosion.
• Cement compositions also may be used in remedial cementing methods, for example, to seal cracks or holes in pipe strings or cement sheaths, to seal highly permeable formation zones or fractures, to place a cement plug, and the like.
• a broad variety of cement compositions have been used in subterranean cementing operations.
• set-delayed cement compositions have been used.
• Set-delayed cement compositions are characterized by remaining in a pumpable fluid state for at least about one day (e.g., at least about 7 days, about 2 weeks, about 2 years or more) at room temperature (e.g., about 80° F) in quiescent storage.
• the set- delayed cement compositions should be capable of being activated whereby reasonable compressive strengths are developed.
• a cement set accelerator may be added to a set-delayed cement composition whereby the composition sets into a hardened mass.
• the set-delayed cement composition may be suitable for use in wellbore applications, for example, where it is desired to prepare the cement composition in advance.
• This may allow, for example, the cement composition to be stored prior to its use.
• this may allow, for example, the cement composition to be prepared at a convenient location and then transported to the job site. Accordingly, capital expenditures may be reduced due to a reduction in the need for on-site bulk storage and mixing equipment. This may be particularly useful for offshore cementing operations where space onboard the vessels may be limited.
• Whi le set-delayed cement compositions have been developed heretofore, challenges exist with their successful use in subterranean cementing operations.
• set-delayed cement compositions may benefit from an increase in compressive strength development.
• boosts to early strength development as well as long term strength development would provide compositions capable of a being used in a broader variety of operations as compared to compositions that develop compressive strength slower or do not develop as much long term strength.
• FIG. 1 illustrates a system for the preparation and delivery of a set-delayed cement composition to a wellbore in accordance with certain embodiments.
• FIG. 2 illustrates surface equipment that may be used in the placement of a set- delayed cement composition in a wellbore in accordance with certain embodiments.
• FIG. 3 illustrates the placement of a set-delayed cement composition into a wellbore annulus in accordance with certain embodiments.
• Embodiments relate to subterranean cementing operations and, in certain embodiments, to set-delayed cement compositions and methods of using set-delayed cement compositions in subterranean formations.
• the set-delayed cement compositions may be used with strength enhancers, such as cement kiln dust, slag, and/or a silica source (e.g., a pozzolan).
• strength enhancers such as cement kiln dust, slag, and/or a silica source (e.g., a pozzolan).
• Embodiments of the set-delayed cement compositions comprising strength enhancers may accelerate early strength development and/or may also achieve desirable thickening times and late term compressive strength development.
• Embodiments of the set-delayed cement compositions may generally comprise water, pumice, hydrated lime, and a set retarder.
• the set-delayed cement compositions may further comprise a dispersant, slag, cement kiln dust, amorphous silica, a pozzolan, and/or a cement set activator.
• Embodiments of the set-delayed cement compositions may be foamed.
• embodiments of the set-delayed cement compositions may be capable of remaining in a pumpable fluid state for an extended period of time. For example, the set-delayed cement compositions may remain in a pumpable fluid state for at least about 1 day, about 2 weeks, about 2 years, or longer.
• the set-delayed cement compositions may develop reasonable compressive strengths after activation at relatively low temperatures. While the set-delayed cement compositions may be suitable for a number of subterranean cementing operations, they may be particularly suitable for use in subterranean formations having relatively low bottom hole static temperatures, e.g., temperatures less than about 200 °F or ranging from about 100 °F to about 200 °F. In alternative embodiments, the set-delayed cement compositions may be used in subterranean formations having bottom hole static temperatures up to 450 °F or higher.
• the water may be from any source provided that it does not contain an excess of compounds that may undesirably affect other components in the set-delayed cement compositions.
• a set-delayed cement composition may comprise fresh water or salt water.
• Salt water generally may include one or more dissolved salts therein and may be saturated or unsaturated as desired for a particular application. Seawater or brines may be suitable for use in embodiments.
• the water may be present in an amount sufficient to form a pumpable slurry. In certain embodiments, the water may be present in the set-delayed cement composition in an amount in the range of from about 33% to about 200% by weight of the pumice.
• the water may be present in the set-delayed cement compositions in an amount in the range of from about 35% to about 70% by weight of the pumice.
• the water may be present in the set-delayed cement compositions in an amount in the range of from about 35% to about 70% by weight of the pumice.
• Pumice may be present in the -delayed cement compositions.
• pumice is a volcanic rock that can exhibit cementitious properties in that it may set and harden in the presence of hydrated lime and water.
• the pumice may also be ground.
• the pumice may have any particle size distribution as desired for a particular application.
• the pumice may have a mean particle size in a range of from about 1 micron to about 200 microns. The mean particle size corresponds to d50 values as measured by particle size analyzers such as those manufactured by Malvern Instruments, Worcestershire, United Kingdom.
• the pumice may have a mean particle size in a range of from about 1 micron to about 200 microns, from about 5 microns to about 100 microns, or from about 10 microns to about 50 microns. In one particular embodiment, the pumice may have a mean particle size of less than about 15 microns.
• An example of a suitable pumice is available from Hess Pumice Products, Inc., Malad, Idaho, as DS-325 lightweight aggregate, having a particle size of less than about 15 microns. It should be appreciated that particle sizes too small may have mixability problems while particle sizes too large may not be effectively suspended in the compositions.
• One of ordinary skill in the art, with the benefit of this disclosure, should be able to select a particle size for the pumice suitable for a chosen application.
• Hydrated lime may be present in the set-delayed cement compositions.
• the term "hydrated lime” will be understood to mean calcium hydroxide.
