Geopolymer slurries and geopolymer compositions including fluid loss control materials, and related methods

Abstract

A geopolymer slurry includes comprising at least one aluminosilicate source including an amorphous aluminosilicate material, an activator, a fluid loss control material including a crosslinked polymer, and an aqueous base fluid. The crosslinked polymer includes a reaction product of one or more monomers including one or more of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N‑dimethylacrylamide, N,N‑diethylacrylamide, vinyl acetate, or another monomer, and a crosslinker including one or more of methylene bisacrylamide, triallyl amine, pentaerythritol allyl ether, triallyl-triazine-trione, or another material. Related geopolymer compositions and methods of cementing a subterranean borehole are also disclosed.

Description

PATENTDocket No. IS24.1340-WOGEOPOLYMER SLURRIES AND GEOPOLYMER COMPOSITIONS INCLUDING FLUID LOSS CONTROL MATERIALS, AND RELATED METHODSCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 746,069, filed on 16 January 2025, the disclosure of which is incorporated herein in its entirety by this reference.BACKGROUND

[0002] Wellbore drilling operations includes drilling a bore in a formation to access reservoirs of hydrocarbons and other subsurface resources. After a drilling operation, a casing string may be run through the wellbore and cemented into place. The cement may facilitate isolating a section of the formation from other portions of the formation. Cementing may be performed in a single stage where the cement is pumped into the casing, down a cement shoe, and then up into an annulus between the casing and the formation. In other cases, such as where the casing string is long or the formation cannot support the hydrostatic pressure of a column of the cement, the cementing may be performed in a multi-stage operation. For example, the wellbore may include a conductor casing proximate the surface, a surface casing extending beyond (e.g., below) the conductor casing, an intermediate casing beyond the surface casing, and a production line beyond the intermediate casing. Cement may be located between the formation and each of the casings, as well as between the neighboring casing sections.

[0003] Geopolymers are a class of amorphous materials that are formed by chemical reaction (e.g., chemical dissolution and subsequent recondensation) of various aluminosilicates, oxides, and silicates to form an amorphous three-dimensional framework cement-like structure. Geopolymers include a three-dimensional aluminosilicate mineral polymer. 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 onPATENTDocket No. IS24.1340-WOMacromolecules, Stockholm (1976). Geopolymers are polymers of aluminum, silicon, and oxygen which form an aluminosilicate matrix having repeated tetrahedral arrangements of aluminum, oxygen, and silicon atoms. Such aluminosilicate polymers can include other entrapped components, which may or may not be chemically bonded to the aluminosilicate matrix. Other terms have been used to describe materials synthesized utilizing a similar chemistry, such as alkali activated cement, geocement, alkali-bonded ceramic, inorganic polymer, and hydroceramic. Generally, the polymeric portions of such materials can be termed polysialates, and the polymerization reaction that makes them can be referred to as a polysialation reaction. Therefore, a geopolymer is a three-dimensional aluminosilicate mineral polymer.

[0004] Geopolymers based on alumino-silicates are designated as poly(sialate), which is an abbreviation for poly(silicon-oxo-alum inate) or (-Si-O-AI-O)n or (-Si-O-Al-O-Si-O)n, wherein n corresponds to the degree of polymerization of the geopolymer. Such geopolymers include silicon atoms and aluminum atoms that are bridged with one another via oxygen atoms. The sialate network comprises SiO4and AIO4 tetrahedra linked alternately by sharing all the oxygen atoms, with Al3+and Si4+in IV-fold coordination with oxygen. Positive ions (Na+, K+, Li+, Ca2+) may be present in the framework cavities to balance the negative charge of Al3+in IV-fold coordination.

[0005] The empirical formula of polysialates is Mn[-(SiO2)z-AIO2]n, where M is a cation such as potassium, sodium, or calcium, n is a degree of polymerization, and z is the silicon to aluminum ratio (the Si / AI ratio). The three-dimensional geopolymer networks are summarized in Table 1.PATENTDocket No. IS24.1340-WOTable 1wherein M is a cation such as K+, Na+, or Ca2+, and n is the degree of polymerization of the geopolymer.

[0006] The preparation of geopolymers generally involves mixing a blend of reactive solid materials and activating the polymerization reaction by adding an alkaline solution. The slurry mixture may then be applied and allowed to harden in place. Geopolymers have been employed as alternatives for wellbore cement.

[0007] The properties and application fields of aluminosilicate polymers depend principally on their chemical structure, such as on the Si / AI molar ratio. Aluminosilicate polymers 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. Such polymers are also recognized as being rapid setting and hardening materials. They exhibit superior hardness and chemical stability. The preparation of aluminosilicate polymers generally involves mixing a blend of reactive solid materials and activating the polymerization reaction by adding an alkaline solution. Typically, the initial slurry mixture is then applied and allowed to harden in place. In construction, faster hardening is usually valued, while in well construction for the hydrocarbon exploration and production industry, cementitious materials are deployed in a well to provide wall strength and isolation. Deployment of cementitious materials to a well requires the precursor slurry be pumpable into the well before the precursor begins to harden.

[0008] Conventionally, precursors for making aluminosilicate polymers are waste products such as slags and ashes, byproducts of combustion, or other thermalPATENTDocket No. IS24.1340-WOprocesses that contain oxidized aluminum and oxidized silicon. Aluminosilicate polymers have the advantage that a wide range of properties can be accessed by adjusting the mixture of materials in the precursor. Due to the sizes and morphologies of the materials used to make aluminosilicate polymers, the precursors can be more flexible in composition than for traditional cementitious materials.

[0009] In the hydrocarbon industry, cement-like materials are used to line wellbores to provide isolation and structural support within the wellbore. Use of cement-like materials in hydrocarbon wellbores 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 wellbore applications presents challenges of density, temperature, and pressure not faced in the construction industry.BRIEF SUMMARY

[0010] In some embodiments, a geopolymer slurry includes at least one aluminosilicate source including an amorphous aluminosilicate material, an activator, and a fluid loss control material including a crosslinked polymer including a reaction product of one or more monomers including one or more of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, vinyl acetate, an N-substituted acrylamide, methacrylamide, an N-substituted methacrylamide, an acrylate, a methacrylate, acrylic acid, methacrylic acid, an N-vinylamide, an N-allylamide, vinyl alcohol, a vinyl ether, a vinyl ester, allyl alcohol, an allyl ether, an allyl ester, vinylpyridine, a vinyl sulfonate, vinyl sulfonic acid, styrene sulfonate, an allyl sulfonate, vinylimidazole, allylimidazole, or diallyldimethylammonium chloride, and a crosslinker including one or more of methylene bisacrylamide, triallyl amine, pentaerythritol allyl ether, triallyl-triazine-trione, divinyl ether, diallyl ether, a vinyl orPATENTDocket No. IS24.1340-WOallyl ether of polyglycols, a vinyl or allyl ether of polyols, divinylbenzene, 1,3-divinylimidazolidin-2-one, divinyltetrahydropyrimidin-2(1H)-one, a diene, an allyl amine, N-vinyl-3(E)-ethylidene pyrrolidone, or ethylidene bis(N-vinylpyrrolidone). The geopolymer slurry further includes an aqueous base fluid.

