WO2008017414A1 - Formulation de géopolymère pompable pour application à un champ pétrolifère - Google Patents

Formulation de géopolymère pompable pour application à un champ pétrolifère Download PDF

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Publication number
WO2008017414A1
WO2008017414A1 PCT/EP2007/006815 EP2007006815W WO2008017414A1 WO 2008017414 A1 WO2008017414 A1 WO 2008017414A1 EP 2007006815 W EP2007006815 W EP 2007006815W WO 2008017414 A1 WO2008017414 A1 WO 2008017414A1
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WIPO (PCT)
Prior art keywords
suspension
activator
retarder
accelerator
thickening
Prior art date
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PCT/EP2007/006815
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English (en)
Inventor
Véronique Barlet-Gouedard
Benedicte Zusatz-Ayache
Olivier Porcherie
Original Assignee
Services Petroliers Schlumberger
Schlumberger Technology B.V.
Schlumberger Holdings Limited
Schlumberger Canada Limited
Prad Research And Development Nv
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/462,724 external-priority patent/US7794537B2/en
Priority claimed from EP20060291275 external-priority patent/EP1887065B1/fr
Application filed by Services Petroliers Schlumberger, Schlumberger Technology B.V., Schlumberger Holdings Limited, Schlumberger Canada Limited, Prad Research And Development Nv filed Critical Services Petroliers Schlumberger
Priority to CA 2644991 priority Critical patent/CA2644991C/fr
Priority to MX2009001400A priority patent/MX2009001400A/es
Priority to NO20090602A priority patent/NO347297B1/no
Priority to AU2007283146A priority patent/AU2007283146B2/en
Publication of WO2008017414A1 publication Critical patent/WO2008017414A1/fr

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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
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • 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
    • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0067—Function or property of ingredients for mortars, concrete or artificial stone the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the present invention broadly relates to well cementing. More particularly the invention relates to the use of geopolymers, to pumpable geopolymer formulations and the related methods of placing the geopolymer formulations in a well using conventional or unconventional cementing techniques.
  • Geopolymers are a novel class of materials that are formed by chemical dissolution and subsequent recondensation of various aluminosilicate oxides and silicates to form an amorphous three-dimensional framework structure. Therefore, a geopolymer is a three-dimensional aluminosilicate mineral polymer.
  • the term geopolymer was proposed and first used by J. Davidovits (Synthesis of new high-temperature geopolymers for reinforced plastics/composites, SPE PACTEC 79, Society of Plastics Engineers) in 1976 at the IUPAC International Symposium on Macromolecules held in Sweden.
  • Geopolymers based on alumino-silicates are designated as poly(sialate), which is an abbreviation for poly(silicon-oxo-aluminate) or (-Si-O-Al-O-) n (with n being the degree of polymerization).
  • the sialate network consists of SiO 4 and AlO 4 tetrahedra linked alternately by sharing all the oxygens, with Al 3+ and Si 4+ in IV-fold coordination with oxygen.
  • Positive ions Na + , K + , Li + , Ca 2+ ...) must be present in the framework cavities to balance the negative charge OfAl 3+ in IV-fold coordination.
  • the empirical formula of polysialates is: M n ⁇ -(SiO 2 ) z -AlO 2 ⁇ n , w H 2 O, wherein M is a cation such as potassium, sodium or calcium, n is a degree of polymerization and z is the atomic ratio Si/Al which may be 1, 2, 3 or more, until 35 as known today.
  • M is a cation such as potassium, sodium or calcium
  • n is a degree of polymerization
  • z is the atomic ratio Si/Al which may be 1, 2, 3 or more, until 35 as known today.
  • Table 1 Geopolymers chemical designation (wherein M is a cation such as potassium, sodium or calcium, and n is a degree of polymerization).
  • geopolymers have been investigated for use in a number of applications, including as cementing systems within the construction industry, as refractory materials and as encapsulants for hazardous and radioactive waste streams. Geopolymers are also referenced as rapid setting and hardening materials. They exhibit superior hardness and chemical stability.
  • the invention discloses a suspension comprising an aluminosilicate source, a carrier fluid, an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator or a combination thereof, and wherein the suspension is a pumpable composition in the oilfield industry and the suspension is able to set under well downhole conditions. All the three components do not need necessarily to be added separately: for example the activator can be already within a carrier fluid.
  • the aluminosilicate source can be in the form of a solid component; the metal silicate can be in the form of a solid or of a mix of metal silicate within a carrier fluid; the activator can be in the form of a solid or of a mix of activator within a carrier fluid. Importance is to have a carrier fluid to make suspension if aluminosilicate source, metal silicate and activator are all in solid state. If aluminosilicate source, metal silicates are in solid state and activator is in liquid state, activator is considered to already have a carrier fluid within. Further, as it is understood, unicity of the carrier fluid is not required, two or more carrier fluids can be used.
  • the geopolymeric composition has such rheological properties that the suspension of said geopolymeric composition has a good pumpability and stability.
  • a pumpable composition in the oilfield industry has a rheology lesser than or equal to 300 cP, preferably in other embodiment lesser than or equal to 250 cP, more preferably in another embodiment lesser than or equal to 200 cP. Further, the suspension made is a stable suspension.
  • the geopolymeric composition is mixable and pumpable; therefore applications in the oilfield industry are possible.
  • the alkali activator is chosen with a given pH, and/or a retarder is added and/or an accelerator is added to the suspension of said geopolymeric composition.
  • the alkali activator can be generally an alkali metal hydroxide, more preferably a sodium or potassium hydroxide; it can be also a carbonate material.