• the hydrated lime may be provided as quicklime (calcium oxide) which hydrates when mixed with water to form the hydrated lime.
• the hydrated lime may be included in embodiments of the set-delayed cement compositions, for example, to form a hydraulic composition with the pumice.
• the hydrated lime may be included in a pumice- to-hydrated-lime weight ratio of about 10: 1 to about 1 : 1 or 3: 1 to about 5: 1.
• the hydrated lime may be included in the set-delayed cement compositions in an amount in the range of from about 10% to about 100% by weight of the pumice, for example. In some embodiments, the hydrated lime may be present in an amount ranging between any of and/or including any of about 10%, about 20%, about 40%, about 60%, about 80%, or about 100% by weight of the pumice.
• the cementitious components present in the set-delayed cement composition may consist essentially of the pumice and the hydrated lime. For example, the cementitious components may primarily comprise the pumice and the hydrated lime without any additional components (e.g., Portland cement, fly ash, slag cement) that hydraulically set in the presence of water.
• additional components e.g., Portland cement, fly ash, slag cement
• a set retarder maybe present in the set-delayed cement compositions.
• a broad variety of set retarders may be suitable for use in the set-delayed cement compositions.
• the set retarder may comprise phosphonic acids, such as ethylenediamine tetra(methylene phosphonic acid), diethylenetriamine penta(methylene phosphonic acid), etc.; lignosulfonates, such as sodium lignosulfonate, calcium lignosulfonate, etc.; salts such as stannous sulfate, lead acetate, monobasic calcium phosphate, organic acids, such as citric acid, tartaric acid, etc.; cellulose derivatives such as hydroxyl ethyl cellulose (HEC) and carboxymethyl hydroxyethyl cellulose (C HEC); synthetic co- or ter-polymers comprising sulfonate and carboxylic acid groups such as sulfonate-functionalized acrylamide-acrylic acid co-polymers; bo
• Suitable set retarders include, among others, phosphonic acid derivatives.
• One example of a suitable set retarder is Micro Matrix ® cement retarder, available from Halliburton Energy Services, Inc.
• the set retarder may be present in the set-delayed cement compositions in an amount sufficient to delay the setting for a desired time. In some embodiments, the set retarder may be present in the set-delayed cement compositions in an amount in the range of from about 0.01 % to about 10% by weight of the pumice.
• the set retarder may be present in an amount ranging between any of and/or including any of about 0.01 %, about 0.1 %, about 1 %, about 2%, about 4%, about 6%, about 8%, or about 10% by weight of the pumice.
• the appropriate amount of the set retarder to include for a chosen appl ication.
• a strength enhancer may be included in the set-delayed cement compositions.
• the strength enhancer may comprise cement kiln dust, slag, or combination thereof.
• the cement kiln dust or slag may be added to the set-delayed cement compositions prior to, concurrently with, or after activation.
• Cement kiln dust (“CKD”) as that term is used herein, refers to a partially calcined kiln feed which is removed from the gas stream and collected in a dust collector during the manufacture of cement.
• CKD cement kiln dust
• the chemical analysis of CKD from various cement manufactures varies depending on a number of factors, including the particular kiln feed, the efficiencies of the cement production operation, and the associated dust collection systems.
• CKD generally may comprise a variety of oxides, such as S1O2, AI2O3, Fe2Cb, CaO, MgO, SO3, Na20, and K2O.
• Slag refers to a granulated, blast furnace by-product formed in the production of various metals from their corresponding ores.
• the production of cast iron can produce slag as a granulated, blast furnace by- product with the slag generally comprising the oxidized impurities found in iron ore.
• the slag may provide an easily soluble calcium silicate and calcium aluminate source that can aid strength development of the set-delayed cement compositions.
• the strength enhancer may be included in the set-delayed cement composition at any suitable time as desired for a particular application. By way of example, the strength enhancer may be included before or after activation of the set-delayed cement composition.
• the CKD and/or slag may be included in embodiments of the set-delayed cement compositions in an amount suitable for a particular application.
• the CKD and/or slag may be present in an amount of about 1 % to about 400% by weight of the pumice, for example, about 1 %, about 10%, about 50%, about 100%, about 250%, or about 400%.
• the CKD and/or slag may be used to enhance the 24 hour compressive strength by about 100% or greater.
• the CKD or slag may be used to enhance the 24 hour compressive strength by about 100%, about 125%, about 150%, about 200% or more.
• the CKD and/or slag may be used to enhance the 72 hour compressive strength by about 50% or greater.
• the CKD or slag may be used to enhance the 72 hour compressive strength by about 50%, about 60%, about 75%, about 100% or more.
• One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the strength enhancer to include for a chosen application.
• embodiments of the set-delayed cement compositions may optionally comprise a dispersant.
• suitable dispersants include, without limitation, sulfonated-formaldehyde-based dispersants (e.g., sulfonated acetone formaldehyde condensate), examples of which may include Daxad ® 19 dispersant available from Geo Specialty Chemicals, Ambler, Pennsylvania.
• Other suitable dispersants may be polycarboxylated ether dispersants such as Liquiment ® 5581F and Liquiment ® 514L dispersants available from BASF Corporation Houston, Texas; or EthacrylTM G dispersant available from Coatex, Genay, France.
• a suitable commercially available dispersant is CFRTM-3 dispersant, available from Halliburton Energy Services, Inc, Houston, Texas.
