WO2024078758A1 - Low dense settable geopolymer-forming slurry comprising a swellable clay, and settable treatment fluids obtainable from the slurry - Google Patents

Low dense settable geopolymer-forming slurry comprising a swellable clay, and settable treatment fluids obtainable from the slurry Download PDF

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Publication number
WO2024078758A1
WO2024078758A1 PCT/EP2023/070284 EP2023070284W WO2024078758A1 WO 2024078758 A1 WO2024078758 A1 WO 2024078758A1 EP 2023070284 W EP2023070284 W EP 2023070284W WO 2024078758 A1 WO2024078758 A1 WO 2024078758A1
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Prior art keywords
slurry
settable
geopolymer
fluid
forming composition
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PCT/EP2023/070284
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French (fr)
Inventor
Pouya KHALILI
Mahmoud KHALIFEH
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The University Of Stavanger
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Publication of WO2024078758A1 publication Critical patent/WO2024078758A1/en

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—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
    • 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
    • C09K8/473—Density reducing additives, e.g. for obtaining foamed cement compositions
    • 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
    • C09K8/48—Density increasing or weighting additives
    • 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 relates to subterranean treatment operations, such as zonal isolation and well abandonment, and more particularly to a low dense settable geopolymerforming slurry comprising a swellable clay, which slurry can also be used for preparing settable treatment fluids, such as a spacer fluid or wash fluid, for use in such subterranean treatment operations.
  • Geopolymers (introduced by Davidovits in 1976) are aluminosilicate inorganic polymers produced by mixing liquid hardener with reactive aluminum and silicate source (precursor) such as fly ash, slag, rice husk ash, metakaolin, red mud, and naturally occurring rocks.
  • precursor reactive aluminum and silicate source
  • Mechanisms that are involved in geopolymerization are dissolution of aluminosilicate solid particles in high pH environment and creation of Si-O-H, transportation of molecules because of higher activity of ions and yielding oligomers, and polycondensation by gluing the oligomers which results in a 3D structure.
  • the product is a combination of amorphous, semi crystalline and crystalline three-dimensional aluminosilicate chains.
  • WO 2014/052705 discloses settable spacer fluids comprising pumicite and methods of using such fluids in subterranean formations.
  • the treatment fluids taught therein could optionally comprise various additives, i.a. a viscosifying agent.
  • Suitable viscosifying agents could include colloidal agents, emulsion forming agents, diatomaceous earth, starches, biopolymers, synthetic polymers, or mixtures thereof.
  • the colloidal agents in turn, could e.g., include a clay.
  • suitable clays, listed therein, in turn, include, i.a., montmorillonite and bentonite.
  • WO 2008/017413 teaches a pumpable geopolymer formulation and application for carbon dioxide storage.
  • the aluminosilicate source used is selected from a group comprising, i.a., bentonite.
  • a lightweight particle and/or a heavyweight material can be added to control the density of the geopolymeric composition.
  • the lightweight particles also called fillers are selected from the group constituted of: cenospheres, sodium-calcium-borosilicate glass, and silica-alumina microsphere.
  • 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.
  • 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
  • WO 2029/156547 relates to a pumpable geopolymer cement composition and its application as a well cement.
  • low dense slurries e.g., to avoid fluid loss, slurry loss and formation damage.
  • Reducing the density of a geopolymeric composition can be done by foaming, or utilizing low dense particles such as taught in WO 2008/017413 above.
  • the low dense particles are sensitive to pressure and mechanical damage, and foaming a geopolymer slurry with e.g., nitrogen is a sensitive operation and bears operational complexity.
  • the above problem has been solved by utilization of a swellable clay.
  • the present inventors have found that a swellable clay can be used as a filler or extender in a geopolymer-forming slurry, to reduce the density of the slurry.
  • the solution offered by the invention has a minimum impact on desirable fluid-state and solid-state properties of the geopolymer-forming slurry and the resulting geopolymer, respectively.
  • the present invention relates to a geopolymer-forming composition in the form of a slurry, for use in subterranean treatment operations comprising: a source of aluminosilicate selected from the group consisting of fly ash, slag, metakaolin, kaolin, norite, granite, aplite, or aluminosilicate obtained from rice husk, and a combination of any two or more thereof; an alkaline activator selected from the group consisting of LiOH, NaOH, KOH, Li2SiOs, Na2SiOs, SiCh, Na2SO4, K2SO4, NaAIO2, and KAIO2, and a combination of any two or more thereof; and water, which composition additionally comprises a swellable clay selected from the group consisting of bentonite, montmorillonite, and a synthetic layered clay with a capability of swelling, and a combination of two or three thereof, and, a booster salt selected from the group consisting of NaCI, KCI
  • the present invention relates to a geopolymer-forming settable treatment fluid for use in subterranean treatment operations, which treatment fluid can be formed from the inventive slurry.