[0011] In some embodiments, a geopolymer composition includes at least one aluminosilicate source including an amorphous aluminosilicate material, an activator, and a fluid loss control material including a crosslinked polymer. The crosslinked polymer includes a reaction product of one or more monomers including one or more of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, vinyl acetate, an N-substituted acrylamide, methacrylamide, an N-substituted methacrylamide, an acrylate, a methacrylate, acrylic acid, methacrylic acid, an N-vinylamide, an N-allylamide, vinyl alcohol, a vinyl ether, a vinyl ester, allyl alcohol, an allyl ether, an allyl ester, vinylpyridine, a vinyl sulfonate, vinyl sulfonic acid, styrene sulfonate, an allyl sulfonate, vinylimidazole, allylimidazole, or diallyldimethylammonium chloride; and a crosslinker including one or more of methylene bisacrylamide, triallyl amine, pentaerythritol allyl ether, trially l-triazine-trione, divinyl ether, diallyl ether, a vinyl or allyl ether of polyglycols, a vinyl or allyl ether of polyols, divinylbenzene, 1,3-divinylimidazolidin-2-one, divinyltetrahydropyrimidin-2(1 H)-one, a diene, an allyl amine, N-vinyl-3(E)-ethylidene pyrrolidone, or ethylidene bis(N-vinylpyrrolidone).

[0012] In some embodiments, a method of cementing a subterranean borehole includes mixing water with a geopolymer composition to form a geopolymer slurry. The geopolymer composition includes at least one aluminosilicate source including an amorphous aluminosilicate material, an activator, and a fluid loss control material including a crosslinked polymer including a reaction product of one or more monomers including one or more of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, vinyl acetate, an N-substituted acrylamide, methacrylamide, an N-substituted methacrylamide, an acrylate, a methacrylate, acrylic acid, methacrylic acid, an N-vinylamide, an N-allylamide, vinyl alcohol, a vinyl ether, a vinyl ester, allyl alcohol, an allyl ether, an allyl ester, vinylpyridine, a vinyl sulfonate, vinyl sulfonic acid,PATENTDocket No. IS24.1340-WOstyrene sulfonate, an allyl sulfonate, vinylimidazole, allylimidazole, or diallyldimethylammonium chloride; and a crosslinker including one or more of methylene bisacrylamide, triallyl amine, pentaerythritol allyl ether, triallyl-triazine-trione, divinyl ether, diallyl ether, a vinyl or allyl ether of polyglycols, a vinyl or allyl ether of polyols, divinylbenzene, 1 ,3-divinylimidazolidin-2-one, divinyltetrahydropyrimidin-2(1H)-one, a diene, an allyl amine, N-vinyl-3(E)- ethylidene pyrrolidone, or ethylidene bis(N-vinylpyrrolidone). The method further includes pumping the geopolymer slurry into an annular space between a casing and a subterranean formation defining the subterranean borehole.

[0013] This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

[0014] Additional features and advantages of embodiments of the disclosure will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of such embodiments. The features and advantages of such embodiments may be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. These and other features will become more fully apparent from the following description and appended claims, or may be learned by the practice of such embodiments as set forth hereinafter.BRIEF DESCRIPTION OF DRAWINGS

[0015] In order to describe the manner in which the above-recited and other features of the disclosure can be obtained, a more particular description will be rendered by reference to specific implementations thereof which are illustrated in the appended drawings. For better understanding, the like elements have been designated by like reference numbers throughout the various accompanying figures. While some of the drawings may be schematic or exaggerated representations of concepts, at least some of the drawings may be drawn to scale. Understanding that the drawings depict some example implementations, thePATENTDocket No. IS24.1340-WOimplementations will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:

[0016] FIG. 1 is a simplified schematic of a drilling system for drilling an earth formation to form a wellbore, according to at least one embodiment of the disclosure;

[0017] FIG. 2 is a simplified, partial cross-sectional view illustrating a portion of a downhole system including the earth formation after one or more cementing operations have been performed in the wellbore, according to at least one embodiment of the disclosure;

[0018] FIG. 3 is a simplified chemical structure showing a chemical structure of a crosslinked polymer, according to at least one embodiment of the disclosure;

[0019] FIG. 4 is a simplified flow chart illustrating a method of performing a cementing operation, according to at least one embodiment of the present disclosure;

[0020] FIG. 5 is a simplified flow chart illustrating a method for rapid screening of a fluid loss control material, according to at least one embodiment of the disclosure;

[0021] FIG. 6 is a graph illustrating the fluid loss of different non-activated systems at 36°C;

[0022] FIG. 7 is a graph illustrating the fluid loss of different non-activated systems at 66°C;

[0023] FIG. 8 is a graph illustrating the fluid loss of different alkali activated systems at 36°C;

[0024] FIG. 9 is a graph illustrating the effect of the activator’s chemistry on fluid loss performance;

[0025] FIG. 10 is a graph illustrating the fluid loss value of slag geopolymer slurries activated by sodium carbonate (6% BWOC) and calcium hydroxide (5% BWOC);PATENTDocket No. IS24.1340-WO

[0026] FIG. 11 is a graph illustrating the measured fluid loss value of 15.8 ppg geopolymer slurries including different fluid loss control materials versus a control slurry without a fluid loss control material;

[0027] FIG. 12 is a graph illustrating the measured fluid loss value of the different geopolymer slurries (at 11.4 ppg density) including two different fluid loss control materials versus the control slurry without a fluid loss control material; and

[0028] FIG. 13 is a graph illustrating the measured fluid loss value of fluid 7 (in 11.4 ppg density) having different concentrations of the same fluid loss control material that was synthesized using AMPS, acrylamide, methylene bisacrylamide, and maleic anhydride.DETAILED DESCRIPTION