  • the retarder is selected from the group constituted of boron containing compound, lignosulfate, sodium gluconate, sodium glucoheptonate, tartaric acid and phosphorus containing compounds.
  • the retarder is an anhydrous or hydrated alkali metal borate or a pure oxide of boron.
  • the retarder is a sodium pentaborate decahydrate, boric acid, or borax.
  • the accelerator is an alkali metal preferably: a lithium or potassium containing compound.
  • the accelerator is a salt of lithium. More preferably, the accelerator is lithium chloride.
  • the control of the setting time is here efficient from 20 0 C to 200°C.
  • Sodium pentaborate decahydrate and borax are able to control setting time from 20 0 C, preferably from 25°C to 150 0 C.
  • the type of alumino silicate is specifically chosen depending of the temperature application.
  • a lightweight particle and/or a heavyweight material can be added.
  • the lightweight particles also called fillers are selected from the group constituted of: cenospheres, sodium-calcium-borosilicate glass, and silica-alumina microspheres.
  • the heavy particles also called the weighting agents are typically selected from the group constituted of: manganese tetraoxide, iron oxide (hematite), barium sulfate (barite), silica and iron/titanium oxide (ilmenite).
  • the geopolymeric compositions can also be foamed by foaming the suspension of said geopolymeric composition with a gas as for example air, nitrogen or carbon dioxide.
  • the geopolymeric composition can further comprise a gas generating additive which will introduce the gas phase in the suspension.
  • a gas generating additive which will introduce the gas phase in the suspension.
  • the density of the suspension of said geopolymeric slurry compositions varies between 1 gram per cubic centimeter and 2.5 grams per cubic centimeter, more preferably between 1.2 grams per cubic centimeter and 1.8 grams per cubic centimeter.
  • the suspension of said geopolymeric composition can further comprise a mixture of two or more aluminosilicate source.
  • the suspension of said the geopolymeric composition can comprise a second binder component which may be a conventional cementing material such as Portland cement, micro-cement or silica fume.
  • the suspension of said geopolymeric composition can comprise a gas phase so the gas phase or part of the gas phase remains in the geopolymeric composition.
  • the gas phase can be a water-immiscible dispersed nitrogen phase.
  • the suspension of said geopolymeric composition can comprise a water-immiscible phase.
  • this can be a water-immiscible dispersed oil-based phase.
  • the geopolymeric composition further comprises an additive selected from the group constituted of: an activator, an antifoam, a defoamer, silica, a fluid loss control additive, a flow enhancing agent, a dispersant, a rheology modifier, a foaming agent, a surfactant and an anti-settling additive.
  • an additive selected from the group constituted of: an activator, an antifoam, a defoamer, silica, a fluid loss control additive, a flow enhancing agent, a dispersant, a rheology modifier, a foaming agent, a surfactant and an anti-settling additive.
  • the geopolymeric composition according to the invention are preferably poly(sialate), poly(sialate-siloxo) or poly(sialate-disiloxo). More preferably, the geopolymeric composition are poly(sialate-siloxo) components and therefore the silicon to aluminum atomic ratio is substantially equal to two, between 1.8 and 2.8.
  • a suspension comprising an aluminosilicate source, a carrier fluid, an activator taken from the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof, and a retarder able to retard the thickening and/or the setting times of the suspension and/or an accelerator able to accelerate the thickening and/or the setting times of the suspension, wherein the metal is an alkali metal and the oxide molar ratio M 2 O/SiO 2 is greater than 0.20 wherein M is the metal.
  • the retarder when used, it is preferably a boron containing compound and the suspension of said geopolymeric composition has preferably an oxide molar ratio B 2 O 3 /H 2 O ofless than 0.03.
  • the accelerator is preferably a lithium or potassium containing compound.
  • the suspension of said geopolymeric composition has preferably an oxide molar ratio Li 2 CVH 2 O of less than 0.2. More preferably, the geopolymeric slurry composition has an oxide molar ratio Li 2 OZH 2 O of less than or equal to 0.1.
  • the geopolymeric composition according to the invention uses aluminosilicate source which is selected from the group constituted of ASTM type C fly ash, ASTM type F fly ash, ground blast furnace slag, calcined clays, partially calcined clays (such as metakaolin), aluminium-containing silica fume, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite and pumice.
  • the geopolymeric composition is made with metakaolin, kaolin, ground granulated blast furnace slag and/or fly ash.
  • the geopolymeric composition according to the invention uses a metal silicate, with the metal selected from the group constituted of lithium, sodium, potassium, rubidium and cesium.
  • the metal is sodium or potassium.
  • the metal silicates can be replaced by ammonium silicates.
  • the metal silicate in another embodiment can be encapsulated.
  • the geopolymeric composition according to the invention uses for the alkali activator, for example an alkali metal hydroxide.
  • the alkali metal hydroxide is sodium or potassium hydroxide.
  • the alkali activator and/or the metal silicate may be encapsulated.
  • Alkali carbonates can also be used as alkali activator.
  • the alkali activator in another embodiment can be encapsulated.
  • the geopolymeric composition according to the invention uses for the carrier fluid preferably an aqueous solution such as fresh water.
  • a method to control the setting time of a geopolymeric suspension for oilfield applications comprises the step of providing said suspension within a carrier fluid by adding: (i) a retarder and/or an accelerator; (ii) an aluminosilicate source; (iii) an activator taken in the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof.
  • the previous steps can be realized in another order.
  • the nature and/or the pH and/or the concentration of the activator and/or the concentration of the metal silicate is changed.
