WO2026010905A1 - Raw material compositions for geopolymers - Google Patents

Raw material compositions for geopolymers

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Publication number
WO2026010905A1
WO2026010905A1 PCT/US2025/036011 US2025036011W WO2026010905A1 WO 2026010905 A1 WO2026010905 A1 WO 2026010905A1 US 2025036011 W US2025036011 W US 2025036011W WO 2026010905 A1 WO2026010905 A1 WO 2026010905A1
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WO
WIPO (PCT)
Prior art keywords
geopolymer
aluminum
silicon
geopolymer precursor
precursor
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/US2025/036011
Other languages
French (fr)
Inventor
Christopher Parton
Mark Meade
Geoffrey LANDRY
Nathan Fischer
Yeukayi NENJERAMA
Veronica McDonald
Ruben ANGEL
Rudy BEJARANO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schlumberger Canada Ltd
Services Petroliers Schlumberger SA
Schlumberger Technology BV
Schlumberger Technology Corp
Original Assignee
Schlumberger Canada Ltd
Services Petroliers Schlumberger SA
Schlumberger Technology BV
Schlumberger Technology Corp
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
Application filed by Schlumberger Canada Ltd, Services Petroliers Schlumberger SA, Schlumberger Technology BV, Schlumberger Technology Corp filed Critical Schlumberger Canada Ltd
Publication of WO2026010905A1 publication Critical patent/WO2026010905A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10Coating or impregnating
    • C04B20/1018Coating or impregnating with organic materials
    • C04B20/1029Macromolecular compounds
    • C04B20/1048Polysaccharides, e.g. cellulose, or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467Compositions 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034Physico-chemical characteristics of the mixtures
    • C04B2111/00146Sprayable or pumpable mixtures
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • Geopolymers have been investigated for use in several applications, including as concrete systems within the construction industry, as refractory materials and as encapsulants for hazardous and radioactive waste streams. Geopolymers are also recognized as being rapid setting and hardening materials. They exhibit superior hardness and chemical stability.
  • the preparation of geopolymers generally involves mixing a blend of reactive solid materials and activating the polymerization reaction by adding an alkaline solution. Typically, the slurry mixture is then applied and allowed to harden in place. In construction, faster hardening is usually valued.
  • cement-like materials are used to line wells to provide isolation and structural support within the well. Use of cement-like materials in hydrocarbon wells presents unique challenges.
  • the slurry mixture precursor is typically pumped over long distances to the location where the mixture is to set, so the mixture must be pumpable without undue burden on equipment.
  • ambient conditions encountered in a typical hydrocarbon well are much more extreme than those encountered in a typical construction application.
  • the large vertical extent of hydrocarbon well applications presents challenges of density, temperature, and pressure not faced in the construction industry.
  • Other applications, like plugs, squeeze, and injector wells for water or carbon dioxide, also require a cementitious precursor to be pumped to an application site, so geopolymer compositions find broad use where pumping is required.
  • geopolymers are made using waste materials, such as fly ash and blast furnace slag, that contain aluminum, silicon, and oxygen in varying amounts. These materials are not usually controlled in any way, and the composition of such materials can vary widely, creating variability in composition and performance characteristics of geopolymers. Such variability is conventionally compensated using additives to achieve certain properties in the resulting geopolymers. Improved geopolymer compositions having less uncertain and variable performance are needed.
  • Embodiments described herein provide a geopolymer precursor, comprising a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material; an aqueous medium; and an alkali activator.
  • a method comprising forming a geopolymer precursor by dispersing a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material into an aqueous medium; and dispersing an alkali activator into the aqueous medium; pumping the geopolymer precursor to a target location; and hardening the geopolymer precursor to form a geopolymer at the target location.
  • a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material into an aqueous medium
  • an alkali activator into the aqueous medium
  • a method comprising obtaining a geopolymer precursor comprising a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material; and an alkali activator; pumping the geopolymer precursor to a target location; and hardening the geopolymer precursor to form a geopolymer at the target location.
  • Geopolymer materials are formed by disposing one or more sources of oxidized aluminum and silicon, along with an alkali activator in a water mixture.
  • the alkali activator produces a high pH aqueous solution that causes polymerization of the aluminum, silicon, and oxygen to form a geopolymer.
  • the methods described herein use individual sources of oxidized aluminum, silicon, or both aluminum and silicon, as raw materials for making geopolymers. Materials such as aluminum oxide, aluminum hydroxide, silica flour, and silica sand are used to make a blend having a selected content of aluminum, silicon, and oxygen to target properties of a geopolymer made from such materials.
  • Alumina-silica polymers such as sol gels formed from reaction of organoaluminum and organosilicon sols can also be used. Unoxidized aluminum and silicon can be included in the blend as well. Other reactive materials such as calcium oxide, metal silicates, metal sodium silicates, metal oxides, and metal carbonates can also be included.
  • a geopolymer precursor mixture can be made using a first reactant material consisting essentially of aluminum and oxygen, or of aluminum, oxygen, and hydrogen, or of aluminum, silicon, and oxygen, or of aluminum, silicon, oxygen, and hydrogen and a second reactant material consisting essentially of silicon and oxygen. Such materials are added to water, or to an aqueous mixture. An alkali source is added to raise pH of the geopolymer precursor and to activate polymerization of the aluminum, silicon, and oxygen of the reactant material.
  • a geopolymer precursor can be made by dispersing a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, and oxygen, a second material consisting essentially of aluminum, silicon, oxygen, and hydrogen, or a mixture of the first and second materials, into an aqueous medium.
  • An alkali activator is also dispersed into the aqueous medium to activate a polymerization reaction of the reactant material.
  • the geopolymer precursor can be made pumpable by adjusting water content, and thereby adjusting solids fraction, in the precursor.
  • a pumpable geopolymer precursor generally defined as a precursor that produces a dial reading of less than 300 using a Cuvette viscometer equipped with an R1 B1 F1 rotor:bob:spring configuration, can be pumped to a target location for setting and hardening. Multiple materials consisting essentially of aluminum, silicon, and oxygen, and optionally hydrogen can be used to form the geopolymer precursor mixture.
  • a geopolymer precursor that includes the reactant materials can be obtained, for example received, formed, or a combination thereof.
  • the geopolymer precursor may also include activators, additives, or both.
  • the geopolymer precursor can be deployed to a target location, for example by pumping where the precursor is pumpable, and allowed to harden to form a geopolymer.
  • the reactant materials described above can be pure materials or a mixture of materials.