[0029] As used herein, “geopolymer composition” means and includes a mixture (blend) of one or more alkali-activated materials (such as aluminosilicate materials, silicate materials, polysialate materials) to which water may be added to form a slurry, referred to herein as a “geopolymer slurry.” During hardening (also referred to as “setting”), the geopolymer slurry undergoes polycondensation wherein the composition included in the slurry (e.g., aluminosilicate) polymerizes and forms a crosslinked network (e.g., an amorphous three-dimensional framework structure, such as a three-dimensional aluminosilicate mineral polymer), which may be referred to herein as a “geopolymer,” a “set geopolymer,” or a “hardened geopolymer.” Geopolymers may include and / or be formed from alkali-activated materials having the general formula Mn[-(SiO2)z-AIO2]n, where M is a cation such as potassium, sodium, or calcium, n is a degree of polymerization, and z is the silicon to aluminum ratio (the Si / AI ratio). Accordingly, geopolymers may include materials synthesized from one or more aluminosilicates and / or polysialates that have been activated with one or more activators (e.g., alkali activators and / or silicate activators) and may also be referred to as alkali-activated cement, geocement, alkali-bonded ceramic, inorganic polymer, and hydroceramic. Activation of the aluminosilicate material may polymerize the alkali-activated material to form the geopolymer.PATENTDocket No. IS24.1340-WO

[0030] This disclosure generally relates to devices, systems, and methods for geopolymer compositions, geopolymer slurries, and geopolymers including at least one aluminosilicate material and a fluid loss control material. In use and operation, when the geopolymer slurry is placed across a permeable subterranean earth formation under pressure, portions of the geopolymer slurry may be filtered by the subterranean earth formation to form a filter cake. Aqueous portions of the geopolymer slurry may filter through the subterranean earth formation, leaving the cement, inert solids, and / or aluminosilicate particles in the filtercake on surfaces of the subterranean earth formation. The fluid loss control materials in the geopolymer compositions and geopolymer slurries described herein may prevent further loss or reduce the loss of the aqueous fluid into the subterranean earth formation. In some embodiments, the fluid loss control material reduces the loss of the geopolymer slurry (e.g., the aqueous phase of the geopolymer slurry) to the earth formation.

[0031] The fluid loss control material may include a crosslinked, but water-swellable polymer (e.g., a hydrogel) formulated and configured to plug pore throats of the earth formation to reduce fluid loss of the geopolymer slurry to the earth formation. The fluid loss control material may include a polymer formed from one or more monomers and may be crosslinked with one or more crosslinkers. In some embodiments, the fluid loss control material further includes one or more anchoring materials, which may be incorporated into the backbone of the polymer. The one or more monomers may include one or more of acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, vinyl acetate, and 2-acrylamido-2-methyl propane sulfonic acid. The one or more crosslinkers may include one or more of methylene bisacrylamide, triallyl amine, and pentaerythritol allyl ether. In some embodiments, the polymer may be formed of and include one or more anchoring materials, which may include one or more of maleic anhydride, carbonyl phosphonic acid, vinyl phosphonic acid, and itaconic acid.

[0032] In some embodiments, the fluid loss control material is present in the geopolymer composition as a fine powder or solid particles. In some embodiments, the fluid loss control material is provided to the geopolymer composition as anPATENTDocket No. IS24.1340-WOemulsion (e.g., a latex) or a gel. The geopolymer slurry may include the fluid loss control material, which may reduce the amount (e.g., volume) of geopolymer slurry that filters through the earth formation during cementing operations. Geopolymer slurries and geopolymers formed from the geopolymer compositions including the fluid loss control material may exhibit reduced fluid loss compared to geopolymer slurries and geopolymers not including the fluid loss control material.

[0033] FIG. 1 shows one example of a drilling system 100 for drilling an earth formation 101 to form a wellbore 102 during a drilling operation. The drilling system 100 includes a drill rig 103 used to turn a drilling tool assembly 104 which extends downward into the wellbore 102. The drilling tool assembly 104 may include a drill string 105, a bottomhole assembly (“BHA”) 106, and a bit 110, attached to the downhole end of drill string 105.

[0034] The drill string 105 may include several joints of drill pipe 108 connected end-to-end through tool joints 109. The drill string 105 transmits drilling fluid through a central bore and transmits rotational power from the drill rig 103 to the BHA 106. In some embodiments, the drill string 105 may further include additional components such as subs, pup joints, etc. The drill pipe 108 provides a hydraulic passage through which drilling fluid is pumped from the surface. The drilling fluid discharges through selected-size nozzles, jets, or other orifices in the bit 110 for the purposes of cooling the bit 110 and cutting structures thereon, and for lifting cuttings out of the wellbore 102 as it is being drilled.

[0035] After a section of the wellbore 102 has been drilled, the drill string 105 may be tripped (removed from the wellbore 102), and at least a portion of the earth formation 101 may be lined with a casing 107. After placing the casing 107, a cementing operation may be performed during which cement is pumped through the casing 107, through the bottom of the casing 107, and out of the annulus between the casing 107 and the earth formation 101. After the cement sets, additional wellbore operations (e.g., additional drilling, completion) may be performed.PATENTDocket No. IS24.1340-WO

[0036] FIG. 2 is a simplified, partial cross-sectional view illustrating a portion of a downhole system 200 including the earth formation 101 after one or more cementing operations have been performed in the wellbore 102 (FIG. 1), in accordance with embodiments of the disclosure. The downhole system 200 may include multiple sections of casing, each extending from the surface (at the drill rig 103 (FIG. 1)) through a portion of the earth formation 101 and progressively extending farther into the earth formation 101. For example, the casing may include a conductor casing 202 extending from the surface through a portion of the earth formation 101, a surface casing 204 extending from the surface beyond the conductor casing 202, an intermediate casing 206 extending beyond the surface casing 204, and a production casing 208 (also referred to as a “production liner”) extending from the surface beyond the intermediate casing 206. The conductor casing 202 may be configured to protect shallow portions of the earth formation 101 from contamination, such as by drilling fluids. The surface casing 204 may facilitate maintaining integrity of the wellbore 102 (FIG. 1) and / or prevent (substantially prevent) contamination of groundwater by hydrocarbons, subterranean brines, and drilling fluids. The intermediate casing 206 may be configured to isolate hydrocarbon-bearing portions of the earth formation 101 and fractured and lost circulation zones. The production casing 208 may be configured to isolate zones of the earth formation 101 above and within a production zone.

[0037] The sections of casing may individually be isolated from the earth formation 101 by a geopolymer 210. For example, the geopolymer 210 may be located in the annular space between the earth formation 101 and each of the conductor casing 202, the surface casing 204, the intermediate casing 206, and the production casing 208. In some embodiments, the geopolymer 210 may be located in the annular space between neighboring sections of the casing, such as between the conductor casing 202 and the surface casing 204, between the surface casing 204 and the intermediate casing 206, and between the intermediate casing 206 and the production casing 208.