  • the inventive treatment fluids all contain a swellable clay selected from the group consisting of bentonite, montmorillonite, and a synthetic layered clay with a capability of swelling.
  • the inventive slurry additionally comprises one or more of a low dense fluid, fluid loss admixtures, weighting agent for tuning the density, admixtures to tune viscosity profile, retarding and accelerating admixtures.
  • the inventive treatment fluid preferably additionally comprises one or more of the following, a surfactant, a solvent, and a pH adjuster.
  • the inventive treatment fluid is a spacer liquid.
  • inventive slurry and treatment fluid are compatible with different types of geopolymers known in the art.
  • the inventive slurry and treatment fluid will water-wet formation and steel and make bonding to them.
  • the inventive slurry and treatment fluid can be designed so as to be compatible with water-based and oil-based drilling fluids.
  • geopolymer and “alkali-activated materials”, respectively, are used synonymously to denote same materials.
  • the term “geopolymer” is distinguished from cement in that the geopolymerization reaction is resulting in geopolymers, while the cement reaction with water, known as hydration, is the mechanism behind setting of cement. Geopolymerization reaction produces water, while cement hydration consumes water.
  • the product of cement hydration is C-S-H (Calcium-Silicate-Hydrate) while geopolymers are 3D networks of aluminosilicates produced through geopolymerization. Accordingly, using this meaning, as opposed to the compositions disclosed herein, the compositions taught in WO 2029/156547 are cement compositions.
  • Figure 1 shows the compressive strength of a low dense geopolymer with 1.52 sg density after 1 and 7 days, respectively, of curing of an embodiment of the inventive slurry.
  • Samples were cured in cylindrical molds at a temperature of 50°C and a 2000 pressure of psi, and thereafter crushed with the rate of 30 kN/min using MTS servo hydraulic testing machine.
  • Figure 2 shows the flow curve of a sample of the inventive slurry from which the geopolymer shown in Fig. 1 has been prepared.
  • the viscosity profile was measured using OFITE model 900 viscometer at a temperature of 50°C and atmospheric pressure.
  • Swellable clays which are used according to the invention, mainly consist of aluminium and silicate which makes them more chemically compatible with a geopolymer compared to other swellable particles, since geopolymers are made from aluminosilicates and crosslinked with alkali metal ions.
  • Bentonite has a layered structure that, upon contact with water, has the ability to absorb water molecules between sheets within the layered structure. This results in the swelling of bentonite, as the water is incorporated within its structure.
  • Geopolymerization reaction involves the production of water. This reduces the strength of geopolymers if too much water is present in the slurry.
  • Laponite is a synthesized layered silicate.
  • the inventive low dense geopolymer is preferably produced by mixing the swellable clay, and the alkali liquid or solid activator with reactive aluminosilicate source.
  • alkali activators are LiOH, NaOH, KOH, Li2SiOs, Na2SiOs, SiCh, Na2SO4, K2SO4, NaAIO2, and KAIO2.
  • the alkali activator is preferably included in an amount of 0.1-3 % by weight of the slurry.
  • a preferred activator is selected from the group consisting of SiCh, KOH, K2SO4, and KAIO2.
  • the reactive aluminosilicate source can be fly ash, slag, metakaolin, kaolin, norite, granite, aplite, olivine, quick clay, or aluminosilicate obtained from rice husk, and a combination of any two or more thereof.
  • the preferred aluminosilicate source is a combination of slag and granite, and more preferably merely slag.
  • the concentration of aluminosilicate source can vary from from 30 % to 90 % by weight of the slurry.
  • the inventive settable geopolymer-forming composition preferably comprises calcium. A calcium content will provide for making sufficient early strength through C-A-S-H gels and then they are turned to geopolymers in a later stage.
  • the total calcium content should preferably be within the range of 2-18 wt.% of the total dry substances, and more preferably within the range of 2-14 wt.% of the total dry substances.
  • This calcium can include free Ca or calcium in the structure of crystals.
  • Calcium containing aluminosilicate sources are slag, fly ash, wollastonite, olivine, granite.
  • the alkali activator and the reactive aluminosilicate source are preferably included in a ratio of alkali activator to reactive aluminosilicate source within the range of 1.4-3 by weight of the slurry.
  • the molarity of the alkali activator in the slurry is preferably 0.1 to 4M.
  • the inventive low dense geopolymer contains swellable clay as an extender to decrease the density and free water.
  • swellable clays are bentonite, laponite, and montmorillonite.
  • the preferred swellable clay is bentonite.