  • a reactant material for purposes herein can include oxidized aluminum having chemical formula Al20x, where x is about 3, for example 2.9 to 3.1 , or 2.95 to 3.05, or 2.99 to 3.01 . That is, the oxidized aluminum can be aluminum oxide, but the aluminum oxide can be oxygen depleted, oxygen rich, or oxygen balanced (3 oxygen atoms for every 2 aluminum atoms).
  • the reactant material can include an aluminum hydroxide material having the general formula AIOaHb where b can be a small number representing hydrogen impurities or b can be a number close to a, such that a ratio of b/a is near 1 , for example 0.95 to 1 .05.
  • the aluminum hydroxide material may be hydrogen-depleted aluminum hydroxide or hydrogen-enriched aluminum hydroxide.
  • the oxygen content a is a number near 3, for example 2.95 to 3.05.
  • the reactant material can include oxidized silicon having chemical formula SiO y , where y is about 2, for example 1 .9 to 2.1 , or 1 .95 to 2.05, or 1.99 to 2.01. That is, the oxidized silicon can be silica or silicon oxide, but the silica or silicon oxide can be oxygen depleted, oxygen rich, or oxygen balanced (2 oxygen atoms for every silicon atom).
  • An oxidized aluminum material usable for the geopolymer precursors herein can be a homogeneous material, having substantially constant or consistent composition throughout the material, or the oxidized aluminum can be a heterogeneous material having varying composition throughout the material.
  • the oxidized aluminum can be a mixture of aluminum and aluminum oxide, for example an aluminum powder mixed with an aluminum oxide powder.
  • the oxidized aluminum can be a particulate material of oxide-coated aluminum particles or particles having two or more layers of aluminum oxide having the same or different compositions.
  • the oxidized silicon material can be homogeneous or heterogeneous.
  • An example of a heterogeneous oxidized silicon material is a mixture of silicon powder and silicon oxide powder or a particulate material of oxide-coated silicon particles.
  • a reactant material can be made from a first reactant material consisting essentially of silicon and oxygen and a second reactant material consisting essentially of aluminum and oxygen.
  • a reactant material can be made from a first reactant material consisting essentially of silicon and oxygen and a second reactant material consisting essentially of aluminum and oxygen.
  • Use of such reactant materials to form a geopolymer precursor allows precise control of the composition of the geopolymer.
  • the general chemical formula of a geopolymer is M n ⁇ -(SiO2)z-AIO2 ⁇ n, w H2O, wherein M is a cation such as potassium, sodium or calcium, n is a degree of polymerization and z is the Si/AI atomic ratio.
  • silica can be readily used as ingredients to make a geopolymer precursor described herein.
  • the silica can be crystalline silica.
  • Use of crystalline silica can help in achieving geopolymer characteristics such as precursor pumpability, solids fraction, density, viscosity, and the like. Crystalline silica having particle size from 1 -50 pm can be useful to tune particle size distribution of the geopolymer slurry.
  • Particulate materials described above can be coated with a material designed to affect development of a polymerization reaction in the geopolymer precursor material.
  • particles can be coated with a resin coating designed to dissolve or degrade over time to release geopolymerization reactants into the mixture.
  • the resin coating may be water soluble and/or acid soluble, and mixtures or multiple layers of coatings can be used.
  • particulate materials consisting essentially of aluminum and oxygen; aluminum, silicon, and oxygen; aluminum, hydrogen and oxygen; or silicon and oxygen can be coated with a polysaccharide coating, such as a starch or cellulose material, to delay entry of the reactants into the aqueous reaction medium.
  • such particulate materials can be coated with polyvinyl alcohol, polyethylene imine, polyacrylamide, polyethylene glycol, polyvinyl pyrrolidone, or another water-soluble polymer instead of, or in addition to, a polysaccharide.
  • a layered coating structure can be applied to such particulates where a first layer contains a first water-soluble polymer and a second layer contains a second water-soluble polymer, which may the same as, or different from, the first water-soluble polymer.
  • Polymers can also be used to coat particulates herein that degrade slowly at high pH, the conditions of the aqueous medium of the geopolymer precursor.
  • a polymer coating can include a hydrolysable component and a stable component such that degradation of the hydrolysable component in the high pH environment of the geopolymer precursor slowly releases the reactants encapsulated therein into the reactive aqueous environment.
  • Such methods can be used to slow thickening of a geopolymer precursor so that the precursor can be pumped, or otherwise deployed, to the target location before setting.
  • Such polymer materials can be copolymers or multipolymers of a stable component and a hydrolysable component, or the polymer materials can be mixtures, such as melt blends, of polymers.
  • a hydrolysable polymer such as a polyester or polyacid, for example polyvinyl acetate or polylactic acid
  • a stable polymer such as a polyolefin
  • the alkaline activators used herein can be dry materials, to which water or a non-activating aqueous material is added.
  • Examples include metal silicates M2xSi y C>2y+x where x is 1 , 2, or 3 and y is 1 or 2 (for example silicates, metasilicates, orthosilicates, and pyrosilicates), where M can be Li, Na, K, Rb, or Cs, or combination thereof, for example a mixed metal silicate like a metal sodium silicate, alkaline earth metal hydroxides such as Ca(OH)2, Sr(OH)2, Mg(OH)2 and/or Ba(OH)2, alkaline earth metal oxides such as CaO, SrO, MgO and/or BaO, and alkaline earth metal peroxides such as MgO2 and CaO2 or a combination thereof.
  • Such activators can be combined with an alkali metal salt such as a metal carbonate M2CO3, metal sulphate M2SO4, metal sulphite M2SO3, metal phosphate M3PO4, metal oxalate M2C2O4, metal silicate M2xSiyO2y+x where x is 1 , 2, or 3 and y is 1 or 2 (for example silicates, metasilicates, orthosilicates, and pyrosilicates), metal fluoride MF, metal hexafluoridosilicate M2SiFe, metal iodate MIO3, metal molybdate M2MOO4, where M can be Li, Na, K, Rb, or Cs, or combination thereof, where such salts can have a combination of different metals and a combination of different anions.
  • an alkali metal salt such as a metal carbonate M2CO3, metal sulphate M2SO4, metal sulphite M2SO3, metal phosphate M3PO4, metal
  • Lime and hydrated lime are examples of materials that contain calcium oxide and/or calcium hydroxide.
  • Hydrogenated metal salts such as MHCO3, MHSO4, MHPO4, MHC2O4, M2HPO4, MH2PO4, and MHSO3 can also be used, alone or in combination with other activators described herein, where M is as listed above. These activators raise pH in a slurry upon addition of water such that the aluminum, oxygen, and silicon in the geopolymer precursor composition dissolve and begin to react to form geopolymer.