• the Liquiment ® 514L dispersant may comprise 36% by weight of the polycarboxylated ether in water. While a variety of dispersants may be used in accordance with embodiments, polycarboxylated ether dispersants may be particularly suitable for use in some embodiments. Without being limited by theory, it is believed that polycarboxylated ether dispersants may synergistically interact with other components of the set-delayed cement composition.
• the polycarboxylated ether dispersants may react with certain set retarders (e.g., phosphonic acid derivatives) resulting in formation of a gel that suspends the pumice and hydrated lime in the composition for an extended period of time.
• certain set retarders e.g., phosphonic acid derivatives
• the dispersant may be included in the set-delayed cement compositions in an amount in the range of from about 0.01 % to about 5% by weight of the pumice. In specific embodiments, the dispersant may be present in an amount ranging between any of and/or including any of about 0.01 %, about 0.1 %, about 0.5%, about 1 %, about 2%, about 3%, about 4%, or about 5% by weight of the pumice.
• One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the dispersant to include for a chosen application.
• additives suitable for use in subterranean cementing operations also may be included in embodiments of the set-delayed cement compositions.
• additives include, but are not limited to: weighting agents, lightweight additives, gas- generating additives, mechanical-property-enhancing additives, lost-circukom materials, filtration-control additives, fluid-loss-control additives, defoaming agents, foaming agents, thixotropic additives, and combinations thereof.
• one or more of these additives may be added to the set-delayed cement compositions after storing but prior to the placement of a set-delayed cement composition into a subterranean formation.
• a person having ordinary skill in the art, with the benefit of this disclosure should readily be able to determine the type and amount of additive useful for a particular application and desired result.
• the set-delayed cement compositions generally should have a density suitable for a particular application.
• the set-delayed cement compositions may have a density in the range of from about 4 pounds per gallon ("lb/gal") to about 20 lb/gal.
• the set-delayed cement compositions may have a density in the range of from about 8 lb/gal to about 17 lb/gal.
• Embodiments of the set-delayed cement compositions may be foamed or unfoamed or may comprise other means to reduce their densities, such as hollow microspheres, low-density elastic beads, or other density-reducing additives known in the art.
• the density may be reduced after storing the composition, but prior to placement in a subterranean formation.
• the set-delayed cement compositions may have a delayed set in that they remain in a pumpable fluid state for at least one day (e.g., at least about 1 day, about 2 weeks, about 2 years or more) at room temperature (e.g., about 80 °F) in quiescent storage.
• the set-delayed cement compositions may remain in a pumpable fluid state for a period of time from about 1 day to about 7 days or more.
• the set-delayed cement compositions may remain in a pumpable fluid state for at least about 1 day, about 7 days, about 10 days, about 20 days, about 30 days, about 40 days, about 50 days, about 60 days, or longer.
• a fluid is considered to be in a pumpable fluid state where the fluid has a consistency of less than 70 Bearden units of consistency ("Be"), as measured on a pressurized consistometer in accordance with the procedure for determining cement thickening times set forth in API RP Practice 10B-2, Recommended Practice for Testing Well Cements, First Edition, July 2005.
• Be Bearden units of consistency
• cement set activator or “activator”, as used herein, refers to an additive that activates a set-delayed or heavily retarded cement composition and may also accelerate the setting of the set-delayed, heavily retarded, or other cement composition.
• embodiments of the set-delayed cement compositions may be activated to form a hardened mass in a time period in the range of from about 1 hour to about 12 hours.
• embodiments of the set-delayed cement compositions may set to form a hardened mass in a time period ranging between any of and/or including any of about 1 day, about 2 days, about 4 days, about 6 days, about 8 days, about 10 days, or about 12 days.
• the set-delayed cement compositions may set to have a desirable compressive strength after activation.
• Compressive strength is generally the capacity of a material or structure to withstand axially di rected pushing forces. The compressive strength may be measured at a specified time after the set-delayed cement composition has been activated and the resultant composition is maintained under specified temperature and pressure conditions. Compressive strength can be measured by either destructive or nondestructive methods.
• the destructive method physically tests the strength of treatment fluid samples at various points in time by crushing the samples in a compression-testing machine.
• the compressive strength is calculated from the failure load divided by the cross-sectional area resisting the load and is reported in units of pound-force per square inch (psi).
• Nondestructive methods may employ a UCATM ultrasonic cement analyzer, available from Fann Instrument Company, Houston, TX. Compressive strength values may be determined in accordance with API RP 10B-2, Recommended Practice for Testing Well Cements, First Edition, July 2005.
• the set-delayed cement compositions may develop a 24- hour compressive strength in the range of from about 50 psi to about 5000 psi, alternatively, from about 100 psi to about 4500 psi, or alternatively from about 500 psi to about 4000 psi.
• the set-delayed cement compositions may develop a compressive strength in 24 hours of at least about 50 psi, at least about 100 psi, at least about 500 psi, or more.
• the compressive strength values may be determined using destructive or non-destructive methods at a temperature ranging from 100 °F to 200 °F.
• the set-delayed cement compositions may have desirable thickening times after activation.
• Thickening time typically refers to the time a fluid, such as a set-delayed cement composition, remains in a fluid state capable of being pumped.
• a number of different laboratory techniques may be used to measure thickening time.
• a pressurized consistometer operated in accordance with the procedure set forth in the aforementioned API RP Practice 10B-2, may be used to measure whether a fluid is in a pumpable fluid state.
• the thickening time may be the time for the treatment fluid to reach 70 Be and may be reported as the time to reach 70 Be.