  • the concentration of the activator By increasing the concentration of the activator, the setting time is shortened and by changing the nature and/or pH, different setting times are obtained.
  • the nature and/or the concentration of the retarder is changed.
  • the concentration of the retarder By increasing the concentration of the retarder, the setting time is lengthened and by changing the nature, different setting times are obtained.
  • the nature and/or the concentration of the accelerator is changed. By increasing the concentration, the setting time is shortened and by changing the nature, different setting times are obtained.
  • the three solutions can be used separately or in combination.
  • the use of a special activator does not give sufficiently long setting time and the use of a retarder may be preferred.
  • the use of a special activator may not give sufficiently short setting time and the use of an accelerator would be preferred.
  • a method to control the density of a suspension for oilfield industry comprises the step of providing said suspension within a carrier fluid by adding: (i) lightweight particles and/or heavy particles; (ii) an aluminosilicate source; (iii) an alkali activator taken in the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof.
  • the previous steps can be realized in another order.
  • the method further comprises the step of adding a retarder and/or an accelerator to the suspension.
  • the method further comprises the step of foaming the suspension of said geopolymeric composition.
  • a method to control the density of a suspension for oilfield industry comprises the step of: (i) providing said suspension within a carrier fluid by mixing an aluminosilicate source, a metal silicate and an activator taken in the list constituted by: a metal silicate, a metal aluminate, an alkali activator, or a combination thereof in a carrier fluid, (ii) foaming the suspension of said geopolymeric composition. Still, in another aspect of the invention the method further comprises the step of adding a retarder and/or an accelerator to the suspension.
  • the method to control the density of geopolymer compositions of the invention applies for density range varying between 1 gram per cubic centimeter and 2 grams per cubic centimeter, but could also be applied to density range varying between 0.8 gram per cubic centimeter and 2.5 grams per cubic centimeter.
  • a method to place a geopolymeric composition in a borehole and isolate subterranean formations comprises the step of: (i) providing a suspension as described above (ii) pumping said suspension into the borehole, and (iii) allowing said suspension to set under wellbore downhole conditions and thereby form the geopolymeric composition.
  • the step of providing a suspension of said geopolymeric composition further comprises adding a retarder and/or an accelerator and/or an activator. Effectively, it can be useful to lengthen the set of the geopolymeric composition by adding a retarder as seen above and/or it can be useful to accelerate the set of the geopolymeric composition by adding an accelerator as seen above.
  • the method comprises the step of activating in situ the suspension of said geopolymeric composition. Effectively, the method also applies if activation has to be realized downhole in the well, the activation does not necessarily refer to the alkali activator.
  • the activation refers to activation via the alkali activator, the alkali activator is encapsulated as described previously or is released with a downhole device.
  • the activation refers to any type of activation when various additives that need activation are used, as for example activation can be physical (by heat, UV radiation or other radiations); the activation can be made also with chemical components encapsulated and released at a predefined time or event.
  • the capsule can be self destructed as previously explained or can be destroyed with help of stress and/or sonic perturbation.
  • the method comprises the step of activating the suspension of said geopolymeric composition just before use.
  • an inactivated suspension of geopolymer composition is made so that said suspension is stable for a long time.
  • Said composition is storable, transportable and accessorily perishable after a period varying between one day and some months, preferably some days and three months.
  • the storable suspension is taken to rig site in liquid form and is activated before pumping or downhole in situ as explained previously.
  • the pumping and placement of geopolymer suspension below surface encompasses several other conventional cementing techniques such as the grouting of platform piles, skirts or the like, the squeeze operation for repair or plugging of an undesired leak, perforation, formation or the like, and the setting of a geopolymer composition plug for any purpose of a cement plug.
  • the methods apply also to the placement of the geopolymeric composition to squeeze a zone of the borehole.
  • the methods can apply for water well, geothermal well, steam injection well, Toe to Heel Air Injection well or acid gas well.
  • the composition can withstand temperature above 250 0 C, even above 45O 0 C and 550 0 C.
  • Figure 1 shows the impact of temperature on the thickening time of geopolymer formulations.
  • the geopolymer formulations involve the use of an aluminosilicate source, a metal silicate and an alkali activator in a carrier fluid at near- ambient temperature.
  • the carrier fluid is preferably a fresh water solution.
  • the alkali activator can be already within water.
  • the aluminosilicate source can be in the form of a solid component
  • the metal silicate can be in the form of a solid or of an aqueous solution of metal silicate
  • the alkali activator can be in the form of a solid or of an aqueous solution of alkali activator.
  • Formation of the geopolymer concrete involves an aluminosilicate source.
  • aluminosilicate source from which geopolymers may be formed include ASTM type C fly ash, ASTM type F fly ash, ground blast furnace slag, calcined clays, partially calcined clays (such as metakaolin),, aluminium-containing silica fume, natural aluminosilicate, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite and pumice. These materials contain a significant proportion of amorphous aluminosilicate phase, which reacts in strong alkali solutions.
  • the preferred aluminosilicates are fly ash, metakaolin, kaolin and blast furnace slag. Mixtures of two or more aluminosilicate sources may also be used if desired.
  • the aluminosilicate component comprises a first aluminosilicate binder and optionally one or more secondary binder components which may be chosen in the list: ground granulated blast furnace slag, Portland cement, kaolin, metakaolin or silica fume.
  • the alkali activator is generally an alkali metal hydroxide.
  • Alkali metal hydroxides are generally preferred as sodium and potassium hydroxide.
  • the metal hydroxide may be in the form of a solid or an aqueous mixture.
  • the alkali activator in another embodiment can be encapsulated.