  • the concentration of swellable clay can preferably vary from 0.5 % to 20 % by weight of the slurry.
  • the swellable clay is typically included in an amount of 0.3-15%, more preferably 0.4-5% by weight of the slurry.
  • Especially preferred is a low amount of swellable clay, within the range of 0.5-3.
  • Bentonite typically consists of up to about 70% by weight of swellable clay (i.e. montmorillonite).
  • the inventive treatment liquid typically comprises 0.3-15% by weight of swellable clay, more preferably 0.4-5% by weight of the treatment fluid.
  • a low amount of swellable clay within the range of 0.5-3.
  • bentonite has been included in the long list of materials from which a source of aluminosilicate is to be selected according to WO 2008/017413
  • ICP-MS analysis performed by the present inventors has shown that the dissolution rate of bentonite is almost null, and that bentonite does not participate in the geopolymer-forming reactions.
  • the present inventors have found bentonite to be a suitable extender. An extender which is moreover swellable and reduces the density of the geopolymer-forming composition.
  • the low dense geopolymer-forming composition in the form of a slurry contains one or more booster salts such as NaCI, KCI, CaCl2, Na2COs, K2CO3, MgCCh, and CaCCh to increase the early strength.
  • booster salts such as NaCI, KCI, CaCl2, Na2COs, K2CO3, MgCCh, and CaCCh to increase the early strength.
  • the sodium-containing and calcium-containing salts are preferred due to small size of sodium and capacity of calcium to great extend balance the negative charges of [SiO4] -1 .
  • the concentration of booster salt in the inventive slurry can vary from 0.5 to 10 % by weight of the slurry.
  • booster salt is included in a range of 0.5-5% by weight of the slurry.
  • the low dense geopolymer-forming composition in the form of a slurry contains a viscosifier to increase the viscosity, such as of polymers and clays.
  • a viscosifier to increase the viscosity
  • suitable polymer viscosifiers are hydroxyethyl cellulose (HEC), xanthan gum, guar gum, and We- lan gum.
  • HEC hydroxyethyl cellulose
  • the viscosifier which is included in the inventive spacer fluid can be used to tune the viscosity of the spacer fluid according to viscosity of the cementitious material and drilling fluid. Drilling fluid is the displaced fluid, and cementitious material is displacing fluid in the wellbore.
  • the concentration of viscosifiers can vary from 0.2 to 20 % by weight of the slurry.
  • the inventive low dense geopolymer-forming composition in the form of a slurry and treatment fluid contain fluid loss control additives.
  • fluid loss control additives are starch, lignite, polyacrylamide, polyethyleneamines, carboxymethyl hydroxyethyl cellulose (CMHEC), and hydroxyethyl cellulose (HEC), polyanionic cellulose (PAC), carboxymethyl cellulose (CMC), fine silica, and fiber-based materials.
  • CCMHEC carboxymethyl hydroxyethyl cellulose
  • HEC hydroxyethyl cellulose
  • PAC polyanionic cellulose
  • CMC carboxymethyl cellulose
  • the low dense geopolymer-forming composition in the form of a slurry contains a weighting agent to increase the density of the slurry.
  • weighting agents are barite, granite, hematite, norite, aplite, and ilmenite. Accordingly, each one of norite, granite, and aplite, can be included as a source of aluminosilicate, or a weighting agent, or both. Hence, the weighting agents may or may not participate in the reaction in a later stage.
  • a weighting agent can help adjusting the density of the spacer fluid according to the density of the drilling fluid and cementitious material to have better displacement in the wellbore.
  • the concentration of weighting agents can be up to 60 % by weight of the slurry.
  • the inventive treatment fluid contains a surfactant to water-wet the surface of casing and formation, and stabilizing the emulsion.
  • surfactants are fatty alcohol and polyoxyethylene ethers.
  • the surface-active agent when used in the inventive spacer fluid, reduces the incompatibility with drilling fluid. Incompatibility can be in different ways such as viscosification and particle settling.
  • the concentration of surfactant can vary from 0.5 to 8 % by weight of the slurry.
  • the inventive treatment fluid contains a solvent to clean and remove the oil.
  • a solvent is 2-butoxyethanol.
  • concentration of solvent can vary from 0.5 to 8 % by weight of slurry.
  • the activator(s) can be added as a solid, or dissolved, i.e. in liquid form.
  • the swellable clay e.g. bentonite
  • solid activator is introduced, followed by solid precursors, and, subsequently, liquid activator is added.
  • a weighting agent When used in the spacer fluid, a weighting agent can help adjusting the density of spacer fluid according to the density of the drilling fluid and cementitious material to have better displacement in the wellbore.