  • activators are typically added in a quantity that is 2 to 40 parts per hundred based on the weight of the dry geopolymer precursor particulate blend, for example 4 to 20 parts per hundred or 4 to 40 parts per hundred based on the weight of the total dry geopolymer precursor particulate blend.
  • the activators used herein can also be aqueous solutions of the above materials and/or alkali metal hydroxides. Such activators can be added to the aqueous medium to be used for the geopolymer precursor before or after dispersing the reactant materials in the aqueous medium.
  • Thickening time of the geopolymer precursors described herein can be influenced by adding retarders and accelerators.
  • retarders may delay the setting and hardening of geopolymer systems, for example by as much as 2 hours.
  • Retarders such as sodium pentaborate decahydrate, borax, sucrose, boric acid, lignosulphonates, sodium glucoheptonate, tartaric acid, citric acid, or phosphorus containing compounds such as phosphoric acid, salts thereof, or mixtures thereof can be added to the geopolymer precursor particulate mixture in amounts of 0.01 to 5 part per hundred by weight of the total particulate precursor mixture.
  • Metal chlorides can also be accelerators and/or retarders.
  • the amount of retardation of the polymerization reaction, and the setting of the slurry depends on the type of raw materials used for the slurry and the type and relative quantity of retarder used. Adding too much retarder reagent to a geopolymer slurry can cause the slurry to remain unhardened by interfering with the polymerization reaction so the geopolymer does not set.
  • a retarder solution can be added to the carrier fluid or to the geopolymer slurry, or both. By this means, the same geopolymer precursor could be pumped into different sections of a well and setting time of geopolymer slurry in the different sections can be controlled through addition of a different amount of the retarder solution.
  • the geopolymer precursors described herein, using retarders can add at least 2 hours to time to reach 70 Be (Bearden consistency units) or 50 Be using a pressurized consistometer.
  • Accelerators can also be added to the geopolymer precursor particulate mixture in amounts up to about 0.01 -10, such as 1 -5, parts per hundred weight of the total particulate precursor mixture.
  • the amount of acceleration of the polymerization reaction, and the setting of the slurry depends on the type of raw materials used for the slurry and the type and relative quantity of accelerating reagent used. Adding too much accelerator to a geopolymer slurry can cause the slurry to thicken too quickly making it difficult to deploy the slurry to target locations downhole.
  • the retarders and accelerants described herein can be included as particulate materials in the geopolymer precursor composition, or such reagents can be added to water before the water is added to a geopolymer precursor composition described herein.
  • Geopolymer slurries for use in well lining applications typically have a slurry density range from 0.84 g/cm 3 (7 Ibm/gal) to 2.87 g/cm 3 (24 Ibm/gal), such as 1.32 g/cm 3 (11 Ibm/gal) to 2.4 g/cm 3 (20 Ibm/gal) or 1 .32 g/cm 3 (11 Ibm/gal) to 2.16 g/cm 3 (18 Ibm/gal), for example 1 .36 g/cm 3 (11 .3 Ibm/gal) to 1 .90 g/cm 3 (15.8 Ibm/gal).
  • the slurry density can be influenced by quantity of water added and/or by adding density modifiers.
  • Water typically makes up from about 20% by weight to about 60% by weight of a geopolymer slurry.
  • Density modifiers can include density increasing particles and density lowering particles.
  • Low-density particles may be added to the geopolymer precursor particulate mixture to achieve lower slurry densities for a given amount of water added, or heavy particles may be added to achieve higher slurry densities.
  • the lightweight or low-density particles may have densities lower than 2 g/cm 3 , or lower than 1.3 g/cm 3 .
  • Examples include hollow glass or ceramic microspheres (cenospheres), plastic particles such as polypropylene beads, rubber particles, uintaite (sold as GILSONITETM), bentonite, vitrified shale, petroleum coke or coal or combinations thereof.
  • the lightweight particles may be present in the compositions at concentrations between about 0.06 kg/L and 0.6 kg/L (20 Ib/bbl and 200 Ib/bbl).
  • the particle size range of the low-density particles may be between about 38 pm and 3350 pm (6 mesh and 400 mesh).
  • the heavy particles typically may have densities exceeding 2 g/cm 3 , or more than 3 g/cm 3 . Examples include hematite, barite, ilmenite, crushed granite and also manganese tetroxide commercially available under the trade names of MicroMaxTM and MicroMax FFTM.
  • additives such as anti-foam agents, defoamers, fluid-loss control additives, viscosifiers, dispersants, expanding agents, anti-settling additives or combinations thereof, can be included. 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 fluid-loss control agent may comprise a latex, one or more acrylic polymers, or combination thereof.
  • the latex may be an alkali-swellable latex.
  • the latex may be present in the compositions at a concentration between 0.02 L/L and 0.3 L/L or between 0.05 L/L and 0.15 L/L.
  • the acrylic polymers may be present at concentrations between 0.1 % and 10% by weight of the total dry geopolymer precursor.
  • Cellulosic materials and derivatives such as carboxyethylcellulose (CEC), hydroxymethylcellulose (HEC), carboxymethylcellulose (CMC), and polyanionic cellulose (PAC), can be used as a fluid-loss control agent herein.
  • Viscosifiers may comprise diutan gum having a molecular weight higher than about 1 x 10 6 .
  • the diutan gum may be present at a concentration between 0.14 g/L and 1 .4 g/L (0.05 Ibm/bbl and 0.5 Ibm/bbl).
  • viscosifiers are present in the dry geopolymer precursor at a concentration of 0.1 -5% by weight of the total dry geopolymer precursor.
  • Other viscosifiers may comprise a polysaccharide material, which may be a biopolymer.
  • Welan gum is an example of a polysaccharide material that can be used as a viscosifier herein.
  • PAC and CMC which are also polysaccharide materials, can also be used, alone or combined, or combined with any other viscosifier.
  • One or more polysaccharide materials which may be biopolymers, may be present at a concentration between 0.14 g/L and 1.4 g/L (0.05 Ibm/bbl and 0.5 Ibm/bbl).
  • the molecular weight of the polysaccharide material which may be a biopolymer, may be between 100,000 and 1 ,000,000.