  • the alkali activator when in solid and/or liquid state can be trapped in a capsule that will break when subject for example, to stress on the capsule, to radiation on the capsule.
  • the alkali activator when in solid and/or liquid state can be trapped in a capsule that will naturally destroy due to the fact that for example, the capsule is made with biodegradable and/or self destructive material.
  • the alkali activator when in liquid state can be adsorbed onto a porous material and will be released after a certain time or due to a predefined event.
  • the metal silicate is generally an alkali metal silicate.
  • Alkali metal silicates, particularly sodium silicate or potassium silicate, are preferred.
  • Sodium silicates with a molar ratio of SiO 2 /Na 2 O equal to or less than 3.2 are preferred.
  • Potassium silicates with a molar ratio of SiO 2 /K 2 O equal to or less than 3.2 are preferred.
  • the metal silicate in another embodiment can be encapsulated.
  • the method of the invention is applicable to the oilfield, preferably in completion of the well bore of oil or gas wells.
  • a pumpable geopolymer formulation is formed where the components are mixed with a carrier fluid.
  • Various additives can be added to the suspension and the suspension is then pumped into the well bore. The suspension is then allowed to set up in the well to provide zonal isolation in the well bore.
  • a typical property of geopolymer systems is their ability to set without delay after mixing. However for oilfield applications, mixable and pumpable geopolymer suspension is needed. For this reason, a way to retard the thickening of the geopolymer suspension or a way to control thickening times of the geopolymer is required.
  • Table 2 Examples of ISO10426-2 thickening time measured with HPHT consistometer (hours:min) obtained with different retarders at different temperature.
  • Sample A2 is made by dissolving the retarder amount in 358 g of water, adding the blend comprising 314 g of metakaolin and 227 g of sodium disilicate in the solution under mixing, adding 17.2 g of sodium hydroxide under ISO 1026-2 mixing, pouring the suspension in HPHT cell. Sample A2 is then tested by measuring the thickening time with the HPHT consistometer.
  • Sample B2 is made by dissolving the retarder amount in 265 g of water, adding the blend comprising 232 g of metakaolin, 168 g of sodium disilicate and 414 g of silica particles as filler in the solution under mixing, adding 13 g of sodium hydroxide under ISO 10426-2 mixing, pouring the suspension in HPHT cell. Sample B2 is then tested by measuring the thickening time with the HPHT consistometer.
  • Sample C2 is made by dissolving the retarder amount in 422 g of sodium hydroxide solution, adding the blend comprising 440 g of type F fly ash and 88 g of sodium disilicate in the solution under mixing following ISO 10426-2 mixing, pouring the suspension in HPHT cell. Sample C2 is then tested by measuring the thickening time with the HPHT consistometer.
  • Sample D2 is made by dissolving the retarder amount in 374 mL of water, adding the blend comprising 411 g of type F fly ash and 82 g of sodium disilicate under mixing at 4000 rpm, adding 75 g of sodium hydroxide under ISO 10426-2 mixing, pouring the suspension in HPHT cell. Sample D2 is then tested by measuring the thickening time with the HPHT consistometer.
  • the retardation of geopolymeric formulations can be and is controlled at different BHCT by using either boron containing compounds as for example sodium pentaborate decahydrate, boric acid, borax, or lignosulphonate, or phosphorus containing compounds, or a mixture of them. Retardation of geopolymeric formulations will be sensitive to boron valence for boron containing compounds or phosphate valence for phosphorus containing compounds and/or to retarder concentration.
  • boron containing compounds as for example sodium pentaborate decahydrate, boric acid, borax, or lignosulphonate, or phosphorus containing compounds, or a mixture of them.
  • Retardation of geopolymeric formulations will be sensitive to boron valence for boron containing compounds or phosphate valence for phosphorus containing compounds and/or to retarder concentration.
  • Vicat apparatus allows to measure when the setting of the material starts (1ST) and ends (FST). It is based on the measurements of the penetration of a needle in a soft material. This apparatus is often used to realize pre-study at ambient temperature and atmospheric pressure.
  • Table 3 Examples of initial setting time (hours:min) obtained with different retarders with Vicat apparatus at ambient temperature and atmospheric pressure.
  • Sample A3 is made by dissolving the retarder amount in 139 g of sodium hydroxide solution, adding the blend comprising 105 g of metakaolin, 48 g of sodium metasilicate and 17 g of silica particles as filler in the solution under mixing. Sample A3 is then tested by pouring the suspension in a Vicat cell to measure setting time at 25°C.
  • Sample B3 is made by dissolving the retarder amount in 358 g of water, adding the blend comprising 314 g of metakaolin and 227 g of sodium disilicate in the solution under mixing, adding 17.2 g of sodium hydroxide under ISO 10426-2 mixing. Sample B3 is then tested by pouring the suspension in a Vicat cell to measure setting time at 25°C.
  • Retardation of geopolymeric formulations is sensitive to temperature.
  • two boron-based retarders sodium pentaborate decahydrate and borax are able to strongly retard different types of geopolymer suspensions even at 25°C.
  • Figure 1 illustrates the impact of temperature on the thickening time for a geopolymer composition made by adding a blend comprising 411 g of type F fly ash and 82 g of sodium disilicate in 374 mL of water under mixing (retarder being predissolved in this water) and by adding 36.5 g of sodium hydroxide under ISO 10426-2 mixing. This way, retarders are efficient even at high temperature to control geopolymer suspension thickening time.
  • Control of the thickening time can also be realized by other means.
  • the nature of the alkali activator and its pH have an impact on the thickening time.