• the cement compositions may have a thickening time of greater than about 1 hour, alternatively, greater than about 2 hours, alternatively greater than about 5 hours at 3,000 psi and temperatures in a range of from about 50 °F to about 400 °F, alternatively, in a range of from about 80 °F to about 250 °F, and alternatively at a temperature of about 140 °F.
• Embodiments may include the addition of a cement set activator to the set- delayed cement compositions.
• suitable cement set activators include, but are not l imited to: zeolites, amines such as triethanolamine, diethanolamine; sil icates such as sodium silicate; zinc formate; calcium acetate; Groups IA and 1IA hydroxides such as sodium hydroxide, magnesium hydroxide, and calcium hydroxide; monovalent salts such as sodium chloride; divalent salts such as calcium chloride; nanosilica (i.e., silica having a particle size of less than or equal to about 100 nanometers); polyphosphates; and combinations thereof.
• a combination of the polyphosphate and a monovalent salt may be used for activation.
• the monovalent salt may be any salt that dissociates to form a monovalent cation, such as sodium and potassium salts.
• suitable monovalent salts include potassi um sulfate, and sodium sulfate.
• a variety of different polyphosphates may be used in combination with the monovalent salt for activation of the set-delayed cement compositions, including polymeric metaphosphate salts, phosphate salts, and combinations thereof.
• polymeric metaphosphate salts that may be used include sodium hexametaphosphate, sodium tri metaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate, and combinations thereof.
• a specific example of a suitable cement set activator comprises a combination of sodium sulfate and sodium hexametaphosphate.
• the activator may be provided and added to the set-delayed cement composition as a liquid additive, for example, a liquid additive comprising a monovalent salt, a polyphosphate, and optionally a dispersant.
• Some embodiments may include a cement set activator comprising nanosilica.
• the term “nanosilica” refers to silica having a particle size of less than or equal to about 100 nanometers ("nm").
• the size of the nanosilica may be measured using any suitable technique. It should be understood that the measured size of the nanosilica may vary based on measurement technique, sample preparation, and sample conditions such as temperature, concentration, etc.
• One technique for measuring the particle size of the nanosilica is Transmission Electron Microscopy (TEM).
• TEM Transmission Electron Microscopy
• An example of a commercially available product based on laser diffraction is the ZETASIZER Nano ZS particle size analyzer supplied by Malvern Instruments, Worcerstershire, UK.
• the nanosilica may comprise colloidal nanosilica.
• the nanosilica may be stabilized using any suitable technique.
• the nanosilica may be stabilized with a metal oxide, such as lithium oxide, sodium oxide, potassium oxide, and/or a combination thereof. Additionally the nanosilica may be stabilized with an amine and/or a metal oxide as mentioned above.
• a metal oxide such as lithium oxide, sodium oxide, potassium oxide, and/or a combination thereof.
• the nanosilica may be stabilized with an amine and/or a metal oxide as mentioned above.
• Embodiments of the nanosilicas have an additional advantage in that they have been known to fill in pore space in cements which can result in superior mechanical properties in the cement after it has set.
• Some embodiments may include a cement set activator comprising a combination of a monovalent salt and a polyphosphate. The monovalent salt and the polyphosphate may be combined prior to addition to the set-delayed cement composition or may be separately added to the set-delayed cement composition.
• the monovalent salt may be any salt that dissociates to form a monovalent cation, such as sodium and potassium salts.
• suitable monovalent salts include potassium sulfate and sodium sulfate.
• a variety of different polyphosphates may be used in combination with the monovalent salt for activation of the set-delayed cement compositions, including polymeric metaphosphate salts, phosphate salts, and combinations thereof, for example.
• polymeric metaphosphate salts that may be used include sodium hexametaphosphate, sodium trimetaphosphate, sodium tetrametaphosphate, sodium pentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate, and combinations thereof.
• a specific example of a suitable cement set activator comprises a combination of sodium sulfate and sodium hexametaphosphate.
• sodium hexametaphosphate is also known in the art to be a strong retarder of Portland cements.
• polyphosphates may be used as a cement set activator for embodiments of the set-delayed cement compositions disclosed herein.
• the ratio of the monovalent salt to the polyphosphate may range, for example, from about 5: 1 to about 1 :25 or from about 1 : 1 to about 1 : 10.
• Embodiments of the cement set activator may comprise the monovalent salt and the polyphosphate salt in a ratio (monovalent salt to polyphosphate) ranging between any of and/or including any of about 5: 1 , 2: 1 , about 1 : 1 , about 1 :2, about 1 :5, about 1 : 10, about 1 :20, or about 1 :25.
• the combination of the monovalent salt and the polyphosphate may be mixed with a dispersant and water to form a liquid additive for activation of a set-delayed cement composition.
• suitable dispersants include, without limitation, the previously described dispersants, such as sulfonated-formaldehyde- based dispersants and polycarboxylated ether dispersants.
• a suitable sulfonated-formaldehyde-based dispersant is a sulfonated acetone formaldehyde condensate, available from Halliburton Energy Services, Inc., as CFR-3TM dispersant.
• a suitable polycarboxylated ether dispersant is Liquiment ® 514L or 5581 F dispersants, available from BASF Corporation, Houston, Texas.
• the cement set activator may be added to embodiments of the set-delayed cement composition in an amount sufficient to induce the set-delayed cement composition to set into a hardened mass.
• the cement set activator may be added to the set-delayed cement composition in an amount in the range of about 0.1% to about 20% by weight of the pumice.
• the cement set activator may be present in an amount ranging between any of and/or including any of about 0.1 %, about 1 %, about 5%, about 10%. about 1 5%, or about 20% by weight of the pumice.