  • Carboxylic acids including gluconic acid and soluble salts thereof, glucoheptonic acid and soluble salts thereof, tartaric acid and soluble salts thereof, citric acid and soluble salts thereof, glycolic acid and soluble salts thereof, lactic acid and soluble salts thereof, formic acid and soluble salts thereof, acetic acid and soluble salts thereof, proprionic acid and soluble salts thereof, oxalic acid and soluble salts thereof, malonic acid and soluble salts thereof, succinic acid and soluble salts thereof, adipic acid and soluble salts thereof, malic acid and soluble salts thereof, nicotinic acid and soluble salts thereof, benzoic acid and soluble salts thereof, and ethylenediamine tetraacetic acid (EDTA) and soluble salts thereof may be included in the compositions as retarders or dispersants or both. Phosphoric acids may be present for the same purpose. Salts of these acids may also be employed. These materials
  • Expanding agents may comprise calcium sulphate hemihydrate, metal oxides such as MgO or combinations thereof.
  • the expanding agents may be present in the compositions at concentrations between 0.01 kg/L and 0.2 kg/L of slurry, or between 0.05 and 0.1 kg/L.
  • Aluminum oxide and aluminum hydroxide can be used in a concentration range of 5-95% by volume of blend (BVOB).
  • Crystalline silica having particle size of 1-50 pm, for example crystalline silica having a particle size distribution such that 65% of the crystalline silica will pass a 325 mesh screen, can be used in a concentration range from 5-95% by volume of blend (”BVOB”).
  • Calcium oxide can be used in the concentration range of 0-50% by weight of blend (“BWOB”). Hydrated lime can be used in a concentration of 4-16% BWOB, and soda ash can be used in a concentration range of 4-16% BWOB.
  • Glucoheptonates, lignosulfonates, diutan gum, bentonite, sodium chloride, hollow beads, and metal metasilicate are nominal adds and can be used up to 20% BWOB.
  • the solid volume fraction (SVF) of a geopolymer precursor, as described herein, can be between 15-45%, and slurry density of the precursor can be between 11 .6-14.8 pounds per gallon (ppg), or lower or higher as described herein above.
  • the wells described herein can be wells for hydrocarbon production or for other uses.
  • the wellbore may be used for carbon capture, utilization, and storage (CCUS) and/or for recovery and use of geothermal energy.
  • Geothermal energy is a promising source of renewable energy that captures energy from heat generated or stored within the earth.
  • geothermal energy may be used to perform climate control (e.g., heating, cooling) for structures (e.g., buildings) using heat pumps and/or to generate electricity (e.g., by heating water to generate steam and drive a turbine with the steam).
  • climate control e.g., heating, cooling
  • structures e.g., buildings
  • electricity e.g., by heating water to generate steam and drive a turbine with the steam.
  • the wellbores described herein may be used to circulate a working fluid that exchanges heat within the earth formation through which the wellbore extends.
  • the working fluid may be circulated to the surface where a surface heat exchanger is used to transfer thermal energy to another fluid used to generate electricity and/or for climate control. After the thermal energy is transferred from the working fluid in the surface heat exchanger, the working fluid is circulated back to the earth formation to continue the cycle.
  • CCUS facilitates the capture, use, and/or storage of carbon (e.g., carbon dioxide), which has a goal of achieving carbon neutrality and/or net zero carbon emissions (NZE).
  • Carbon capture may include the capture of carbon dioxide from large point sources, such as power plants, refineries, cement plants, other industrial processing plants, or other industrial facilities that use fossil fuels, biomass fuels, or other fuels that generate carbon dioxide.
  • the captured carbon dioxide may be converted into valuable products such as, for example, ethanol, sustainable aviation fuel, chemicals, mineral aggregates, and/or other products.
  • the carbon dioxide may be stored in geologic formations, such as in depleted hydrocarbon reservoirs.
  • the carbon dioxide may be introduced into the earth formation through a wellbore, such as the wellbores described herein.
  • the carbon in the carbon dioxide may be dispersed in an aqueous phase and stored as carbon dioxide, may be stored in mineral form (e.g., as a carbonate, such as calcium carbonate, magnesium carbonate, iron(ll) carbonate), or as another form of carbon

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  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Geopolymer precursor compositions are presented that are made using materials consisting essentially of aluminum, silicon, and oxygen, or materials consisting essentially of aluminum, silicon, oxygen, and hydrogen, or mixtures thereof. Such materials are dispersed in an aqueous medium, along with an alkali activator, to form a geopolymer precursor. The geopolymer precursor may be pumpable, and may be pumped to a target location. The geopolymer precursor is hardened to form a geopolymer.

Description

RAW MATERIAL COMPOSITIONS FOR GEOPOLYMERS
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application claims priority benefit of United States Provisional Patent Application Serial Numbers 63/666,480, filed 1 July 2024, which is entirely incorporated herein by reference.
FIELD
[0002] This application for patent relates to geopolymer compositions. More particularly the invention relates to the use of geopolymer compositions that do not use strong alkaline solutions to activate polymerization.
BACKGROUND
[0003] Geopolymers are a class of materials that are formed by chemical reaction of various aluminosilicates, oxides, and silicates to form an amorphous three- dimensional framework cement-like structure. The term geopolymer was proposed and first used by J. Davidovits. His work is described in Davidovits, J: “Synthesis of New High-Temperature GeoPolymers for Reinforced Plastics/Composites.' Society of Plastics Engineers, IUPAC International Symposium on Macromolecules, Stockholm (1976). Other terms have been used to describe materials synthesized utilizing a similar chemistry, such as alkali-activated cement, geocement, alkali- bonded ceramic, inorganic polymer, hydroceramic. In the following description, the term geopolymer will be used.
[0004] Geopolymers have been investigated for use in several applications, including as concrete systems within the construction industry, as refractory materials and as encapsulants for hazardous and radioactive waste streams. Geopolymers are also recognized as being rapid setting and hardening materials. They exhibit superior hardness and chemical stability. The preparation of geopolymers generally involves mixing a blend of reactive solid materials and activating the polymerization reaction by adding an alkaline solution. Typically, the slurry mixture is then applied and allowed to harden in place. In construction, faster hardening is usually valued. [0005] In the hydrocarbon industry, cement-like materials are used to line wells to provide isolation and structural support within the well. Use of cement-like materials in hydrocarbon wells presents unique challenges. The slurry mixture precursor is typically pumped over long distances to the location where the mixture is to set, so the mixture must be pumpable without undue burden on equipment. Additionally, ambient conditions encountered in a typical hydrocarbon well are much more extreme than those encountered in a typical construction application. Further, the large vertical extent of hydrocarbon well applications presents challenges of density, temperature, and pressure not faced in the construction industry. Other applications, like plugs, squeeze, and injector wells for water or carbon dioxide, also require a cementitious precursor to be pumped to an application site, so geopolymer compositions find broad use where pumping is required.