  • Table 4 illustrates the influence of the alkali activator on the thickening time of geopolymeric suspensions. It demonstrates the ability to select the alkali activator source according to the downhole conditions.
  • Table 4 Examples of ISO 10426-2 thickening time measured with HPHT consistometer (hoursrmin) with different alkali activators measured at 85°C.
  • Sample A4 is made by adding the blend comprising 314 g of metakaolin and 227 g of sodium disilicate in 358 g of water under mixing, adding 17.2 g of sodium hydroxide under ISO 10426-2 mixing, pouring the suspension in HPHT cell. Sample A4 is then tested by measuring the thickening time with a HPHT consistometer.
  • Sample B4 is made by adding the blend comprising 314 g of metakaolin and 227 g of sodium disilicate in 357 g of water under mixing, adding 23.4 g of sodium bicarbonate under ISO 10426-2 mixing, pouring the suspension in HPHT cell. Sample A4 is then tested by measuring the thickening time with a HPHT consistometer.
  • Control of the thickening and setting times by these methods of retardation can also be efficiently done with geopolymer having different silicon versus aluminum ratio.
  • Table 5 illustrates the accelerating effect of lithium compounds on the thickening time of geopolymeric suspensions at temperature of 85 0 C. It demonstrates the ability of using lithium salts to control the thickening time of geopolymer suspensions.
  • Table 5 Examples of ISO 10426-2 thickening time measured with HPHT consistometer (hours:min) obtained with typ eF fly ashes and accelerators.
  • Sample A5 is made by adding the blend comprising 480 g of superfine typer F fly ash and 96 g of sodium disilicate in 406 g of the sodium hydroxide solution containing an accelerator following ISO 10426-2 mixing, pouring the suspension in HPHT cell. Sample A5 is then tested by measuring the thickening time with a HPHT consistometer.
  • Sample B5 is made by adding the blend comprising 442 g of standard type F fly ash and 88 g of sodium disilicate in 423 g of the sodium hydroxide solution containing an accelerator following ISO 10426-2 mixing, pouring the suspension in HPHT cell. Sample B5 is is then tested by measuring the thickening time with a HPHT consistometer.
  • Figure 2 illustrates the accelerating effect of lithium compounds on the thickening time for a geopolymer composition made by adding the blend comprising 480 g of superfine type F fly ash and 96 g of sodium disilicate in 406 g of the sodium hydroxide solution containing the accelerator following ISO 10426-2 mixing.
  • the thickening time versus time of the suspension is then measured at temperature of 85°C.
  • accelerators such as lithium salts are shown to efficiently decrease the thickening time of geopolymer suspensions.
  • the degree of acceleration of geopolymeric formulations is sensitive to accelerator type and/or concentration.
  • a real control of the thickening time of the suspension can be established.
  • nature of the retarder used can be changed, concentration of the retarder can be increased, nature of the alkali activator used can be changed, and nature of the aluminosilicate used can be changed.
  • the geopolymer suspension has to be pumpable.
  • Table 6 hereunder illustrates the rheological properties of geopolymer suspensions measured at a bottom hole circulating temperature (BHCT) of 6O 0 C. Rheological values demonstrate the pumpability and the stability of geopolymeric suspensions for application in the oilfield industry.
  • BHCT bottom hole circulating temperature
  • Sample A6 is made by adding the blend comprising 411 g of type F fly ash and 82 g of sodium disilicate in 374 mL of water under mixing, adding 75 g of sodium hydroxide under mixing. Sample A6 is then tested by measuring the rheological properties of the suspension after mixing and after conditioning at 6O 0 C according to the ISO 1026-2 standard procedure.
  • Sample B6 is made by dissolving the 0.65 %bwob of sodiumpentaborate decahydrate in 422 g of sodium hydroxide solution, adding the blend comprising 440 g of type F fly ash and 88 g of sodium disilicate in the solution under ISO 10426-2 mixing, adding 36.5 g of sodium hydroxide under mixing. Sample B6 is then tested by measuring the rheological properties of the geopolymer suspension after mixing and after conditioning at 60 0 C according to the ISO 10426-2 standard procedure.
  • Sample C6 is made by adding the blend comprising 480 g of type F fly ash and 96 g of sodium disilicate in 406 g of the sodium hydroxide solution following ISO 10426-2 mixing conditions. Sample C6 is then tested by measuring the rheological properties of the suspension after mixing and after conditioning at 60 0 C according to the ISO 1-0426-2 standard procedure.
  • Table 7 shows the difference of setting time according to the conditions of setting.
  • the geopolymer formulation will set more rapidly in static than in dynamic conditions. Also normally, the geopolymer suspension should set rapidly after placement.
  • Sample A7 is made by adding the blend comprising 440 g of type F fly ash and 88 g of sodium disilicate in 422 g of the water under mixing following ISO 10426-2 mixing, pouring the suspension in HPHT cell or the Vicat cell..
  • Sample B7 is made by adding the blend comprising 442 g of standard type F fly ash and 88 g of sodium disilicate in 424 g of the sodium hydroxide solution containing 2 %bwob LiOH, H 2 O following ISO 10426-2 mixing, pouring the suspension in HPHT consistometer or in the Vicat cell.
  • the geopolymer suspension has to have a large range of densities.
  • the tested geopolymer formulations propose a density range between 1.45 g/cm 3 [12.1 lbm/gal] up to 1.84 g/cm 3 [15.4 lbm/gal] either in reducing the water content, or in adding fillers.
  • Table 8 Examples of suspension density obtained with some geopolymeric formulations.