  • the density range of the inventive slurry and treatment fluids are preferably tuned so as to be in the range of 1.2 to 1.9 sg, preferably 1.2 to 1.7 sg, more preferably 1.2 to 1.6 sg, as measured at ambient temperature and elevated pressure by use of pressurized mud balance.
  • a weighting agent can be added to the slurry or treatment fluid, and, conversely, in order to decrease the density, water and/or additional swellable clay can be added to the slurry or treatment fluid.
  • the pH range of the slurry and treatment fluid is preferably adjusted so as to be within the range of 8 to 13, preferably 9 to 13, and more preferably 11 to 13.
  • the inventive slurry and treatment fluid can be designed for different temperatures.
  • the operational temperature of the slurry or treatment fluid is typically 10 to 150°C, preferably 20 to 150°C, and more preferably 25 to 140°C.
  • the inventive slurry and treatment fluids do not contain fragile lightweight particles such as cenospheres, sodium-calcium-borosilicate glass, and silica-alumina microspheres. Accordingly, in preferred embodiments of the inventive slurry and treatment fluids, fragile lightweight particles are absent.
  • the inventive slurry is not foamed, such as using a gas. Accordingly, in preferred embodiments of the inventive slurry and treatment fluids, the inventive slurry and treatment liquids do not contain a foaming gas.
  • Spacer fluid is an example of a treatment fluid that can be prepared from the inventive low dense geopolymer-forming composition in the form of a slurry using admixtures such as surfactants, solvents and viscosifiers, and weighting agents.
  • Other treatment fluids that can be prepared from the inventive slurry are, preflush, wash fluid, and buffer fluid.
  • a retarder such as gluconic acid, and lignosulfonate, is preferably not included in the inventive compositions.
  • the composition and method of preparation of the samples shown in Fig. 1 are described below.
  • the bentonite used consisted of about 70% by weight of swellable clay, i.e. montmorillonite.
  • the calcium content is 18% by weight of the total dry substances.
  • the ingredients are mixed in the order of appearance in the table.
  • the density of the example sample is 1.52 sg and the flow curve is shown in Figure 2.
  • the bentonite used consisted of about 70% by weight of swellable clay, i.e. montmorillonite.
  • the calcium content is 13 % by weight of the total dry substances.
  • the ingre-transients are mixed in the order of appearance in table 2 below.

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Abstract

A low dense settable geopolymer-forming slurry for use in subterranean treatment operations comprising a swellable clay is disclosed, which slurry can be used for preparation of treatment liquids, e.g. a spacer fluid and a wash fluid.

Description

LOW DENSE SETTABLE GEOPOLYMER-FORMING SLURRY COMPRISING A SWELLABLE CLAY,
AND SETTABLE TREATMENT FLUIDS OBTAINABLE FROM THE SLURRY
FIELD OF THE INVENTION
The present invention relates to subterranean treatment operations, such as zonal isolation and well abandonment, and more particularly to a low dense settable geopolymerforming slurry comprising a swellable clay, which slurry can also be used for preparing settable treatment fluids, such as a spacer fluid or wash fluid, for use in such subterranean treatment operations.
BACKGROUND ART
In cementing operations, water is used to dilute a cement slurry and subsequently reducing the density. Due to concern associated with CO2 emission and long-term durability of conventional cement, researchers and engineers have been trying to replace the Ordinary Portland Cement as used in conventional cement with geopolymers and alkali-activated materials. Recently, geopolymers have attracted lots of attention in oil and gas industry with application in primary cementing and plug and abandonment operation.
Geopolymers (introduced by Davidovits in 1976) are aluminosilicate inorganic polymers produced by mixing liquid hardener with reactive aluminum and silicate source (precursor) such as fly ash, slag, rice husk ash, metakaolin, red mud, and naturally occurring rocks. Mechanisms that are involved in geopolymerization are dissolution of aluminosilicate solid particles in high pH environment and creation of Si-O-H, transportation of molecules because of higher activity of ions and yielding oligomers, and polycondensation by gluing the oligomers which results in a 3D structure. The product is a combination of amorphous, semi crystalline and crystalline three-dimensional aluminosilicate chains.
WO 2014/052705 discloses settable spacer fluids comprising pumicite and methods of using such fluids in subterranean formations. The treatment fluids taught therein could optionally comprise various additives, i.a. a viscosifying agent. Suitable viscosifying agents, in turn, could include colloidal agents, emulsion forming agents, diatomaceous earth, starches, biopolymers, synthetic polymers, or mixtures thereof. The colloidal agents, in turn, could e.g., include a clay. The examples of suitable clays, listed therein, in turn, include, i.a., montmorillonite and bentonite.