[0006] Typically, geopolymers are made using waste materials, such as fly ash and blast furnace slag, that contain aluminum, silicon, and oxygen in varying amounts. These materials are not usually controlled in any way, and the composition of such materials can vary widely, creating variability in composition and performance characteristics of geopolymers. Such variability is conventionally compensated using additives to achieve certain properties in the resulting geopolymers. Improved geopolymer compositions having less uncertain and variable performance are needed.
SUMMARY
[0007] Embodiments described herein provide a geopolymer precursor, comprising a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material; an aqueous medium; and an alkali activator.
[0008] Other embodiments described herein provide a method, comprising forming a geopolymer precursor by dispersing a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material into an aqueous medium; and dispersing an alkali activator into the aqueous medium; pumping the geopolymer precursor to a target location; and hardening the geopolymer precursor to form a geopolymer at the target location.
[0009] Other embodiments described herein provide a method, comprising obtaining a geopolymer precursor comprising a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material; and an alkali activator; pumping the geopolymer precursor to a target location; and hardening the geopolymer precursor to form a geopolymer at the target location.
DETAILED DESCRIPTION
[0010] In the following description, numerous details are set forth to provide an understanding of the present disclosure. However, it may be understood by those skilled in the art that the methods of the present disclosure may be practiced without these details and that numerous variations or modifications from the described embodiments may be possible.
[0011] At the outset, it should be noted that in the development of any such actual embodiment, numerous implementation — specific decisions are made to achieve the developer's specific goals, such as compliance with system related and business related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time consuming but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure. In addition, the composition used/disclosed herein can also comprise some components other than those cited. In the summary of the disclosure and this detailed description, each numerical value should be read once as modified by the term "about" (unless already expressly so modified), and then read again as not so modified unless otherwise indicated in context. The term “about” should be understood as any amount or range within 10% of the recited amount or range (for example, a range from about 1 to about 10 encompasses a range from 0.9 to 11 ). Also, in the summary and this detailed description, it should be understood that a concentration range listed or described as being useful, suitable, or the like, is intended that any concentration within the range, including the end points, is to be considered as having been stated. For example, “a range of from 1 to 10” is to be read as indicating each possible number along the continuum between about 1 and about 10. Furthermore, one or more of the data points in the present examples may be combined together, or may be combined with one of the data points in the specification to create a range, and thus include each possible value or number within this range. Thus, even if specific data points within the range, or even no data points within the range, are explicitly identified or refer to a few specific data points, it is to be understood that inventors appreciate and understand that any data points within the range are to be considered to have been specified, and that inventors possessed knowledge of the entire range and the points within the range.
[0012] Regarding chemical formulas, it should be noted that measurements may not conform precisely to the chemical formulas described herein due to various sources of error that can affect real-world testing. The chemical formulas described herein should therefore be understood as expressing the nominal chemical makeup of compounds, where real-world testing may show close, but not exact, conformity to the formulas.
[0013] As used herein, “embodiments” refers to non-limiting examples disclosed herein, whether claimed or not, which may be employed or present alone or in any combination or permutation with one or more other embodiments. Each embodiment disclosed herein should be regarded both as an added feature to be used with one or more other embodiments, as well as an alternative to be used separately or in lieu of one or more other embodiments. It should be understood that no limitation of the scope of the claimed subject matter is thereby intended, any alterations and further modifications in the illustrated embodiments, and any further applications of the principles of the application as illustrated therein as would normally occur to one skilled in the art to which the disclosure relates are contemplated herein. [0014] Geopolymer materials, and other alkali activated materials, are formed by disposing one or more sources of oxidized aluminum and silicon, along with an alkali activator in a water mixture. The alkali activator produces a high pH aqueous solution that causes polymerization of the aluminum, silicon, and oxygen to form a geopolymer. The methods described herein use individual sources of oxidized aluminum, silicon, or both aluminum and silicon, as raw materials for making geopolymers. Materials such as aluminum oxide, aluminum hydroxide, silica flour, and silica sand are used to make a blend having a selected content of aluminum, silicon, and oxygen to target properties of a geopolymer made from such materials. Alumina-silica polymers such as sol gels formed from reaction of organoaluminum and organosilicon sols can also be used. Unoxidized aluminum and silicon can be included in the blend as well. Other reactive materials such as calcium oxide, metal silicates, metal sodium silicates, metal oxides, and metal carbonates can also be included.
[0015] A geopolymer precursor mixture can be made using a first reactant material consisting essentially of aluminum and oxygen, or of aluminum, oxygen, and hydrogen, or of aluminum, silicon, and oxygen, or of aluminum, silicon, oxygen, and hydrogen and a second reactant material consisting essentially of silicon and oxygen. Such materials are added to water, or to an aqueous mixture. An alkali source is added to raise pH of the geopolymer precursor and to activate polymerization of the aluminum, silicon, and oxygen of the reactant material.
[0016] A geopolymer precursor can be made by dispersing a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, and oxygen, a second material consisting essentially of aluminum, silicon, oxygen, and hydrogen, or a mixture of the first and second materials, into an aqueous medium. An alkali activator is also dispersed into the aqueous medium to activate a polymerization reaction of the reactant material. The geopolymer precursor can be made pumpable by adjusting water content, and thereby adjusting solids fraction, in the precursor. A pumpable geopolymer precursor, generally defined as a precursor that produces a dial reading of less than 300 using a Cuvette viscometer equipped with an R1 B1 F1 rotor:bob:spring configuration, can be pumped to a target location for setting and hardening. Multiple materials consisting essentially of aluminum, silicon, and oxygen, and optionally hydrogen can be used to form the geopolymer precursor mixture. As described in this document, a geopolymer precursor that includes the reactant materials can be obtained, for example received, formed, or a combination thereof. The geopolymer precursor may also include activators, additives, or both. The geopolymer precursor can be deployed to a target location, for example by pumping where the precursor is pumpable, and allowed to harden to form a geopolymer.