  • Sample A8 is made by dissolving the retarder amount in 265 g of water, adding the blend comprising 232 g of metakaolin, 168 g of sodium disilicate and 414 g of silica particles as filler in the solution under mixing, adding 13 g of sodium hydroxide under ISO 10426-2 mixing.
  • Sample B8 is made by dissolving the retarder amount in 139 g of sodium hydroxide solution, adding the blend comprising 105 g of metakaolin, 48 g of sodium metasilicate and 17 g of silica particles as filler in the solution under mixing.
  • lightweight particles are added to reach lower densities or heavy particles to reach higher densities.
  • the lightweight particles typically have density of less than 2 g/cm 3 , and generally less than 1.3g/cm 3 .
  • hollow microspheres in particular of silico- aluminate, known as cenospheres, a residue that is obtained from burning coal and having a mean diameter of about 150 micrometers.
  • synthetic materials such as hollow glass bubbles, and more particularly preferred are bubbles of sodium- calcium-borosilicate glass presenting high compression strength or indeed microspheres of a ceramic, e.g. of the silica-alumina type.
  • the lightweight particles can also be particles of a plastics material such as beads of polypropylene.
  • the heavy particles typically have density of more than 2 g/cm 3 , and generally more than 3 g/cm 3 .
  • the gas utilized to foam the composition can be air or nitrogen, nitrogen being the most preferred.
  • the amount of gas present in the cement composition is that amount which is sufficient to form a foam having a density in the range of from about 1 g.cm "3 to 1.7 g.cm "3 (9 to 14 lbm/gal).
  • additives can be used with the geopolymer according to the present invention.
  • Additives known to those of ordinary skill in the art may be included in the geopolymer compositions of the present embodiments. Additives are typically blended with a base mix or may be added to the geopolymer suspension.
  • An additive may comprise an activator, an antifoam, a defoamer, silica, a fluid loss control additive, a flow enhancing agent, a dispersant, an anti-settling additive or a combination thereof, for example. Selection of the type and amount of additive largely depends on the nature and composition of the set composition, and those of ordinary skill in the art will understand how to select a suitable type and amount of additive for compositions herein.
  • the particle size of the components is selected and the respective proportion of particles fractions is optimized in order to have at the same time the highest Packing Volume Fraction (PVF) of the solid, and obtaining a mixable and pumpable slurry with the minimum amount of water, i.e., at slurry Solid Volume Fraction (SVF) of 35-75% and preferably of 50-60%. More details can be found in European patent EP 0 621 247. The following examples do not constitute a limit of the invention but rather indicate to those skilled in the art possible combinations of the particle size of the various components of the geopolymer compositions of the invention to make a stable and pumpable suspension.
  • PVF Packing Volume Fraction
  • SVF slurry Solid Volume Fraction
  • the geopolymeric composition can be a "trimodal" combination of particles: "large” for example sand or crushed wastes (average dimension 100-1000 micrometers), “medium” for example materials of the type of glass beads or fillers (average dimension 10-100 micrometers), “fines” like for example a micromaterial, or micro fly ashes or other micro slags (average dimension 0.2-10 micrometers).
  • the geopolymeric composition can also be a "tetramodal" combination of particles type: with “large” (average dimension about 200-350 micrometers), “medium” glass beads, or fillers (average dimension about 10 - 20 micrometers), “fine” (average dimension about 1 micrometer), “very fine” (average dimension about 0.1 - 0.15 micrometer).
  • the geopolymeric composition can also be a further combinations between the further categories: "very large”, for example glass maker sand, crushed wastes (average dimension superior to 1 millimeter) and/or "large”, for example sand or crushed wastes (average dimension about 100-1000 micrometers) and/or “medium” like glass beads, or fillers, or crushed wastes (average dimension 10-100 micrometers) and “fine” like, for example, micro fly ashes or other micro slags (average dimension 0.2-10 micrometer) and/or "very fine” like, for example, a latex or pigments or polymer microgels like a usual fluid loss control agent (average dimension 0.05-0.5 micrometer) and/or "ultra fine” like some colloidal silica or alumina (average dimension 7-50 nanometers).
  • very large for example glass maker sand, crushed wastes (average dimension superior to 1 millimeter) and/or “large”, for example sand or crushed wastes (average dimension about 100-1000 micrometers) and/or “medium
  • Table 9 and 10 illustrate that geopolymer formulations proposed by this invention exhibit acceptable compressive strengths with low Young Modulus for oilfield applications with or without retarder.
  • Sample A9 is made by dissolving the retarder amount (if necessary) in 358 g of water, adding the blend comprising 314 g of metakaolin and 227 g of sodium disilicate in the solution under mixing, adding 17.2 g of sodium hydroxide under ISO 10426-2 mixing, pouring the suspension into moulds and placing the moulds in a curing chamber for 7 days at 90°C - 20.7 MPa [3000 psi] according to ISO 10426-2 procedure. Sample A9 is then tested by measuring the compressive strength and Young's modulus.
  • Sample B9 is made by dissolving the retarder amount (if necessary) in 265 g of water, adding the blend comprising 232 g of metakaolin, 168 g of sodium disilicate and 414 g of silica particles as filler in the solution under mixing, adding 13 g of sodium hydroxide under ISO 10426-2 mixing, pouring the suspension into moulds and placing the moulds in a curing chamber for 7 days at 90°C - 20.7 MPa [3000 psi] according to ISO 10426-2 procedure. Sample B9 is then tested by measuring the compressive strength and Young's modulus.