[0038] The geopolymer 210 may be formed from a geopolymer slurry including a geopolymer composition mixed with a carrier fluid (e.g., water or an aqueousPATENTDocket No. IS24.1340-WOsolution). The geopolymer composition may include a base composition and one or more additives, such as one or more of an activator, a retarder, an accelerator, a binder, a density modifier, a viscosifier, another fluid loss agent, an extender, a dispersant, an antifoam agent, silica, an expanding agent, an anti-settling additive, a coagulant, or combinations thereof.

[0039] The base composition may include a fluid loss control material formulated and configured to reduce fluid loss during pumping and circulation of the geopolymer slurry into a borehole and cementing operations with the fluid loss control material. The geopolymer slurry may be stable and exhibit a desired rheological profile at temperatures encountered within the borehole.

[0040] The base composition may include at least one of an aluminosilicate source, a fluid loss control material, and an activator. In some embodiments, the base composition further includes an additional fluid loss control material exhibiting synergistic properties with the fluid loss control material.

[0041] The at least one aluminosilicate source may be in the form of a solid or an aqueous solution of metal silicate. The at least one aluminosilicate source may include, but is not limited to, fly ashes such as ASTM type C fly ash, ASTM type F fly ash, and fly ashes not classified by ASTM, volcanic ash, volcanic glass, slag, ferrous slag, ferroalloy slag, non-ferrous slag (e.g., copper slag, nickel slag, tin slag, zinc slag), blast furnace slag, basic oxygen furnace slag, electric arc furnace slag, ground granulated blastfurnace slag (GGBS), diatomaceous earths, pumice, calcined or partially calcined clays (such as metakaolin), aluminum-containing silica fume, natural aluminosilicate, feldspars (which may be dehydrated), alumina and silica sols, synthetic aluminosilicate glass powder, zeolite, scoria, allophone, bentonite, red mud, which may be calcined, and pumice. Such materials may include a significant proportion of an amorphous aluminosilicate phase, which reacts in strong alkaline solutions. In embodiments from which the at least one aluminosilicate source is formed from a clay such as bentonite or metakaolin, the at least one aluminosilicate source may be amorphous silicon. For example, thePATENTDocket No. IS24.1340-WObentonite or metakaolin may be calcined to convert the material from a crystalline state to an amorphous material.

[0042] In some embodiments, the at least one aluminosilicate source may include a source of aluminosilicate polymer materials. The aluminosilicate polymer materials may include materials having the general formula, 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. In some embodiments, the at least one aluminosilicate source includes at least one of fly ash, metakaolin, blast furnace slag, or Portland cement. In some embodiments, the at least one aluminosilicate source includes fly ash, such as ASTM type C fly ash. In some embodiments, the at least one aluminosilicate source includes a mixture of two or more aluminosilicate sources. In addition, alumina and silica sources may be added separately, for example, as a blend of bauxite and silica fume. Other amorphous silica sources can also be used, which may include soda-lime glass dust, borosilicate glass dust, microsilica, fumed silica, precipitated silica, nanosilica, rice husk ash, or a combination thereof. It should be noted that some of the aluminosilicate sources mentioned above, such as GGBS and ASTM Class C fly ash, also contain calcium oxide, so these materials can also be considered activator sources. Suitable aluminosilicate sources for purposes herein can have at least 2%, at least 7%, at least 12%, at least 18%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, or at least 50% by weight calcium oxide. These aluminosilicate sources become reactive when placed in strongly alkaline environments, typically at pH greater than 11. The aluminosilicate sources described above react under such conditions to form geopolymers and other materials derived from alkali active materials.

[0043] The at least one aluminosilicate source may be amorphous. In some embodiments, the at least one aluminosilicate source is substantially free of crystalline aluminosilicate. For example, in some embodiments, the at least one aluminosilicate source may be subjected to a calcination process such that the aluminosilicate is amorphous.PATENTDocket No. IS24.1340-WO

[0044] The at least one aluminosilicate source may be present in the geopolymer composition at a weight percent within a range of from about 50 weight percent to about 99 weight percent, such as from about 50 weight percent to about 60 weight percent, from about 60 weight percent to about 70 weight percent, from about 70 weight percent to about 80 weight percent, from about 80 weight percent to about 90 weight percent, from about 90 weight percent to about 95 weight percent, from about 95 weight percent to about 97 weight percent, or from about 97 weight percent to about 99 weight percent, based on the weight of the blend (BWOB), wherein the weight of the blend includes the weight of the geopolymer composition (including the aluminosilicate source and other materials in the geopolymer composition). However, the disclosure is not so limited, and the weight percent of the at least one aluminosilicate source in the geopolymer composition may be different than that described.

[0045] As described above, the base composition may further include a fluid loss control material formulated and configured to reduce fluid loss of geopolymer slurries formed from the geopolymer composition in the earth formation. For example, in use and operation, such as during pumping of the geopolymer slurry into an annulus between a borehole and a casing, the geopolymer slurry may form a filtercake including the fluid loss control material. The fluid loss control material in the filtercake may reduce and / or prevent fluid loss of the geopolymer slurry or components thereof to the earth formation. Without being bound by any particular theory, in some embodiments, the fluid loss control material may swell (e.g., in the filtercake) and form a filtercake that is substantially impermeable to fluids (e.g., the aqueous phase of the geopolymer slurry) to reduce and / or prevent losses of the geopolymer water through the filtercake to the earth formation.

[0046] The fluid loss control material may include one or more crosslinked polymers that are formulated and configured to be water-swellable (e.g., expand in size responsive to exposure to water). The fluid loss control material may be configured to plug pore throats of the earth formation 101 during pumping and circulation of the geopolymer slurry including the fluid loss control material during cementing operations with the geopolymer slurry.PATENTDocket No. IS24.1340-WO

[0047] The fluid loss control material may include one or more hydrogels. The fluid loss control material may include one or more polymers formed from one or more monomers. The polymer may further include one or more crosslinkers and / or one or more anchoring materials. In some embodiments, the fluid loss control material includes one or more crosslinked polymers. The crosslinked polymers may be formed from monomers of one or more of acrylamide, N,N-dimethylacrylamide (NNDMA), N,N-diethylacrylamide, vinyl acetate (VA), 2-acrylamido-2-methyl propane sulfonic acid (AMPS), N-substituted acrylamides, methacrylamide, N-substituted methacrylamides, acrylates, methacrylate, acrylic acid, methacrylic acid, N-vinylamides, N-allylamides, vinyl alcohol, vinyl ethers, vinyl esters, allyl alcohol, allyl ethers, allyl esters, vinylpyridine, vinyl sulfonates, vinyl sulfonic acid, styrene sulfonate, allyl sulfonates, vinylimidazole, allylimidazole, or diallyldimethylammonium chloride. By way of non-limiting example, the crosslinked polymer may include a crosslinked copolymer of acrylamide and AMPS; a crosslinked copolymer of AMPS and NNDMA; a crosslinked terpolymerof acrylamide, AMPS, and NNDMA; or crosslinked polyvinyl acetate. The polymer may further include one or more anchoring materials, as described herein. In some embodiments, polymers including NNDMA may be stable at temperatures as high as about 148.9°C (about 300°F).