[0017] The reactant materials described above can be pure materials or a mixture of materials. A reactant material for purposes herein can include oxidized aluminum having chemical formula Al20x, where x is about 3, for example 2.9 to 3.1 , or 2.95 to 3.05, or 2.99 to 3.01 . That is, the oxidized aluminum can be aluminum oxide, but the aluminum oxide can be oxygen depleted, oxygen rich, or oxygen balanced (3 oxygen atoms for every 2 aluminum atoms). The reactant material can include an aluminum hydroxide material having the general formula AIOaHb where b can be a small number representing hydrogen impurities or b can be a number close to a, such that a ratio of b/a is near 1 , for example 0.95 to 1 .05. Where the ratio of b/a is not exactly 1 , the aluminum hydroxide material may be hydrogen-depleted aluminum hydroxide or hydrogen-enriched aluminum hydroxide. The oxygen content a is a number near 3, for example 2.95 to 3.05. The reactant material can include oxidized silicon having chemical formula SiOy, where y is about 2, for example 1 .9 to 2.1 , or 1 .95 to 2.05, or 1.99 to 2.01. That is, the oxidized silicon can be silica or silicon oxide, but the silica or silicon oxide can be oxygen depleted, oxygen rich, or oxygen balanced (2 oxygen atoms for every silicon atom).
[0018] An oxidized aluminum material usable for the geopolymer precursors herein can be a homogeneous material, having substantially constant or consistent composition throughout the material, or the oxidized aluminum can be a heterogeneous material having varying composition throughout the material. For example, the oxidized aluminum can be a mixture of aluminum and aluminum oxide, for example an aluminum powder mixed with an aluminum oxide powder. In another case, the oxidized aluminum can be a particulate material of oxide-coated aluminum particles or particles having two or more layers of aluminum oxide having the same or different compositions. Likewise, the oxidized silicon material can be homogeneous or heterogeneous. An example of a heterogeneous oxidized silicon material is a mixture of silicon powder and silicon oxide powder or a particulate material of oxide-coated silicon particles.
[0019] In one case, a reactant material can be made from a first reactant material consisting essentially of silicon and oxygen and a second reactant material consisting essentially of aluminum and oxygen. Use of such reactant materials to form a geopolymer precursor allows precise control of the composition of the geopolymer. The general chemical formula of a geopolymer is Mn {-(SiO2)z-AIO2}n, w H2O, wherein M is a cation such as potassium, sodium or calcium, n is a degree of polymerization and z is the Si/AI atomic ratio. Use of such materials allows precise control of the ratio of silicon to aluminum in the geopolymer, which in turn enables precise control over properties of the geopolymer and the geopolymer precursor, and also enables broader diversity of geopolymer attributes achievable using pumpable geopolymer precursors.
[0020] Generally, aluminum oxide, aluminum hydroxide, silica flour, amorphous silica, and silica sand can be readily used as ingredients to make a geopolymer precursor described herein. Where silica is used as a reactant, the silica can be crystalline silica. Use of crystalline silica can help in achieving geopolymer characteristics such as precursor pumpability, solids fraction, density, viscosity, and the like. Crystalline silica having particle size from 1 -50 pm can be useful to tune particle size distribution of the geopolymer slurry.
[0021] Particulate materials described above can be coated with a material designed to affect development of a polymerization reaction in the geopolymer precursor material. For example, particles can be coated with a resin coating designed to dissolve or degrade over time to release geopolymerization reactants into the mixture. The resin coating may be water soluble and/or acid soluble, and mixtures or multiple layers of coatings can be used. In one example, particulate materials consisting essentially of aluminum and oxygen; aluminum, silicon, and oxygen; aluminum, hydrogen and oxygen; or silicon and oxygen can be coated with a polysaccharide coating, such as a starch or cellulose material, to delay entry of the reactants into the aqueous reaction medium. In another example, such particulate materials can be coated with polyvinyl alcohol, polyethylene imine, polyacrylamide, polyethylene glycol, polyvinyl pyrrolidone, or another water-soluble polymer instead of, or in addition to, a polysaccharide. Using water-soluble polymers, a layered coating structure can be applied to such particulates where a first layer contains a first water-soluble polymer and a second layer contains a second water-soluble polymer, which may the same as, or different from, the first water-soluble polymer.
[0022] Polymers can also be used to coat particulates herein that degrade slowly at high pH, the conditions of the aqueous medium of the geopolymer precursor. For example, a polymer coating can include a hydrolysable component and a stable component such that degradation of the hydrolysable component in the high pH environment of the geopolymer precursor slowly releases the reactants encapsulated therein into the reactive aqueous environment. Such methods can be used to slow thickening of a geopolymer precursor so that the precursor can be pumped, or otherwise deployed, to the target location before setting. Such polymer materials can be copolymers or multipolymers of a stable component and a hydrolysable component, or the polymer materials can be mixtures, such as melt blends, of polymers. Thus, a hydrolysable polymer such as a polyester or polyacid, for example polyvinyl acetate or polylactic acid, can be blended with a stable polymer, such as a polyolefin, to form a polymer alloy that can be coated, for example by spraying a molten mixture or liquid solution of the polymers, onto particulates herein to form a slowly-degradable resin coating.
[0023] The alkaline activators used herein can be dry materials, to which water or a non-activating aqueous material is added. Examples include metal silicates M2xSiyC>2y+x where x is 1 , 2, or 3 and y is 1 or 2 (for example silicates, metasilicates, orthosilicates, and pyrosilicates), where M can be Li, Na, K, Rb, or Cs, or combination thereof, for example a mixed metal silicate like a metal sodium silicate, alkaline earth metal hydroxides such as Ca(OH)2, Sr(OH)2, Mg(OH)2 and/or Ba(OH)2, alkaline earth metal oxides such as CaO, SrO, MgO and/or BaO, and alkaline earth metal peroxides such as MgO2 and CaO2 or a combination thereof. Such activators can be combined with an alkali metal salt such as a metal carbonate M2CO3, metal sulphate M2SO4, metal sulphite M2SO3, metal phosphate M3PO4, metal oxalate M2C2O4, metal silicate M2xSiyO2y+x where x is 1 , 2, or 3 and y is 1 or 2 (for example silicates, metasilicates, orthosilicates, and pyrosilicates), metal fluoride MF, metal hexafluoridosilicate M2SiFe, metal iodate MIO3, metal molybdate M2MOO4, where M can be Li, Na, K, Rb, or Cs, or combination thereof, where such salts can have a combination of different metals and a combination of different anions. Lime and hydrated lime are examples of materials that contain calcium oxide and/or calcium hydroxide. Hydrogenated metal salts, such as MHCO3, MHSO4, MHPO4, MHC2O4, M2HPO4, MH2PO4, and MHSO3 can also be used, alone or in combination with other activators described herein, where M is as listed above. These activators raise pH in a slurry upon addition of water such that the aluminum, oxygen, and silicon in the geopolymer precursor composition dissolve and begin to react to form geopolymer. These activators are typically added in a quantity that is 2 to 40 parts per hundred based on the weight of the dry geopolymer precursor particulate blend, for example 4 to 20 parts per hundred or 4 to 40 parts per hundred based on the weight of the total dry geopolymer precursor particulate blend.