WO 2008/017413 teaches a pumpable geopolymer formulation and application for carbon dioxide storage. The aluminosilicate source used is selected from a group comprising, i.a., bentonite. To control the density of the geopolymeric composition, 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 microsphere. 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. Preferably, 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.
US 2008/0028944 Al seems to comprise a similar teaching to that of WO 2008/017413, but for a geopolymer composition and its application in oilfield industry.
WO 2029/156547 relates to a pumpable geopolymer cement composition and its application as a well cement.
In some applications, it would be desirable to utilize low dense slurries, e.g., to avoid fluid loss, slurry loss and formation damage. Reducing the density of a geopolymeric composition can be done by foaming, or utilizing low dense particles such as taught in WO 2008/017413 above. However, the low dense particles are sensitive to pressure and mechanical damage, and foaming a geopolymer slurry with e.g., nitrogen is a sensitive operation and bears operational complexity. Moreover, because of the chemistry and reaction mechanisms of geopolymers and alkali activated materials, application of the above-mentioned solutions significantly impact the setting time, rheological behaviour, and mechanical properties of the geopolymers, and also volume changes, and long-term durability of the resulting product. It is an object of the present invention to provide an alternative way of reducing the density of geopolymers which is not associated with the above drawbacks of the prior art.
SUMMARY OF THE INVENTION
According to the present invention, the above problem has been solved by utilization of a swellable clay. The present inventors have found that a swellable clay can be used as a filler or extender in a geopolymer-forming slurry, to reduce the density of the slurry. The solution offered by the invention has a minimum impact on desirable fluid-state and solid-state properties of the geopolymer-forming slurry and the resulting geopolymer, respectively.
Accordingly, in one aspect the present invention relates to a geopolymer-forming composition in the form of a slurry, for use in subterranean treatment operations comprising: a source of aluminosilicate selected from the group consisting of fly ash, slag, metakaolin, kaolin, norite, granite, aplite, or aluminosilicate obtained from rice husk, and a combination of any two or more thereof; an alkaline activator selected from the group consisting of LiOH, NaOH, KOH, Li2SiOs, Na2SiOs, SiCh, Na2SO4, K2SO4, NaAIO2, and KAIO2, and a combination of any two or more thereof; and water, which composition additionally comprises a swellable clay selected from the group consisting of bentonite, montmorillonite, and a synthetic layered clay with a capability of swelling, and a combination of two or three thereof, and, a booster salt selected from the group consisting of NaCI, KCI, CaCl2, Na2COs, K2CO3, MgCCh, CaCOs and a combination of any two or more thereof.
In another aspect the present invention relates to a geopolymer-forming settable treatment fluid for use in subterranean treatment operations, which treatment fluid can be formed from the inventive slurry. The inventive treatment fluids all contain a swellable clay selected from the group consisting of bentonite, montmorillonite, and a synthetic layered clay with a capability of swelling.
Preferably, the inventive slurry additionally comprises one or more of a low dense fluid, fluid loss admixtures, weighting agent for tuning the density, admixtures to tune viscosity profile, retarding and accelerating admixtures.
The inventive treatment fluid preferably additionally comprises one or more of the following, a surfactant, a solvent, and a pH adjuster. In a preferred embodiment, the inventive treatment fluid is a spacer liquid.
The inventive slurry and treatment fluid are compatible with different types of geopolymers known in the art.
By inclusion of a surfactant, the inventive slurry and treatment fluid will water-wet formation and steel and make bonding to them.
The inventive slurry and treatment fluid can be designed so as to be compatible with water-based and oil-based drilling fluids.
Pumpability of the slurry is tunable based on desired operational conditions.
Further embodiments and advantages of the invention will be apparent from the following detailed description and appended claims.
In the art, the terms "geopolymer" and "alkali-activated materials", respectively, are used synonymously to denote same materials. The term "geopolymer", as used herein, is intended to embrace also materials referred to in the art as "alkali-activated materials". Moreover, as used herein, the term "geopolymer" is distinguished from cement in that the geopolymerization reaction is resulting in geopolymers, while the cement reaction with water, known as hydration, is the mechanism behind setting of cement. Geopolymerization reaction produces water, while cement hydration consumes water. Subsequently, the product of cement hydration is C-S-H (Calcium-Silicate-Hydrate) while geopolymers are 3D networks of aluminosilicates produced through geopolymerization. Accordingly, using this meaning, as opposed to the compositions disclosed herein, the compositions taught in WO 2029/156547 are cement compositions.
The density of the inventive slurry is expressed herein in terms of the specific gravity (sg) of the slurry (specific gravity of slurry=density of slurry/density of water). Measurements have been carried out at room temperature.