• wi ll recognize the appropriate amount of cement set activator to include for a chosen application.
• Some embodiments of the cement set activator may comprise silica sources; for example, amorphous silica and/or a pozzolan for use as a strength enhancer.
• a cement set activator may comprise calcium chloride and a silica source.
• the strength enhancers comprising a silica source may be used for enhancing early strength enhancement in a similar manner to the previously described cement kiln dust and/or slag strength enhancers.
• the strength enhancers comprising silica sources may be added to a cement set activator instead of directly to a set- delayed cement composition.
• adding a strength enhancer comprising a silica source directly to a set-delayed cement composition may induce gelation or flash setting.
• embodiments comprising a cement set activator comprising a silica-source strength enhancer may not induce gelation or flash setting.
• a strength enhancer comprising a silica source may comprise amorphous silica.
• Amorphous silica is a powder that may be included in embodiments of the cement set activators to increase cement compressive strength.
• Amorphous silica is generally a byproduct of a ferrosilicon production process, wherein the amorphous silica may be formed by oxidation and condensation of gaseous silicon suboxide, SiO, which is formed as an intermediate during the process.
• An example of a suitable source of amorphous silica is SilicaliteTM cement additive available from Halliburton Energy Services, Inc., Houston, Texas.
• Embodiments comprising strength enhancers may utilize the additional silica source as needed to enhance compressive strength.
• a strength enhancer comprising a silica source may comprise a pozzolan.
• pozzolans include diatomaceous earth, metakaolin, zeolite, fly ash, volcanic ash, opaline shale, tuff, and combinations thereof.
• Embodiments comprising strength enhancers may utilize the additional silica source as needed to enhance compressive strength.
• fly ashes may be suitable for use as silica sources for embodiments comprising strength enhancers.
• Fly ash may include fly ash classified as Class C and Class F fly ash according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Ed., July 1 , 1990.
• Suitable examples of fly ash include, but are not limited to, POZMIX® A cement additive, commercially available from Halliburton Energy Services, Inc., Houston, Texas.
• Metakaolin may be suitable for use as a silica source for embodiments comprising strength enhancers.
• metakaolin is a white pozzolan that may be prepared by heating kaolin clay to temperatures in the range of about 600° to about 800°C.
• Diatomaceous earth may be suitable for use as a silica source for embodiments comprising strength enhancers.
• Diatomaceous earth is a soft bulky solid material primarily composed of silica.
• diatomaceous earth is derived from the fossilized remains of the skeletons of small prehistoric aquatic plants referred to as diatoms. It is generally available as a powder.
• An example of a suitable source of diatomaceous earth is Diacel D TM cement additive available from Halliburton Energy Services, Inc., Houston, Texas.
• Zeolites may be suitable for use as a silica source for embodiments comprising strength enhancers.
• Zeolites are generally porous alumino-silicate minerals that may be either natural or synthetic.
• Synthetic zeolites are based on the same type of structural cell as natural zeolites and may comprise aluminosilicate hydrates.
• zeolite refers to all natural and synthetic forms of zeolite.
• An example of a suitable source of zeolite is Valfor-100 ® zeolite or Advera ® 401 zeolite available from the PQ Corporation, Malvern, Pennsylvania.
• the silica-source strength enhancer may be added to embodiments of the cement set activator in an amount sufficient to increase the compressive strength of a set- delayed cement composition.
• the silica source may be added to cement set activator in an amount in the range of about 0.1% to about 20% by weight of the pumice.
• the silica-source strength enhancer may be present in the cement set activator in an amount ranging between any of and/or including any of about 0.1%, about 1 %, about 5%, about 10%, about 15%, or about 20% by weight of the pumice.
• One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of silica-source strength enhancer to include for a chosen application.
• a set-delayed cement composition may be used in a variety of subterranean operations, including primary and remedial cementing.
• a set-delayed cement composition may be provided that comprises water, pumice, hydrated lime, a set retarder, and optionally a dispersant.
• a strength enhancer may be included in the set-delayed cement composition.
• the set-delayed cement composition may be introduced into a subterranean formation and allowed to set therein.
• introducing the set-delayed cement composition into a subterranean formation includes introduction into any portion of the subterranean formation, including, without limitation, into a wellbore drilled into the subterranean formation, into a near wellbore region surrounding the wellbore, or into both.
• Embodiments may further include activation of the set-delayed cement composition.
• the activation of the set-delayed cement composition may comprise, for example, the addition of a cement set activator to the set-delayed cement composition.
• a silica-source strength enhancer may be included in the cement set activator.
• a set-delayed cement composition may be provided that comprises water, pumice, hydrated lime, a set retarder, and optionally a dispersant and/or strength enhancer.
• the set-delayed cement composition may be stored, for example, in a vessel or other suitable container.
• the set-delayed cement composition may be permitted to remain in storage for a desired time period.
• the set-delayed cement composition may remain in storage for a time period of about 1 day or longer.
• the set-delayed cement composition may remain in storage for a time period of about 1 day, about 2 days, about 5 days, about 7 days, about 10 days, about 20 days, about 30 days, about 40 days, about 50 days, about 60 days, or longer.
• the set-delayed cement composition may remain in storage for a time period in a range of from about 1 day to about 7 days or longer. Thereafter, the set-delayed cement composition may be activated, for example, by addition of a cement set activator which may comprise a strength enhancer, introduced into a subterranean formation, and allowed to set therein.
• a cement set activator which may comprise a strength enhancer
• the set-delayed cement composition may be introduced into an annular space between a conduit located in a wellbore and the walls of a wellbore (and/or a larger conduit in the wellbore), wherein the wellbore penetrates the subterranean formation.