[0024] The activators used herein can also be aqueous solutions of the above materials and/or alkali metal hydroxides. Such activators can be added to the aqueous medium to be used for the geopolymer precursor before or after dispersing the reactant materials in the aqueous medium.
[0025] Thickening time of the geopolymer precursors described herein can be influenced by adding retarders and accelerators. Several retarders may delay the setting and hardening of geopolymer systems, for example by as much as 2 hours. Retarders such as sodium pentaborate decahydrate, borax, sucrose, boric acid, lignosulphonates, sodium glucoheptonate, tartaric acid, citric acid, or phosphorus containing compounds such as phosphoric acid, salts thereof, or mixtures thereof can be added to the geopolymer precursor particulate mixture in amounts of 0.01 to 5 part per hundred by weight of the total particulate precursor mixture. Metal chlorides can also be accelerators and/or retarders. The amount of retardation of the polymerization reaction, and the setting of the slurry, depends on the type of raw materials used for the slurry and the type and relative quantity of retarder used. Adding too much retarder reagent to a geopolymer slurry can cause the slurry to remain unhardened by interfering with the polymerization reaction so the geopolymer does not set. In other embodiments a retarder solution can be added to the carrier fluid or to the geopolymer slurry, or both. By this means, the same geopolymer precursor could be pumped into different sections of a well and setting time of geopolymer slurry in the different sections can be controlled through addition of a different amount of the retarder solution. The geopolymer precursors described herein, using retarders can add at least 2 hours to time to reach 70 Be (Bearden consistency units) or 50 Be using a pressurized consistometer.
[0026] Accelerators can also be added to the geopolymer precursor particulate mixture in amounts up to about 0.01 -10, such as 1 -5, parts per hundred weight of the total particulate precursor mixture. The amount of acceleration of the polymerization reaction, and the setting of the slurry, depends on the type of raw materials used for the slurry and the type and relative quantity of accelerating reagent used. Adding too much accelerator to a geopolymer slurry can cause the slurry to thicken too quickly making it difficult to deploy the slurry to target locations downhole. It should be noted that the retarders and accelerants described herein can be included as particulate materials in the geopolymer precursor composition, or such reagents can be added to water before the water is added to a geopolymer precursor composition described herein.
[0027] Geopolymer slurries for use in well lining applications typically have a slurry density range from 0.84 g/cm3 (7 Ibm/gal) to 2.87 g/cm3 (24 Ibm/gal), such as 1.32 g/cm3 (11 Ibm/gal) to 2.4 g/cm3 (20 Ibm/gal) or 1 .32 g/cm3 (11 Ibm/gal) to 2.16 g/cm3 (18 Ibm/gal), for example 1 .36 g/cm3 (11 .3 Ibm/gal) to 1 .90 g/cm3 (15.8 Ibm/gal). The slurry density can be influenced by quantity of water added and/or by adding density modifiers. Water typically makes up from about 20% by weight to about 60% by weight of a geopolymer slurry. Density modifiers can include density increasing particles and density lowering particles. Low-density particles may be added to the geopolymer precursor particulate mixture to achieve lower slurry densities for a given amount of water added, or heavy particles may be added to achieve higher slurry densities. The lightweight or low-density particles may have densities lower than 2 g/cm3, or lower than 1.3 g/cm3. Examples include hollow glass or ceramic microspheres (cenospheres), plastic particles such as polypropylene beads, rubber particles, uintaite (sold as GILSONITE™), bentonite, vitrified shale, petroleum coke or coal or combinations thereof. The lightweight particles may be present in the compositions at concentrations between about 0.06 kg/L and 0.6 kg/L (20 Ib/bbl and 200 Ib/bbl). The particle size range of the low-density particles may be between about 38 pm and 3350 pm (6 mesh and 400 mesh). The heavy particles typically may have densities exceeding 2 g/cm3, or more than 3 g/cm3. Examples include hematite, barite, ilmenite, crushed granite and also manganese tetroxide commercially available under the trade names of MicroMax™ and MicroMax FF™.
[0028] Other additives, such as anti-foam agents, defoamers, fluid-loss control additives, viscosifiers, dispersants, expanding agents, anti-settling additives or combinations thereof, can be included. 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.
[0029] The fluid-loss control agent may comprise a latex, one or more acrylic polymers, or combination thereof. The latex may be an alkali-swellable latex. The latex may be present in the compositions at a concentration between 0.02 L/L and 0.3 L/L or between 0.05 L/L and 0.15 L/L. The acrylic polymers may be present at concentrations between 0.1 % and 10% by weight of the total dry geopolymer precursor. Cellulosic materials and derivatives, such as carboxyethylcellulose (CEC), hydroxymethylcellulose (HEC), carboxymethylcellulose (CMC), and polyanionic cellulose (PAC), can be used as a fluid-loss control agent herein.
[0030] Viscosifiers may comprise diutan gum having a molecular weight higher than about 1 x 106. The diutan gum may be present at a concentration between 0.14 g/L and 1 .4 g/L (0.05 Ibm/bbl and 0.5 Ibm/bbl). In some cases, viscosifiers are present in the dry geopolymer precursor at a concentration of 0.1 -5% by weight of the total dry geopolymer precursor. Other viscosifiers may comprise a polysaccharide material, which may be a biopolymer. Welan gum is an example of a polysaccharide material that can be used as a viscosifier herein. PAC and CMC, which are also polysaccharide materials, can also be used, alone or combined, or combined with any other viscosifier. One or more polysaccharide materials, which may be biopolymers, may be present at a concentration between 0.14 g/L and 1.4 g/L (0.05 Ibm/bbl and 0.5 Ibm/bbl). The molecular weight of the polysaccharide material, which may be a biopolymer, may be between 100,000 and 1 ,000,000.
[0031] Carboxylic acids including gluconic acid and soluble salts thereof, glucoheptonic acid and soluble salts thereof, tartaric acid and soluble salts thereof, citric acid and soluble salts thereof, glycolic acid and soluble salts thereof, lactic acid and soluble salts thereof, formic acid and soluble salts thereof, acetic acid and soluble salts thereof, proprionic acid and soluble salts thereof, oxalic acid and soluble salts thereof, malonic acid and soluble salts thereof, succinic acid and soluble salts thereof, adipic acid and soluble salts thereof, malic acid and soluble salts thereof, nicotinic acid and soluble salts thereof, benzoic acid and soluble salts thereof, and ethylenediamine tetraacetic acid (EDTA) and soluble salts thereof may be included in the compositions as retarders or dispersants or both. Phosphoric acids may be present for the same purpose. Salts of these acids may also be employed. These materials may be present in the compositions at concentrations between 0.5 g/L and 10 g/L, or between 1 g/L and 5 g/L.