BRIEF DESCRIPTION OF THE ATTACHED DRAWINGS
Figure 1 shows the compressive strength of a low dense geopolymer with 1.52 sg density after 1 and 7 days, respectively, of curing of an embodiment of the inventive slurry. Samples were cured in cylindrical molds at a temperature of 50°C and a 2000 pressure of psi, and thereafter crushed with the rate of 30 kN/min using MTS servo hydraulic testing machine.
Figure 2 shows the flow curve of a sample of the inventive slurry from which the geopolymer shown in Fig. 1 has been prepared. The viscosity profile was measured using OFITE model 900 viscometer at a temperature of 50°C and atmospheric pressure.
DETAILED DESCRIPTION OF THE INVENTION
Swellable clays, which are used according to the invention, mainly consist of aluminium and silicate which makes them more chemically compatible with a geopolymer compared to other swellable particles, since geopolymers are made from aluminosilicates and crosslinked with alkali metal ions. Bentonite has a layered structure that, upon contact with water, has the ability to absorb water molecules between sheets within the layered structure. This results in the swelling of bentonite, as the water is incorporated within its structure. Geopolymerization reaction involves the production of water. This reduces the strength of geopolymers if too much water is present in the slurry. When bentonite, montmorillonite, or a synthetic layered clay with a capability of swelling (e.g., laponite) is used in the slurry, the amount of free water will be reduced which contributes to strength of the resulting geopolymer formed. Laponite is a synthesized layered silicate.
The inventive low dense geopolymer is preferably produced by mixing the swellable clay, and the alkali liquid or solid activator with reactive aluminosilicate source. Examples of alkali activators are LiOH, NaOH, KOH, Li2SiOs, Na2SiOs, SiCh, Na2SO4, K2SO4, NaAIO2, and KAIO2. The alkali activator is preferably included in an amount of 0.1-3 % by weight of the slurry. A preferred activator is selected from the group consisting of SiCh, KOH, K2SO4, and KAIO2. The reactive aluminosilicate source can be fly ash, slag, metakaolin, kaolin, norite, granite, aplite, olivine, quick clay, or aluminosilicate obtained from rice husk, and a combination of any two or more thereof. The preferred aluminosilicate source is a combination of slag and granite, and more preferably merely slag. The concentration of aluminosilicate source can vary from from 30 % to 90 % by weight of the slurry. The inventive settable geopolymer-forming composition preferably comprises calcium. A calcium content will provide for making sufficient early strength through C-A-S-H gels and then they are turned to geopolymers in a later stage. The total calcium content, calculated as weight of Ca, should preferably be within the range of 2-18 wt.% of the total dry substances, and more preferably within the range of 2-14 wt.% of the total dry substances. This calcium can include free Ca or calcium in the structure of crystals. Calcium containing aluminosilicate sources are slag, fly ash, wollastonite, olivine, granite.
The alkali activator and the reactive aluminosilicate source are preferably included in a ratio of alkali activator to reactive aluminosilicate source within the range of 1.4-3 by weight of the slurry.
The molarity of the alkali activator in the slurry is preferably 0.1 to 4M.
The inventive low dense geopolymer contains swellable clay as an extender to decrease the density and free water. Examples of swellable clays are bentonite, laponite, and montmorillonite. The preferred swellable clay is bentonite. The concentration of swellable clay can preferably vary from 0.5 % to 20 % by weight of the slurry. The swellable clay is typically included in an amount of 0.3-15%, more preferably 0.4-5% by weight of the slurry. Especially preferred is a low amount of swellable clay, within the range of 0.5-3. When bentonite is being used, account should be taken for the actual amount of swellable clay therein. Bentonite typically consists of up to about 70% by weight of swellable clay (i.e. montmorillonite). The inventive treatment liquid typically comprises 0.3-15% by weight of swellable clay, more preferably 0.4-5% by weight of the treatment fluid. Especially preferred is a low amount of swellable clay, within the range of 0.5-3.
While bentonite has been included in the long list of materials from which a source of aluminosilicate is to be selected according to WO 2008/017413, ICP-MS analysis performed by the present inventors has shown that the dissolution rate of bentonite is almost null, and that bentonite does not participate in the geopolymer-forming reactions. The present inventors have found bentonite to be a suitable extender. An extender which is moreover swellable and reduces the density of the geopolymer-forming composition. The low dense geopolymer-forming composition in the form of a slurry contains one or more booster salts such as NaCI, KCI, CaCl2, Na2COs, K2CO3, MgCCh, and CaCCh to increase the early strength. The sodium-containing and calcium-containing salts are preferred due to small size of sodium and capacity of calcium to great extend balance the negative charges of [SiO4]-1. The concentration of booster salt in the inventive slurry can vary from 0.5 to 10 % by weight of the slurry. Preferably, booster salt is included in a range of 0.5-5% by weight of the slurry.