[0048] Non-limiting examples of N-substituted acrylamides include AMPS, N-ethylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N-hydroxyethylacrylamide, dimethylaminopropyl acrylamide. Non-limiting examples of N-substituted methacrylamides include dimethylaminopropyl methacrylamide. Non-limiting examples of acylates include methyl acrylate and hydroxyethyl acrylate. Non-limiting examples of methacrylates include methyl methacrylate, 2-hydroxyethyl methacrylate, and 2-dimethylaminoethyl methacrylate.

[0049] Non-limiting examples of N-vinylamides include N-vinylformamide, N-vinylacetamide, and N-methyl-N-vinylacetamide.PATENTDocket No. IS24.1340-WO

[0050] Non-limiting examples of vinyl ethers include vinyl ethyl ether, ethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, and glycerol monovinyl ether. The vinyl ester may include, for example, vinyl acetate.

[0051] Non-limiting examples of allyl ethers include sodium 3-allyloxy-2-hydroxypropane-1 -sulfonate, glycerol monoallyl ether, ethyelene glycol monoallyl ether, and polyethylene glycol monoallyl ether. The allyl ester may include, for example, allyl acetate.

[0052] In embodiments wherein the polymer includes acrylamide, the polymer may include from about 20.0 mole percent to about 90.0 mole percent of acrylamide, such as from about 20.0 mole percent to about 30.0 mole percent, from about 30.0 mole percent to about 40.0 mole percent, from about 40.0 mole percent to about 50.0 mole percent, from about 50.0 mole percent to about 60.0 mole percent, from about 60.0 mole percent to about 70.0 mole percent, from about 70.0 mole percent to about 80.0 mole percent, or from about 80.0 mole percent to about 90.0 mole percent of acrylamide. In some embodiments, the polymer includes from about 20.0 mole percent to about 30.0 mole percent of acrylamide, such as from about 23.0 mole percent to about 27.0 mole percent acrylamide. In some embodiments, the polymer includes from about 55.0 mole percent to about 65.0 mole percent acrylamide, such as from about 58.0 mole percent to about 62.0 mole percent of acrylamide. In some embodiments, the polymer includes from about 80.0 mole percent to about 90.0 mole percent of acrylamide, such as from about 84.0 mole percent to about 88.0 mole percent of acrylamide.

[0053] In embodiments where the polymer includes a sulfonate-based monomer (such as one or more of AMPS, vinyl sulfonic acid and / or derivatives thereof, styrene sulfonate and / or derivatives thereof, and / or allyl sulfonates), the polymer may include from about 3.0 mole percent to about 80.0 mole percent AMPS, such as from about 3.0 mole percent to about 5.0 mole percent, from about 5.0 mole percent to about 10.0 mole percent, from about 10.0 mole percent to about 20.0 mole percent, from about 20.0 mole percent to about 30.0 mole percent, fromPATENTDocket No. IS24.1340-WOabout 30.0 mole percent to about 40.0 mole percent, from about 40.0 mole percent to about 50.0 mole percent, from about 50.0 mole percent to about 60.0 mole percent, from about 60.0 mole percent to about 70.0 mole percent, or from about 70.0 mole percent to about 80.0 mole percent AMPS.

[0054] In some embodiments, the polymer includes greater than about 50.0 mole percent AMPS, such as greater than about 55.0 mole percent, or greater than about 60.0 mole percent AMPS. In some embodiments, the polymer includes from about 3.0 mole percent to about 7.0 mole percent AMPS. In some embodiments, the polymer includes from about 5.0 mole percent to about 9.0 mole percent AMPS. In some embodiments, the polymer includes from about 20.0 mole percent to about 30.0 mole percent AMPS, such as from about 23.0 mole percent to about 27.0 mole percent AMPS. In some embodiments, the polymer includes from about 30.0 mole percent to about 40.0 mole percent AMPS, such as from about 31.0 mole percent to about 35.0 mole percent AMPS.

[0055] In embodiments where the polymer includes NNDMA, the polymer may include from about 30.0 mole percent to about 95.0 mole percent NNDMA, such as from about 30.0 mole percent to about 50.0 mole percent, from about 50.0 mole percent to about 70.0 mole percent, from about 70.0 mole percent to about 90.0 mole percent, or from about 90.0 mole percent to about 95.0 mole percent NNDMA. In some embodiments, the polymer includes from about 40.0 mole percent to about 50.0 mole percent NNDMA, such as from about 45.0 mole percent to about 50.0 mole percent NNDMA.

[0056] The fluid loss control material may be crosslinked with one or more crosslinkers. In some embodiments, the one or more crosslinkers may include a crosslinker having one or more of an acrylate group, an acrylamide group, an allyl group, a methacrylate group, a methacrylamide group, a vinyl group, or an aldehyde group. For example, the crosslinker may include at least two of any of the foregoing functional groups. In some embodiments, the one or more crosslinkers may include a crosslinker with at least two acrylate groups, at least two acrylamide groups, at least two allyl groups, at least two methacrylate groups,PATENTDocket No. IS24.1340-WOat least two methacrylamide groups, at least two vinyl groups, or at least two aldehyde groups. The crosslinker may include one or more of methylene bisacrylamide (MBA), triallyl amine (TAA), pentaerythritol allyl ether (PAE), triallyl-triazine-trione (TTT), divinyl ether, diallyl ether, vinyl or allyl ethers of polyglycols, vinyl or allyl ethers of polyols, divinylbenzene, 1 ,3-divinylimidazolidin-2-one (also known as 1,3-divinylethyleneurea or divinylimidazolidone), divinyltetrahydropyrimidin-2(1 H)-one (tetrahydropyrimidine-2(1 H)-thione (also referred to as hexahydro-2-thioxopyrimidine or hexahydro-2 -thioxo-1 ,3~diazine); e.g., C4H8N2S), dienes (such as 1,7-octadiene and 1 ,9-decadiene), allyl amines (such as TAA and tetraallylethylene diamine), N-vinyl-3(E)-ethylidene pyrrolidone, or ethylidene bis(N-vinylpyrrolidone). The crosslinkers may constitute from about 1.0 mole percent to about 10.0 mole percent of the polymer, such as from about 1.0 mole percent to about 3.0 mole percent, from about 3.0 mole percent to about 5.0 mole percent, from about 5.0 mole percent to about 7.5 mole percent, or from about 7.5 mole percent to about 10.0 mole percent of the polymer. In some embodiments, the crosslinker constitutes less than about 7.5 mole percent of the polymer, such as less than about 6.0 mole percent of the polymer. In some embodiments, the amount of the crosslinker in the polymer may depend on the amount of AMPS in the polymer. By way of non-limiting example, in some embodiments, the polymer includes less than about 20.0 mole percent AMPS and greater than about 5.0 mole percent (such as 6.0 mole percent or greater than about 6.0 mole percent) of the crosslinker. In some embodiments, the polymer includes 60.0 mole percent or greater of AMPS and 2.0 mole percent or less of the crosslinker.