• the set-delayed cement composition may be allowed to set in the annular space to form an annular sheath of hardened cement.
• the set-delayed cement composition may form a barrier that prevents the migration of fluids in the wellbore.
• the set-delayed cement composition may also, for example, support the conduit in the wellbore.
• a set-delayed cement composition may be used, for example, in squeeze-cementing operations or in the placement of cement plugs.
• the set-delayed composition may be placed in a wellbore to plug an opening (e.g., a void or crack) in the formation, in a gravel pack, in the conduit, in the cement sheath, and/or between the cement sheath and the conduit (e.g., a microannulus).
• An embodiment includes a method of cementing in a subterranean formation comprising: providing a cement composition comprising water, pumice, hydrated lime, a set retarder, and a strength enhancer, wherein the strength enhancer comprises at least one material selected from the group consisting of cement kiln dust, slag, amorphous silica, a pozzolan, and any combination thereof; introducing the cement composition into the subterranean formation; and allowing the cement composition to set in the subterranean formation.
• the components of the cement composition including the strength enhancer are described in more detail in connection with the embodiments discussed above.
• the cement composition may be set- delayed as described in the embodiments discussed above.
• Cement set activators such as those described previously may be used for activation of the cement composition.
• An embodiment includes a cement composition comprising: water; pumice; hydrated lime; a set retarder; and a strength enhancer, wherein the strength enhancer is selected from the group consisting of cement kiln dust, slag, amorphous silica, and a pozzolan.
• the components of the cement composition including the strength enhancer are described in more detail in connection with the embodiments discussed above.
• the cement composition may be set-delayed as described in the embodiments discussed above.
• Cement set activators such as those described previously may be used for activation of the cement composition.
• An embodiment includes a cementing system comprising a cement composition comprising: water, pumice, hydrated lime, a set retarder, and a strength enhancer, wherein the strength enhancer is selected from the group consisting of cement kiln dust, slag, amorphous silica, and a pozzolan.
• the system may further comprise mixing equipment capable of mixing the cement composition.
• the system may further comprise pumping equipment capable of pumping the cement composition.
• the components of the cement composition including the strength enhancer are described in more detail in connection with the embodiments discussed above.
• the cement composition may be set-delayed as described in the embodiments discussed above. Cement set activators such as those described previously may be used for activation of the cement composition.
• FIG. 1 illustrates a system 2 for the preparation of a set-delayed cement composition and subsequent delivery of the composition to a wellbore in accordance with certain embodiments.
• the set-delayed cement composition may be mixed in mixing equipment 4, such as a jet mixer, re-circulating mixer, or a batch mixer, for example, and then pumped via pumping equipment 6 to the wellbore.
• mixing equipment 4 and the pumping equipment 6 may be disposed on one or more cement trucks as will be apparent to those of ordinary skill in the art.
• a jet mixer may be used, for example, to continuously mix the lime/settable material with the water as it is being pumped to the wellbore.
• a re-circulating mixer and/or a batch mixer may be used to mix the set-delayed cement composition, and the activator may be added to the mixer as a powder prior to pumping the cement composition downhole.
• batch mixer type units for the slurry may be pl umbed in line with a separate tank containing a cement set activator. The cement set activator may then be fed in-line with the slurry as it is pumped out of the mixing unit.
• FIG. 2 illustrates surface equipment 1 0 that may be used in placement of a set-delayed cement composition in accordance with certain embodiments.
• the surface equipment 10 may include a cementing unit 12, which may include one or more cement trucks.
• the cementing unit 12 may include mixing equipment 4 and pumping equipment 6 (e.g., FIG. 1 ) as will be apparent to those of ordinary skill in the art.
• the cementing unit 12 may pump a set-delayed cement composition 14 through a feed pipe 16 and to a cementing head 18 which conveys the set-delayed cement composition 14 downhole.
• the set-delayed cement composition 14 may be placed into a subterranean formation 20 in accordance with example embodiments.
• a wellbore 22 may be drilled into the subterranean formation 20. While wellbore 22 is shown extending generally vertically into the subterranean formation 20, the principles described herein are also applicable to wellbores that extend at an angle through the subterranean formation 20, such as horizontal and slanted wellbores.
• the wellbore 22 comprises walls 24.
• a surface casing 26 has been inserted into the wellbore 22. The surface casing 26 may be cemented to the walls 24 of the wellbore 22 by cement sheath 28.
• one or more additional conduits e.g., intermediate casing, production casing, liners, etc.
• casing 30 may also be disposed in the wellbore 22.
• One or more centralizers 34 may be attached to the casing 30, for example, to centralize the casing 30 in the wellbore 22 prior to and during the cementing operation.
• the set-delayed cement composition 14 may be pumped down the interior of the casing 30.
• the set-delayed cement composition 14 may be allowed to flow down the interior of the casing 30 through the casing shoe 42 at the bottom of the casing 30 and up around the casing 30 into the wellbore annulus 32.
• the set- delayed cement composition 14 may be allowed to set in the wellbore annulus 32, for example, to form a cement sheath that supports and positions the casing 30 in the wellbore 22.
• other techniques may also be utilized for introduction of the set-delayed cement composition 14.
• reverse circulation techniques may be used that include introducing the set-delayed cement composition 14 into the subterranean formation 20 by way of the wel lbore annul us 32 instead of through the casing 30.