[0032] Expanding agents may comprise calcium sulphate hemihydrate, metal oxides such as MgO or combinations thereof. The expanding agents may be present in the compositions at concentrations between 0.01 kg/L and 0.2 kg/L of slurry, or between 0.05 and 0.1 kg/L.
[0033] Aluminum oxide and aluminum hydroxide can be used in a concentration range of 5-95% by volume of blend (BVOB). Crystalline silica having particle size of 1-50 pm, for example crystalline silica having a particle size distribution such that 65% of the crystalline silica will pass a 325 mesh screen, can be used in a concentration range from 5-95% by volume of blend (”BVOB”). Calcium oxide can be used in the concentration range of 0-50% by weight of blend (“BWOB”). Hydrated lime can be used in a concentration of 4-16% BWOB, and soda ash can be used in a concentration range of 4-16% BWOB. Glucoheptonates, lignosulfonates, diutan gum, bentonite, sodium chloride, hollow beads, and metal metasilicate are nominal adds and can be used up to 20% BWOB. The solid volume fraction (SVF) of a geopolymer precursor, as described herein, can be between 15-45%, and slurry density of the precursor can be between 11 .6-14.8 pounds per gallon (ppg), or lower or higher as described herein above.
[0034] The wells described herein can be wells for hydrocarbon production or for other uses. In some embodiments, the wellbore may be used for carbon capture, utilization, and storage (CCUS) and/or for recovery and use of geothermal energy. Geothermal energy is a promising source of renewable energy that captures energy from heat generated or stored within the earth. For example, geothermal energy may be used to perform climate control (e.g., heating, cooling) for structures (e.g., buildings) using heat pumps and/or to generate electricity (e.g., by heating water to generate steam and drive a turbine with the steam). The wellbores described herein may be used to circulate a working fluid that exchanges heat within the earth formation through which the wellbore extends. The working fluid may be circulated to the surface where a surface heat exchanger is used to transfer thermal energy to another fluid used to generate electricity and/or for climate control. After the thermal energy is transferred from the working fluid in the surface heat exchanger, the working fluid is circulated back to the earth formation to continue the cycle.
[0035] CCUS facilitates the capture, use, and/or storage of carbon (e.g., carbon dioxide), which has a goal of achieving carbon neutrality and/or net zero carbon emissions (NZE). Carbon capture may include the capture of carbon dioxide from large point sources, such as power plants, refineries, cement plants, other industrial processing plants, or other industrial facilities that use fossil fuels, biomass fuels, or other fuels that generate carbon dioxide. The captured carbon dioxide may be converted into valuable products such as, for example, ethanol, sustainable aviation fuel, chemicals, mineral aggregates, and/or other products. Alternatively, the carbon dioxide may be stored in geologic formations, such as in depleted hydrocarbon reservoirs. The carbon dioxide may be introduced into the earth formation through a wellbore, such as the wellbores described herein. In the earth formation, the carbon in the carbon dioxide may be dispersed in an aqueous phase and stored as carbon dioxide, may be stored in mineral form (e.g., as a carbonate, such as calcium carbonate, magnesium carbonate, iron(ll) carbonate), or as another form of carbon
[0036] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

CLAIMS We claim:
1 . A geopolymer precursor, comprising: a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material; an aqueous medium; and an alkali activator.
2. The geopolymer precursor of claim 1 , wherein the first material comprises an oxidized aluminum material and an oxidized silicon material, the second material comprises an oxidized aluminum material and an oxidized silicon material, or both.
3. The geopolymer precursor of claim 1 , wherein the geopolymer precursor is pumpable.
4. The geopolymer precursor of claim 1 , further comprising unoxidized aluminum, unoxidized silicon, or both.
5. The geopolymer precursor of claim 1 , wherein the reactant material comprises crystalline silica.
6. The geopolymer precursor of claim 1 , wherein the reactant material is the first material and the geopolymer precursor further comprises the second material.
7. The geopolymer precursor of claim 6, further comprising crystalline silica.
8. The geopolymer precursor of claim 7, wherein at least some particles of the geopolymer precursor are coated.
9. A geopolymer made by hardening the geopolymer precursor of any of claims 1-8.
10. A method, comprising: forming a geopolymer precursor by: dispersing a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material into an aqueous medium; and dispersing an alkali activator into the aqueous medium; pumping the geopolymer precursor to a target location; and hardening the geopolymer precursor to form a geopolymer at the target location.
11. A method, comprising: obtaining a geopolymer precursor comprising: a reactant material selected from the group consisting of a first material consisting essentially of aluminum, silicon, oxygen, and hydrogen, a second material consisting essentially of aluminum, silicon, and oxygen, and a combination of the first material and the second material; pumping the geopolymer precursor to a target location; and hardening the geopolymer precursor to form a geopolymer at the target location.
12. The method of claim 10 or 11 , wherein the first material comprises an oxidized aluminum material and an oxidized silicon material, the second material comprises an oxidized aluminum material and an oxidized silicon material, or both.
13. The method of any of claims 10-12, wherein the geopolymer precursor further comprise unoxidized aluminum, unoxidized silicon, or both.
14. The method of claim 10 or claim 11 , wherein the reactant material comprises crystalline silica.
15. The method of claim 10 or claim 11 , wherein the reactant material is the first material and the geopolymer precursor further comprises the second material.
16. The method of claim 15, wherein the geopolymer precursor further comprises crystalline silica.
17. The method of any of claims 10-16, wherein at least some particles of the geopolymer precursor are coated.
18. The method of claim 17, wherein the particles are coated with a polymer that delays a geopolymerization reaction.
19. The method of claim 18, wherein the polymer comprises a hydrolysable component.
20. The method of claim 19, wherein the polymer comprises a polysaccharide.
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Citations (3)

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US20080028995A1 (en) * 2006-08-07 2008-02-07 Veronique Barlet-Gouedard Geopolymer composition and application for carbon dioxide storage
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CN101522853A (en) * 2006-08-07 2009-09-02 普拉德研究及开发股份有限公司 Pumpable geopolymer formulation for oilfield application
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