[0057] Non-limiting examples of vinyl or allyl ethers of polyols include PAE, allyl sucrose, ethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, glycerol diallyl ether, and polyethylene glycol divinyl ether, propylene glycol divinyl ether, and trimethylolpropane diallyl ether.

[0058] In some embodiments, the crosslinker includes MBA, such as from about 0.10 mole percent to about 5.0 mole percent of the polymer, such as from about 0.10 mole percent to about 1.0 mole percent, from about 1.0 mole percent to aboutPATENTDocket No. IS24.1340-WO3.0 mole percent, or from about 3.0 mole percent to about 5.0 mole percent of the polymer. In some embodiments, MBA constitutes from about 1.5 mole percent to about 2.5 mole percent of the polymer.

[0059] In some embodiments, the crosslinker includes TAA. The TAA may constitute from about 3.0 mole percent to about 9.0 mole percent of the polymer, such as from about 3.0 mole percent to about 5.0 mole percent, from about 5.0 mole percent to about 7.0 mole percent, or from about 7.0 mole percent to about 9.0 mole percent of the polymer. In some embodiments, the TAA constitutes from about 5.0 mole percent to about 7.0 mole percent of the polymer.

[0060] In some embodiments, the crosslinker includes PAE, which may constitute from about 1.0 mole percent to about 10.0 mole percent of the polymer, such as from about 1.0 mole percent to about 5.0 mole percent, or from about 5.0 mole percent to about 10.0 mole percent of the polymer.

[0061] In some embodiments, the fluid loss control material includes one or more anchoring materials (also referred to as “anchoring agents”). In some embodiments, the fluid loss control material includes a reaction product of one or more of the monomers described above, one or more of the crosslinkers described above, and one or more anchoring materials. The anchoring material may include one or more functional groups formulated and configured to attach the polymer surfaces of the earth formation 101 and / or to interact with one or more components of the geopolymer slurry. By way of non-limiting example, the anchoring material may include one or more carboxyl (-COOH) groups. In some embodiments, the anchoring material includes one or more phosphoryl groups. The one or more anchoring materials may include one or more of maleic anhydride, maleic acid, carbonyl phosphonic acid, vinyl phosphonic acid, or itaconic acid. In some embodiments, the anchoring material includes maleic anhydride and / or maleic acid. In some embodiments, the anchoring material includes carbonyl phosphonic acid. In some embodiments, the anchoring material includes vinyl phosphonic acid. Without being bound by any particular theory, it is believed that the carboxyl groups, the phosphoryl groups, and / or other groups of the anchoring materialPATENTDocket No. IS24.1340-WOcomplex with divalent cations in the geopolymer slurry, which may reduce the fluid loss of the geopolymer slurry to the earth formation 101.

[0062] The anchoring material may constitute from about 1.0 mole percent to about 10.0 mole percent of the polymer, such as from about 1.0 mole percent to about 3.0 mole percent, from about 3.0 mole percent to about 5.0 mole percent, from about 5.0 mole percent to about 7.5 mole percent, or from about 7.5 mole percent to about 10.0 mole percent of the polymer. In some embodiments, the anchoring material constitutes from about 3.0 mole percent to about 5.0 mole percent of the polymer. In some embodiments, the anchoring material includes maleic anhydride.

[0063] In some embodiments, the polymer comprises, consists essentially of, or consists of at least two of the monomers and at least one crosslinker. In some embodiments, the polymer comprises, consists essentially of, or consists of at least two of the monomers, at least one crosslinker, and at least one anchoring material. In some embodiments, the polymer comprises, consists essentially of, or consists of one of the monomers and at least one crosslinker.

[0064] The fluid loss control material may include a reaction product of 2-acrylamido-2-methyl propane sulfonic acid, methylene bisacrylamide, and at least one of N,N-dimethylacrylamide or N,N-diethylacrylamide. In some embodiments, the fluid loss control material includes a reaction product of 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, and methylene bisacrylamide. In some embodiments, the fluid loss control material includes a reaction product of 2-acrylamido-2-methyl propane sulfonic acid, N,N-diethylacrylamide, and methylene bisacrylamide.

[0065] In some embodiments, the fluid loss control material includes a crosslinked copolymer of AMPS and NNDMA. In some embodiments, the crosslinker may include MBA. By way of non-limiting example, the crosslinked copolymer may include from about 90.0 mole percent to about 95.0 mole percent of NNDMA, from about 3.0 mole percent to about 7.0 mole percent of AMPS, and from about 1.0 mole percent to about 5.0 mole percent of MBA. In somePATENTDocket No. IS24.1340-WOembodiments, the polymer includes about 5.1 mole percent of AMPS, about 92.8 mole percent of NNDMA, and about 2.1 mole percent of MBA. In some embodiments, the polymer may comprise an emulsion.

[0066] In some embodiments, the polymer includes a crosslinked copolymer of acrylamide and AMPS. The crosslinker may include MBA and TAA. In some embodiments, the fluid loss control material includes a reaction product of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, and methylene bisacrylamide. By way of non-limiting example, the crosslinked polymer may include from about 5.0 mole percent to about 10.0 mole percent (e.g., about 7.11 mole percent) of AMPS; from about 0.10 mole percent to about 0.75 mole percent (e.g., about 0.51 mole percent) of MBA; and from about 5.0 mole percent to about 7.0 mole percent (e.g., about 6.0 mole percent) of TAA.