Optionally, the low dense geopolymer-forming composition in the form of a slurry contains a viscosifier to increase the viscosity, such as of polymers and clays. Examples of suitable polymer viscosifiers are hydroxyethyl cellulose (HEC), xanthan gum, guar gum, and We- lan gum. The viscosifier which is included in the inventive spacer fluid can be used to tune the viscosity of the spacer fluid according to viscosity of the cementitious material and drilling fluid. Drilling fluid is the displaced fluid, and cementitious material is displacing fluid in the wellbore. In embodiments of the inventive slurry including a viscosifier, the concentration of viscosifiers can vary from 0.2 to 20 % by weight of the slurry.
Optionally, the inventive low dense geopolymer-forming composition in the form of a slurry and treatment fluid contain fluid loss control additives. Examples of such additives are starch, lignite, polyacrylamide, polyethyleneamines, carboxymethyl hydroxyethyl cellulose (CMHEC), and hydroxyethyl cellulose (HEC), polyanionic cellulose (PAC), carboxymethyl cellulose (CMC), fine silica, and fiber-based materials. When included, the concentration of fluid loss control additives can vary from 0.01 to 3 % by weight of the slurry and treatment fluid, respectively.
Optionally, the low dense geopolymer-forming composition in the form of a slurry contains a weighting agent to increase the density of the slurry. Examples of weighting agents are barite, granite, hematite, norite, aplite, and ilmenite. Accordingly, each one of norite, granite, and aplite, can be included as a source of aluminosilicate, or a weighting agent, or both. Hence, the weighting agents may or may not participate in the reaction in a later stage. When used in the spacer fluid, a weighting agent can help adjusting the density of the spacer fluid according to the density of the drilling fluid and cementitious material to have better displacement in the wellbore. In embodiments wherein a weighting agent is included, the concentration of weighting agents can be up to 60 % by weight of the slurry.
Optionally, the inventive treatment fluid contains a surfactant to water-wet the surface of casing and formation, and stabilizing the emulsion. Examples of surfactants are fatty alcohol and polyoxyethylene ethers. The surface-active agent, when used in the inventive spacer fluid, reduces the incompatibility with drilling fluid. Incompatibility can be in different ways such as viscosification and particle settling. When included, the concentration of surfactant can vary from 0.5 to 8 % by weight of the slurry.
Optionally, the inventive treatment fluid contains a solvent to clean and remove the oil. An example of a solvent is 2-butoxyethanol. The concentration of solvent can vary from 0.5 to 8 % by weight of slurry.
The activator(s) can be added as a solid, or dissolved, i.e. in liquid form. To prepare the slurry, preferably, first, the swellable clay, e.g. bentonite, is pre-hydrated in the water. Thereafter, solid activator is introduced, followed by solid precursors, and, subsequently, liquid activator is added.
When used in the spacer fluid, a weighting agent can help adjusting the density of spacer fluid according to the density of the drilling fluid and cementitious material to have better displacement in the wellbore.
The density range of the inventive slurry and treatment fluids are preferably tuned so as to be in the range of 1.2 to 1.9 sg, preferably 1.2 to 1.7 sg, more preferably 1.2 to 1.6 sg, as measured at ambient temperature and elevated pressure by use of pressurized mud balance. In order to increase the density, a weighting agent can be added to the slurry or treatment fluid, and, conversely, in order to decrease the density, water and/or additional swellable clay can be added to the slurry or treatment fluid.
The pH range of the slurry and treatment fluid is preferably adjusted so as to be within the range of 8 to 13, preferably 9 to 13, and more preferably 11 to 13. The inventive slurry and treatment fluid can be designed for different temperatures. The operational temperature of the slurry or treatment fluid is typically 10 to 150°C, preferably 20 to 150°C, and more preferably 25 to 140°C.
Preferably, the inventive slurry and treatment fluids do not contain fragile lightweight particles such as cenospheres, sodium-calcium-borosilicate glass, and silica-alumina microspheres. Accordingly, in preferred embodiments of the inventive slurry and treatment fluids, fragile lightweight particles are absent.
Preferably, the inventive slurry is not foamed, such as using a gas. Accordingly, in preferred embodiments of the inventive slurry and treatment fluids, the inventive slurry and treatment liquids do not contain a foaming gas.
Examples of different treatment fluids that can be prepared from the inventive slurry.
Spacer fluid is an example of a treatment fluid that can be prepared from the inventive low dense geopolymer-forming composition in the form of a slurry using admixtures such as surfactants, solvents and viscosifiers, and weighting agents. Other treatment fluids that can be prepared from the inventive slurry are, preflush, wash fluid, and buffer fluid.