  • Sample AlO is made by adding the blend comprising 482 g of standard type F fly ash and 96 g of sodium disilicate in 408 g of the sodium hydroxide solution containing the accelerator following ISO 10426-2 mixing, pouring the suspension into moulds and placing the moulds in a curing chamber for 21 days at 9O 0 C - 20.7 MPa [3000 psi], according to ISO 10426-2 procedure. Sample AlO is then tested by measuring the compressive strength and Young's modulus.
  • Sample BlO is made by adding the blend comprising 442 g of standard type F fly ash and 88 g of sodium disilicate in 424 g of the sodium hydroxide solution containing 3 %bwob LiCl following ISO 10426-2 mixing, pouring the suspension into moulds and placing the moulds in a curing chamber for 21 days at 90°C - 20.7 MPa [3000 psi], according to ISO 10426-2 procedure. Sample BlO is then tested by measuring the compressive strength and Young's modulus.
  • Sample ClO is made by adding the blend comprising 480 g of superfine type F fly ash and 96 g of sodium disilicate in 406 g of the sodium hydroxide solution containing 7 %bwob LiCl following ISO 10426-2 mixing, pouring the suspension into moulds and placing the moulds in a curing chamber for 21 days at 90°C - 20.7 MPa [3000 psi], according to ISO 10426-2 procedure. Sample ClO is then tested by measuring the compressive strength and Young's modulus.
  • compositions of the present invention exhibit good compressive strengths with low Young modulus, they would be very useful in oilfield applications.
  • Table 11 illustrates that geopolymer formulations proposed by this invention exhibit acceptable permeability for oilfield applications.
  • Sample Al 1 is made by dissolving the retarder amount in 265g of water, adding the blend comprising 232g of metakaolin, 168g of sodium disilicate and 414g of silica particles as filler in the solution under mixing, adding 13g of sodium hydroxyde under API mixing, pouring the suspension in molds in a curing chamber for 7 days at 90°C - 3000psi according to API procedure. Water permeability of sample Al 1 is then measured on cylindrical core (1-inch diameter by 2-inches length).
  • Sample BI l is made by adding the blend comprising 482g of standard fly ash type F and 96g of sodium disilicate in 408g of the sodium hydroxide solution containing the accelerator following API mixing, pouring the suspension in molds in a curing chamber for 21 days at 90°C - 3000psi, according to API procedure. Water permeability of sample Bl 1 is then measured on cylindrical core (1-inch diameter by 2-inches length).
  • Sample CI l is made by adding the blend comprising 442g of standard fly ash type F and 88g of sodium disilicate in 424g of the sodium hydroxide solution containing 3% bwob LiCl following API mixing, pouring the suspension in molds in a curing chamber for 21 days at 90°C - 3000psi, according to API procedure. Water permeability of sample CI l is then measured on cylindrical core (1-inch diameter by 2-inches length).
  • Sample Dl 1 is made by adding the blend comprising 48Og of superfine fly ash type F and 96g of sodium disilicate in 406g of the sodium hydroxide solution containing 7% bwob LiCl following API mixing, pouring the suspension in molds in a curing chamber for 21 days at 9O 0 C - 3000psi, according to API procedure. Water permeability of sample DI l is then measured on cylindrical core (1-inch diameter by 2-inches length).
  • compositions of the present invention exhibit acceptable water permeability, oilfield applications are possible.
  • the methods of the present invention are useful in completing well, such as for example oil and/or gas well, water well, geothermal well, steam injection well, Toe to Heel Air Injection well, acid gas well, carbon dioxide injection or production well and ordinary well.
  • Placement of the geopolymer composition in the portion of the wellbore to be completed is accomplished by means that are well known in the art of wellbore cementing.
  • the geopolymer composition is typically placed in a wellbore surrounding a casing to prevent vertical communication through the annulus between the casing and the wellbore or the casing and a larger casing.
  • the geopolymer suspension is typically placed in a wellbore by circulation of the suspension down the inside of the casing, followed by a wiper plug and a nonsetting displacement fluid.
  • the wiper plug is usually displaced to a collar, located near the bottom of the casing. The collar catches the wiper plug to prevent overdisplacement of the geopolymer composition and also minimizes the amount of the geopolymer composition left in the casing.
  • the geopolymer suspension is circulated up the annulus surrounding the casing, where it is allowed to harden.
  • the annulus could be between the casing and a larger casing or could be between the casing and the borehole.
  • cementing operation with a geopolymer suspension may cover only a portion of the open hole, or more typically up to inside the next larger casing or sometimes up to surface.
  • This method has been described for completion between formation and a casing, but can be used in any type of completion, for example with a liner, a slotted liner, a perforated tubular, an expandable tubular, a permeable tube and/or tube or tubing.
  • the methods of the present invention are useful in completing well, such as for example oil and/or gas well, water well, geothermal well, steam injection well, acid gas well, carbon dioxide well and ordinary well, wherein placement of the geopolymer composition in the portion of the wellbore to be completed is accomplished by means that are well known in the art of wellbore reverse circulation cementing.
  • the geopolymer composition can also be used in squeeze job and/or in remedial job.
  • the geopolymer material is forced through perforations or openings in the casing, whether these perforations or openings are made intentionally or not, to the formation and wellbore surrounding the casing to be repaired.
  • Geopolymer material is placed in this manner to repair and seal poorly isolated wells, for example, when either the original cement or geopolymer material fails, or was not initially placed acceptably, or when a producing interval has to be shut off.
  • the geopolymer composition can also be used in abandonment and/or plugging job.
  • the geopolymer material is used as a plug to shut off partially or totally a zone of the well.
  • Geopolymer material plug is placed inside the well by means that are well known in the art of wellbore plug cementing.
  • the geopolymer composition can also be used in grouting job to complete a part of the annulus as described in Well Cementing from Erik B. Nelson.