• the set-delayed cement composition 14 may displace other fluids 36, such as drilling fluids and/or spacer fluids that may be present in the interior of the casing 30 and/or the wellbore annulus 32. At least a portion of the displaced fluids 36 may exit the wellbore annulus 32 via a flow line 38 and be deposited, for example, in one or more retention pits 40 (e.g., a mud pit), as shown on FIG. 2.
• a bottom plug 44 may be introduced into the wellbore 22 ahead of the set-delayed cement composition 14, for example, to separate the set-delayed cement composition 14 from the fluids 36 that may be inside the casing 30 prior to cementing.
• a diaphragm or other suitable device should rupture to allow the set-delayed cement composition 14 through the bottom plug 44.
• the bottom plug 44 is shown on the landing collar 46.
• a top plug 48 may be introduced into the wellbore 22 behind the set-delayed cement composition 14. The top plug 48 may separate the set-delayed cement composition 14 from a displacement fluid 50 and also push the set-delayed cement composition 14 through the bottom plug 44.
• the exemplary set-delayed cement compositions disclosed herein may directly or indirectly affect one or more components or pieces of equipment associated with the preparation, delivery, recapture, recycling, reuse, and/or disposal of the disclosed set-delayed cement compositions.
• the disclosed set-delayed cement compositions may directly or indirectly affect one or more mixers, related mixing equipment, mud pits, storage facilities or units, composition separators, heat exchangers, sensors, gauges, pumps, compressors, and the like used generate, store, monitor, regulate, and/or recondition the exemplary set-delayed cement compositions.
• the disclosed set-delayed cement compositions may also directly or indirectly affect any transport or delivery equipment used to convey the set-delayed cement compositions to a well site or downhole such as, for example, any transport vessels, conduits, pipelines, trucks, tubulars, and/or pipes used to compositionally move the set-delayed cement compositions from one location to another, any pumps, compressors, or motors (e.g., topside or downhole) used to drive the set-delayed cement compositions into motion, any valves or related joints used to regulate the pressure or flow rate of the set-delayed cement compositions, and any sensors (i.e., pressure and temperature), gauges, and/or combinations thereof, and the like.
• any transport or delivery equipment used to convey the set-delayed cement compositions to a well site or downhole
• any transport vessels, conduits, pipelines, trucks, tubulars, and/or pipes used to compositionally move the set-delayed cement compositions from one location to another
• any pumps, compressors, or motors
• the disclosed set-delayed cement compositions may also directly or indirectly affect the various downhole equipment and tools that may come into contact with the set-delayed cement compositions such as, but not limited to, wellbore casing, wellbore liner, completion string, insert strings, drill string, coiled tubing, slickline, wireline, drill pipe, drill collars, mud motors, downhole motors and/or pumps, cement pumps, surface- mounted motors and/or pumps, central izers, turbolizers, scratchers, floats (e.g., shoes, collars, valves, etc.), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromechanical devices, etc.), sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, etc.), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive coupler, etc.), control lines (e.g.,
• the following example describes a set-delayed cement composition comprising a cement-kiln-dust strength enhancer.
• Three example set-delayed cement compositions were prepared. The three compositions comprised water; DS-325 lightweight aggregate pumice, available from Hess Pumice Products, Inc., Malad, Idaho; hydrated lime; Liquiment 558I F ® dispersant, available from BASF Corporation, Houston, Texas; Micro Matrix ® cement retarder (MMCR), available from Halliburton Energy Services, Inc., Houston, Texas; co-retarder HR ® -5 cement retarder available from Halliburton Energy Services, Inc., Houston, Texas; MicroMax ® weight additive available from Halliburton Energy Services, Inc., Houston, Texas; viscosifier SA-1015TM suspending agent available from Halliburton Energy Services, Inc., Houston, Texas; and optionally strength enhancer Cement kiln dust.
• Table 1 The compositional makeup of all three samples is presented in Table 1 below.
• liquid additive cement set activator was prepared that comprised water, a polyphosphate (sodium hexametaphosphate), a monovalent salt (sodium sulfate), and Liquiment 5581F ® dispersant, available from BASF Corporation, Houston, Texas. 1 18.9 g of the cement set activator was added to each sample.
• the composition for the liquid additive cement set activator is presented in Table 3 below.
• Example 1 illustrates that cement kiln dust can function as a strength enhancer for set-delayed cement compositions.
• the following example describes a set-delayed cement composition comprising a slag strength enhancer.
• Three example activated set-delayed cement compositions were prepared. The three compositions comprised water; DS-325 lightweight aggregate pumice, available from Hess Pumice Products, Inc., Malad, Idaho; hydrated lime; Liquiment 5581 F ® dispersant, available from BASF Corporation, Houston, Texas; Micro Matrix ® cement retarder (MMCR), available from Halliburton Energy Services, Inc., Houston, Texas; co-retarder HR ® -5 cement retarder available from Halliburton Energy Services, Inc., Houston, Texas; MicroMax ® weight additive available from Halliburton Energy Services, Inc., Houston, Texas; viscosifier SA-1015 TM suspending agent available from Halliburton Energy Services, Inc., Houston, Texas; and optionally strength enhancer Slag. Additionally, the samples were activated with a solution of CaCb. The compositional makeup of all three samples is presented in Table 5 below.
• Example 3 [0057] The following example utilized cement set activators comprising strength enhancers composed of different silica sources to show the effect of different silica sources on the strength enhancement of a set-delayed cement composition.
• a control sample was prepared that comprised only CaCb (43% of total cement set activator solution) and water.
• Each experimental cement set activator solution comprised water, calcium chloride, and a silica source. The makeup of the experimental cement set activators is described in Table 7 below.