[0067] In some embodiments, the polymer includes a crosslinked copolymer of acrylamide and AMPS. The crosslinker may include MBA. In some embodiments, the crosslinked copolymer further includes an anchoring material including maleic anhydride. By way of non-limiting example, the crosslinked copolymer may include from about 55.0 mole percent to about 65.0 mole percent AMPS (e.g., about 60.32 mole percent AMPS); from about 30.0 mole percent to about 36.0 mole percent acrylamide (e.g., about 33.65 mole percent acrylamide); from about 1.0 mole percent and about 3.0 mole percent MBA (e.g., about 2.02 mole percent MBA); and from about 2.0 mole percent to about 6.0 mole percent maleic anhydride (e.g., about 4.01 mole percent maleic anhydride).

[0068] In some embodiments, the polymer includes a reaction product of acrylamide and 2-acrylamido-2-methyl propane sulfonic acid. The crosslinker may include any of the crosslinkers disclosed herein, such as MBA. The crosslinked copolymer may further include a grafted component on an AMPS-acrylamide reaction product backbone, such as one or more polyphenols (e.g., tannin(s)). In some embodiments, the polymer may include tannin grafted onto an N-substituted acrylamide-based copolymer. For example, the polymer may include a copolymer reaction product of two or more of acrylamide, AA, and AMPS. The crosslinker mayPATENTDocket No. IS24.1340-WOinclude any of the crosslinkers disclosed herein, such as MBA. The polymer may include at least one grafted component, such as one or more tannins.

[0069] In some embodiments, the fluid loss control material may include a microgel including tannin grafted onto the polymer matrix of the reaction product of two or more of acrylamide, AA, and AMPS with a crosslinker of MBA. The microgel may be formed by mixing components including at least 90 weight percent tannin grafted copolymer (e.g., about 94 weight percent), at least 1 weight percent water (e.g., about 3 weight percent), at least 1 weight percent sodium sulfate (e.g., about 2.5 weight percent). In some embodiments, the microgel may include a biocide, such as having less than about 1 weight percent of the biocide. In some embodiments, the microgel may include a defoamer (e.g., dimethyl silicone emulsion), such as having less than 1 weight percent of the defoamer. In some embodiments, the mixture used to form the microgel may include a chelating agent (e.g., tetrasodium salt of ethylenediaminetetraacetic acid) for polymerization, such as having less than 1 weight percent of the chelating agent (e.g., less than 0.1 weight percent). In some embodiments, the mixture used to form the microgel may include sulfuric acid to adjust a pH of the reaction mixture used to form the microgel, such as less than 0.01 weight percent of the sulfuric acid. In some embodiments, additional components may be present in the reaction mixture used to form the microgel or in the final microgel, such as Tris (3-hydroxypropyltriazolylmethyl) amine or another triallylamine. Such additional components may be less than 1 weight percent of the mixture used to form the microgel, such as less than 0.1 weight percent.

[0070] In some embodiments, the polymer includes a reaction product of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, and methylene bisacrylamide with one or both of N,N-dimethylacrylamide or N,N-diethylacrylamide. In some embodiments, the polymer includes a reaction product of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, methylene bisacrylamide, and an anchoring material (such as triallyl amine or maleic anhydride). In some embodiments, the polymer includes a crosslinked terpolymer of acrylamide, AMPS, and NNDMA. The crosslinker may include MBA. By way ofPATENTDocket No. IS24.1340-WOnon-limiting example, the terpolymer may include from about 20.0 mole percent to about 30.0 mole percent (e.g., about 25.22 mole percent) of acrylamide; from about 20.0 mole percent to about 30.0 mole percent (e.g., about 25.04 mole percent) of AMPS; from about 45.0 mole percent to about 50.0 mole percent (e.g., about 47.74 mole percent) of NNDMA; and from about 1.0 mole percent to about 3.0 mole percent (e.g., about 2.20 mole percent) MBA. In some embodiments, the polymer may comprise an emulsion.

[0071] In some embodiments, the polymer includes a crosslinked polymer of polyvinyl acetate. The crosslinker may include pentaerythritol allyl ether, TTT, or a combination thereof. In some embodiments, the crosslinker includes pentaerythritol allyl ether. In some embodiments, the crosslinker includes TTT. By way of non-limiting example, in some embodiments, the pentaerythritol allyl ether may constitute from about 5.0 mole percent to about 15.0 mole percent of the crosslinked polymer, such as from about 5.0 mole percent to about 10.0 mole percent, or from about 10.0 mole percent to about 15.0 mole percent of the crosslinked polymer. However, the disclosure is not so limited, and the crosslinker may constitute a different amount of the crosslinked polymer.

[0072] In some embodiments, the fluid loss control material is an emulsion and includes a dispersed polymer in emulsion form. In some embodiments, the fluid loss control material is a solution and / or a suspension including the polymer. In some embodiments, the fluid loss control material is a gel including the polymer. In some embodiments, the fluid loss control material is water-soluble, such as low molecular weight crosslinked polymers such as vinyl acetal polymers, polyvinyl pyrrolidone, and synthetic crosslinked copolymers of AMPS and acrylamide. In some embodiments, the fluid loss control material includes an emulsion and is water soluble. In some embodiments, the pH of the geopolymer slurry and / or the fluid loss control material may affect the solubility of the fluid loss control material in the aqueous phase or an oleaginous phase.

[0073] FIG. 3 is a simplified chemical structure showing a chemical structure of a crosslinked polymer, according to at least one embodiment of the disclosure. ThePATENTDocket No. IS24.1340-WOpolymer illustrated in FIG. 3 may be formed from acrylamide and AMPS, an anchoring material including maleic acid, and a crosslinker including MBA. In FIG.3, the values of x, y, z, and m may be tailored depending on the amount of each of the acrylamide, AMPS, maleic acid, and MBA used during synthesis of the fluid loss control material.

[0074] The fluid loss control material may be present in the geopolymer composition at a weight percent within a range of from about 0.1 weight percent to about 10.0 weight percent by weight of the aluminosilicate. For example, for every about 100 parts by weight of the aluminosilicate, the geopolymer composition may include from about 0.10 part to about 3.0 parts by weight of the fluid loss control material. The fluid loss control material may be present in the geopolymer composition at a weight percent within a range of from about 0.1 weight percent to about 5.0 weight percent, about 5.0 weight percent to about 10.0 weight percent, about 0.1 weight percent to about 0.2 weight percent, from about 0.2 weight percent to about 0.5 weight percent, from about 0.5 weight percent to about 1.0 weight percent, from about 1.0 weight percent to about 1.5 weight percent, from about 1.5 weight percent to about 2.0 weight percent, from about 2.0 weight percent to about 2.5 weight percent, from about 2.5 weight percent to about 3.0 weight percent, from about 3.0 weight percent to about 3.5 weight percent, from about 3.5 weight percent to about 4.0 weight percent, from about 4.0 weight percent to about 4.5 weight percent, or from about 4.5 weight percent to about 5.0 weight percent by weight of the aluminosilicate. In some embodiments, the fluid loss control material is present in the geopolymer composition at a weight percent greater than about 1.0 weight percent of the fluid loss control material by weight of aluminosilicate. In some embodiments, the fluid loss control material is present in the geopolymer composition at about 3.0 weight percent by weight of the aluminosilicate.