  • the geopolymer material is used to complete down this annulus.
  • Geopolymer material is placed inside the well by means that are well known in the art of wellbore cementing.
  • the geopolymer composition can also be used for fast-setting operation, in- situ operation. Effectively, the geopolymer composition can have a setting time perfectly controlled, allowing an instant setting when desired. For example, a retarder/accelerator combination can be added to the geopolymer composition to cause the system to be retarded for an extended period of time and then to set upon addition of an accelerator.
  • the geopolymer composition can also be a storable composition.
  • the suspension is over-retarder and is left intentionally in liquid phase. Said suspension is so, able to be stored and utilized in the well when needed.
  • Geopolymer composition is made in the amounts by weight of the total dry components as follows: 58.1% metakaolin and 41.9% sodium disilicate. Dry components are mixed with the appropriate amount of water, sodium hydroxide and additives. The specific gravity of the suspension is 1.53 g/cm 3 [12.80 lbm/gal].
  • the geopolymer has the following oxide molar ratios:
  • Geopolymer composition is made in the amounts by weight of the total dry components as follows: 28.5% metakaolin, 20.6% sodium disilicate and 50.9% of a blend of silica particles. Dry components are mixed with the appropriate amount of water, sodium hydroxide and additives. The specific gravity of the suspension is 1.84 g/cm 3 [15.40 lbm/gal].
  • the geopolymer matrix has the following oxide molar ratios:
  • Geopolymer composition is made in the amounts by weight of the total dry components as follows: 35.2% metakaolin and 64.2% potassium disilicate. Dry components are mixed with the appropriate amount of water, potassium hydroxide and additives. The specific gravity of the suspension is 1.78 g/cm 3 [14.91 lbm/gal].
  • the geopolymer matrix has the following oxide molar ratios:
  • Geopolymer composition is made in the amounts by weight of the total dry components as follows: 83.3% standard fly ash type F and 16.7% sodium disilicate. Dry components are mixed with the appropriate amount of water, sodium hydroxide and additives. The specific gravity of the suspension is 1.66 g/cm 3 [13.83 lbm/gal]. The geopolymer has the following oxide molar ratios:

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Abstract

L'invention concerne des compositions géopolymériques, qui ont un temps d'épaississement et de prise pouvant être contrôlé pour une large plage de températures et une large plage de densités de suspension de géopolymère. Les compositions de suspension de géopolymère ont une bonne aptitude au mélange et au pompage, tandis que les matériaux durcis développent une bonne résistance à la compression et une bonne perméabilité. L'invention décrit un procédé pour préparer un géopolymère pour des applications de cémentation de champ pétrolifère. Les compositions géopolymériques selon l'invention comprennent une suspension constituée d'une source d'aluminosilicate, d'un fluide porteur, d'un activateur pris dans la liste constituée par : un silicate de métal, un aluminate de métal, un activateur alcalin ou une combinaison de ceux-ci, et la suspension est une composition pouvant être pompée dans l'industrie des champs pétrolifères, et la suspension est capable d'être durcie dans des conditions de fond de puits.
PCT/EP2007/006815 2006-08-07 2007-08-03 Formulation de géopolymère pompable pour application à un champ pétrolifère WO2008017414A1 (fr)

Priority Applications (4)

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CA 2644991 CA2644991C (fr) 2006-08-07 2007-08-03 Formulation de geopolymere pompable pour application a un champ petrolifere
MX2009001400A MX2009001400A (es) 2006-08-07 2007-08-03 Formulacion de geopolimero bombeable para aplicacion en campo petrolifero.
NO20090602A NO347297B1 (no) 2006-08-07 2007-08-03 Pumpbar geopolymerblanding for anvendelse på oljefelt
AU2007283146A AU2007283146B2 (en) 2006-08-07 2007-08-03 Pumpable geopolymer formulation for oilfield application

Applications Claiming Priority (4)

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US11/462,724 2006-08-07
US11/462,724 US7794537B2 (en) 2006-08-07 2006-08-07 Geopolymer composition and application in oilfield industry
EP06291275.3 2006-08-07
EP20060291275 EP1887065B1 (fr) 2006-08-07 2006-08-07 Composition de géopolymère et son application dans l'industrie pétrolière

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WO2011072786A1 (fr) 2009-12-17 2011-06-23 Services Petroliers Schlumberger (Sps) Geopolymeres pompables comprenant un accelerateur de prise
WO2011072784A1 (fr) 2009-12-17 2011-06-23 Services Petroliers Schlumberger Géopolymères aptes au pompage comprenant un auxiliaire de mélange et un agent de dispersion
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WO2009103480A1 (fr) * 2008-02-19 2009-08-27 Services Petroliers Schlumberger Formulation géopolymère pompable pour application à un champ pétrolifère
EP2093200A1 (fr) * 2008-02-19 2009-08-26 Services Petroliers Schlumberger Formulation pompable de géopolymère pour un application dans les champs de pétrole
CN101323778B (zh) * 2008-07-29 2010-12-29 南京工业大学 油田固井用偏高岭土-矿渣基地质聚合物及其高温缓凝剂
US8839862B2 (en) 2008-09-24 2014-09-23 Minova International Limited Method of stabilising a blasthole
EP2389345A2 (fr) * 2009-01-22 2011-11-30 The Catholic University Of America Liants composites géopolymères personnalisés destinés à des applications de ciment et de béton
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RU2009108324A (ru) 2010-09-20
CA2644991A1 (fr) 2008-02-14
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CA2644991C (fr) 2010-10-05
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