• Si lica sources were chosen from an amorphous silica, diatomaceous earth, metakaolin, ground D50 pumice, zeolite, and Class F fly ash. Each silica source was present in an amount of 5% of the weight of the pumice ("bwoP") used in the set-delayed cement composition, and CaCb was present in an amount of 10% bwoP.
• the set-delayed cement composition comprised water; DS-325 lightweight aggregate pumice, available from Hess Pumice Products, Inc., Malad, Idaho; hydrated lime; Liquiment 5581F ® dispersant, available from BASF Corporation, Houston, Texas; Micro Matrix ® cement retarder (MMCR), available from Halliburton Energy Services, Inc., Houston, Texas; co-retarder HR ® -5 cement retarder available from Halliburton Energy Services, Inc., Houston, Texas; MicroMax ® weight additive available from Halliburton Energy Services, Inc., Houston, Texas; viscosifier SA-1015 TM suspending agent available from Halliburton Energy Services, Inc., Houston, Texas; and optionally strength enhancer cement kiln dust.
• the compositional makeup of all three samples is presented in Table 8 below.
• the destructive compressive strength of each sample was measured by allowing the samples to cure for 24 hours in 2" by 4" plastic cylinders that were placed in a water bath at 140 °F to form set cylinders. Immediately after removal from the water bath, destructive compressive strengths were determined using a mechanical press in accordance with API RP 1 OB-2, Recommended Practice for Testing Well Cements. The results of this test are set forth below in Table 9 in units of psi. The reported compressive strengths are an average for three cylinders of each sample.
• the same set-delayed cement composition from Example 3 was activated with cement set activators comprising varying concentrations of a pozzolan.
• the CaCb was held constant and the densities for all samples were kept constant by varying the amount of water, such that the only different in each sample was the amount of the pozzolan.
• the pozzolan chosen for the experiment was diatomaceous earth.
• the destructive compressive strength of each sample was measured by allowing the samples to cure for 24 hours in 2" by 4" plastic cylinders that were placed in a water bath at 160 °F to form set cylinders. Immediately after removal from the water bath, destructive compressive strengths were determined using a mechanical press in accordance with API RP 10B-2, Recommended Practice for Testing Well Cements. The results of this test are set forth below in Table 10 in units of psi. The reported compressive strengths are an average for three cylinders of each sample.
• Example 3 shows that the dissolution of the non-retarded pozzolan is responsible for the compressive-strength development for embodiments utilizing a silica- source strength enhancer comprising a pozzolan.
• the same set-delayed cement composition from Example 3 was split into two separate samples. Sample 7 was conditioned without a cement set activator present, and then a cement set activator comprising 5% CaCh bwoP and 5% diatomaceous earth bwoP was added prior to curing. Sample 8 was conditioned with a cement set activator comprising 5% CaCb bwoP and 5% diatomaceous earth bwoP present. Both samples were conditioned at 183 °F for 60 minutes and then 151 °F for 70 minutes. The results are presented in Table 1 1 below.
• Example 6 the same set-delayed cement composition from Example 3 was activated with cement set activators comprising strength enhancers and a monovalent salt and polyphosphate.
• the strength enhancer was held constant and the densities for all samples were kept constant by varying the amount of water, such that the only different in each sample was the amount of CaCb.
• the pozzolan chosen for the experiment was diatomaceous earth.
• the thickening times were measured on a high-temperature high-pressure consistometer by ramping from room temperature (e.g., about 80 °F) and ambient pressure to 183 °F and 3000 psi in 52 minutes in accordance with the procedure for determining cement thickening times set forth in API RP Practice 10B-2, Recommended Practice for Testing Well Cements, First Edition, July 2005.
• the results of this test are set forth below in Table 14. The reported results are an average for three cylinders of each sample.
• results indicate that the addition of a strength enhancer reduces the thickening time of the set-delayed cement composition and also increases the compressive strength considerably.
• results also indicate that CaCb concentration has a minimal effect on thickening time in the presence of the strength enhancer.
• Example 3 the same set-delayed cement composition from Example 3 was activated with either a control cement set activator (Samples 13 and 15) comprising a monovalent salt (sodium sulfate) and polyphosphate (sodium hexametaphosphate) or an experimental cement set activator (Samples 14 and 16) comprising a monovalent salt (sodium sulfate) and polyphosphate (sodium hexametaphosphate) as well as a strength enhancer (diatomaceous earth).
• the monovalent salt and polyphosphate were utilized in a 1 :1 ratio for all experiments.
• the concentration of the cement set activator was varied over two data points while the strength enhancer was held constant.
• the destructive compressive strength of each sample was measured by allowing the samples to cure for 24 hours in 1 " by 2" plastic cylinders that were placed in an autoclave at 160 °F and 3000 psi to form set cylinders.
• destructive compressive strengths were determined using a mechanical press in accordance with API RP 10B-2, Recommended Practice for Testing Well Cements. The results of this test are set forth below in Table 15. The reported results are an average for three cylinders of each sample.
• the thickening-time data when juxtaposed with the compressive-strength data shows that a silica-source strength enhancer added to a cement set activator does not alter the thickening times of the set-delayed cement compositions but does increase the compressive strength.
• thickening time and compressive strength are linked in a direct relationship such that decreasing one causes a decrease in the other. For this system however, it is clear that thickening time and compressive strength have been decoupled.
• compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of or “consist of the various components and steps.
• indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.
• ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
• any numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed.
• every range of values (of the form, "from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b") disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values even if not explicitly recited.
• every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

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