A retarder, such as gluconic acid, and lignosulfonate, is preferably not included in the inventive compositions.
EXAMPLES
Example 1 - slurry and preparation thereof
The composition and method of preparation of the samples shown in Fig. 1 are described below. The bentonite used consisted of about 70% by weight of swellable clay, i.e. montmorillonite. The calcium content is 18% by weight of the total dry substances. In the example, the ingredients are mixed in the order of appearance in the table.
Table 1 - mix design of the samples shown in Fig.l
Figure imgf000010_0001
Figure imgf000011_0001
The density of the example sample is 1.52 sg and the flow curve is shown in Figure 2.
Example 2 - Slurry and preparation thereof
The bentonite used consisted of about 70% by weight of swellable clay, i.e. montmorillonite.
The calcium content is 13 % by weight of the total dry substances. In the example, the ingre- dients are mixed in the order of appearance in table 2 below.
Table 2 - mix design of the slurry in Example 2
Figure imgf000011_0002

Claims

1. A settable geopolymer-forming composition in the form of a slurry for use in subterranean treatment operations comprising:
- a source of aluminosilicate selected from the group consisting of fly ash, slag, metakaolin, kaolin, norite, granite, aplite, olivine, quick clay, or aluminosilicate obtained from rice husk, and a combination of any two or more thereof;
- an alkaline activator selected from the group consisting of LiOH, NaOH, KOH, Li2SiO3, Na2SiOs, l<2SiO3, NaAIO2, KAIO2, Na2SO4, K2SO4 and a combination of any two or more thereof; and, water, characterized in additionally comprising
- a swellable clay selected from the group consisting of bentonite, montmorillonite, and a synthetic layered clay with a capability of swelling; and,
- a booster salt selected from the group consisting of NaCI, KCI, CaCh, Na2COs, K2CO3, MgCOs, CaCOs and a combination of any two or more thereof.
2. The settable geopolymer-forming composition in the form of a slurry for use in subterranean treatment operations according to claim 1, wherein the swellable clay is included in an amount of 0.5-20% by weight of the slurry.
3. The settable geopolymer-forming composition in the form of a slurry for use in subterranean treatment operations according to claim 1 or 2, wherein slag is included as a source of aluminosilicate, preferably in an amount within the range of 5-50% by weight of the slurry, more preferably 6-45% by weight of the slurry.
4. The settable geopolymer-forming composition in the form of a slurry for use in subterranean treatment operations according to any one of the preceding claims, wherein the booster salt is included in an amount of 0.5-10% by weight of the slurry.
5. The settable geopolymer-forming composition in the form of a slurry, for use in subterranean treatment operations according to any one of the preceding claims, additionally comprising one or more of the following:
- a weighting agent selected from rock minerals, preferably barite, granite, hematite, norite, kaolin, aplite, ilmenite, and/or thermally treated species thereof;
- an organic polymer for adjusting fluid loss properties;
- a viscosifying agent to adjust viscosity; and,
- a solvent.
6. A settable treatment fluid for use in subterranean treatment operations, which can be formed from the settable geopolymer-forming composition in the form of a slurry of claim 1, characterized in being geopolymer-forming, and, in comprising:
- a swellable clay selected from the group consisting of bentonite, montmorillonite and a synthetic layered clay with a capability of swelling.
7. The settable treatment fluid of claim 6, formulated for use as settable spacer fluid, additionally comprising:
- a surfactant;
- a viscosity modifier: and,
- a solvent.
8. The settable treatment fluid of claim 6, formulated for use as settable wash fluid, additionally comprising:
- a surfactant; and,
- a solvent.
PCT/EP2023/070284 2022-10-13 2023-07-21 Low dense settable geopolymer-forming slurry comprising a swellable clay, and settable treatment fluids obtainable from the slurry WO2024078758A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110067868A1 (en) * 2003-05-14 2011-03-24 Sylvaine Le Roy-Delage Self adaptive cement systems
US20080028944A1 (en) 2006-07-25 2008-02-07 Webster Joseph P Multiple beverage brewer
WO2008017413A1 (en) 2006-08-07 2008-02-14 Services Petroliers Schlumberger Pumpable geopolymer formulation and application for carbon dioxide storage
EP2025732A1 (en) * 2007-07-27 2009-02-18 Services Pétroliers Schlumberger Self-repairing isolation systems
WO2014052705A1 (en) 2012-09-28 2014-04-03 Halliburton Energy Services, Inc. Settable spacer fluids comprising pumicite and methods of using such fluids in subterranean formations
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