[0075] The fluid loss control material may constitute from about 0.1 weight percent to about 10.0 weight percent of the geopolymer composition, such as from about 0.1 weight percent to about 5.0 weight percent, about 5.0 weight percent to about 10.0 weight percent, about 0.1 weight percent to about 0.2 weight percent,PATENTDocket No. IS24.1340-WOfrom about 0.2 weight percent to about 0.5 weight percent, from about 0.5 weight percent to about 1.0 weight percent, from about 1.0 weight percent to about 1.5 weight percent, from about 1.5 weight percent to about 2.0 weight percent, from about 2.0 weight percent to about 2.5 weight percent, from about 2.5 weight percent to about 3.0 weight percent, from about 3.0 weight percent to about 3.5 weight percent, from about 3.5 weight percent to about 4.0 weight percent, from about 4.0 weight percent to about 4.5 weight percent, or from about 4.5 weight percent to about 5.0 weight percent of the geopolymer composition.

[0076] In some embodiments, the geopolymer composition further includes at least one surfactant. In some embodiments, surfactant is present in the fluid loss control material, such as when the fluid loss control material includes an emulsion.

[0077] The surfactant may include one or more of a mixture of a fatty acid and a sugar alcohol sorbitol (polyol); sorbitan monooleate; polyoxyethylene (50) sorbitol hexaoleate; or a polymerizable surfactant . In some embodiments, the fatty acid includes oleic acid. The surfactant may constitute from about 2.0 weight percent to about 10.0 weight percent of the fluid loss control material, such as from about 2.0 weight percent to about 4.0 weight percent, from about 4.0 weight percent to about 6.0 weight percent, from about 6.0 weight percent to about 8.0 weight percent, or from about 8.0 weight percent to about 10.0 weight percent of the fluid loss control material. By way of non-limiting example, in some embodiments, the surfactant includes sorbitan monooleate and constitutes about 3.0 weight percent of an emulsion of the fluid loss control material. In some embodiments, the surfactant includes polyoxyethylene (50) sorbitol hexaoleate and constitutes about 7.0 weight percent of an emulsion of the fluid loss control material.

[0078] The geopolymer composition may further include an additional fluid loss control material. The additional fluid loss control material may include a water-soluble polymer. The additional fluid loss control material may include one or more of a polymeric latex material, a latex (emulsion polymer), an alkali-swellable latex, an acrylic polymer, a styrene butadiene latex material, vinylidene chloride, polyvinyl acetate, partially hydrolyzed vinyl acetate, bentonite, a carbonatePATENTDocket No. IS24.1340-WOpowder, carbon black, silica, microsilica, asphaltenes, thermoplastic resins, crosslinked polyvinyl alcohol (PVA), hydroxy ethyl cellulose (HEC), a cellulose polymer containing anionic carboxymethyl and nonionic hydroxyethyl groups added by ether linkages to hydroxyl groups on the cellulose backbone (carboxymethylhydroxyethyl cellulose (CMHEC)), CMHEC with various degrees of carboxymethyl substitution (e.g., ethylene oxide molar substitution), low and medium molecular weight hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl cellulose (HPC), a galactomannan, polyvinylpyrrolidone (PVP), a mixture of polyvinylpyrrolidone and maleic anhydride-N-vinylpyrrolidone copolymer, poly(aryl-vinylbenzyl) ammonium chloride, a copolymer of N-vinylpyrrolidone and styrene sulfonate (SS), gallactomannans, such as a guar derivative (e.g., hydroxypropylated guar), or another fluid loss control material. In some embodiments, the additional fluid loss control material includes a styrene butadiene latex material. In some embodiments, the additional fluid loss control material includes an alkali-swellable latex.

[0079] In some embodiments, the additional fluid loss control material includes one or more non-ionic synthetic water-soluble polymers, such as one or more polyvinyl pyrrolidone (PVP), and polyvinyl alcohol (PVA), polyethylene imine (PEI) (with or without a poly naphthalene dispersant), and polyallyl amine. The additional fluid loss control material may include one or more of a polyester, polylactic acid, a polyamide, an elastomer, a polyolefin, polyethylene, polypropylene, or polyurethane.

[0080] The additional fluid loss control material may include, anionic synthetic water-soluble polymers including copolymers and terpolymers derived from acrylamide, including or partially including hydrolyzed polyacrylamide, acrylic acid (AA), 2-acrylamido-2-methyl propane sulfonic acid, and copolymerized with acrylamide, and with N,N, dimethyl acrylamide, terpolymers of AMPS, acrylamide and itaconic acid, sodium itaconate, terpolymers of AMPS, acrylic acid, and N methyl N-vinyl acetamide (NVMA), terpolymers of AMPS, vinyl sulfonate and NMVA, terpolymers of AA, AMPS, and NMVA, terpolymers of AAm, AMPS, and NMVA, terpolymers of AMPS, NNDMA, AA, or acrylonitrile grafted to lignine,PATENTDocket No. IS24.1340-WOtetrapolymers of AMPS, N-Vinyl Pyrrolidone, acrylamide, tannin grafted AMPS with acrylamide and acrylic acid, tannin grafted onto N-substituted acrylamide-based copolymers (e.g., tannin grafted AMPS and acrylamide copolymer crosslinked with MBA as disclosed above), sulfonate polymers including polyvinyl aromatics, sulfonated polystyrene (SPS), sulfonated polyvinyl toluene (SPVT) and mixtures of SPS, SPVT, and a styrene maleic anhydride copolymer.

[0081] In some embodiments, the additional fluid loss control material is a water-soluble material and / or is cationic. In some embodiments, the additional fluid loss control material includes a copolymer of acrylic acid (also known as partially hydrolyzed polyacrylamide) and AMPS; a copolymer of acrylic acid and NNDMA; a terpolymer of AMPS, acrylamide, and itaconic acid; a terpolymer of AMPS, acrylic acid, and N-methyl N-vinyl acetamide (NVMA); a terpolymer of acrylamide, AMPS, and NMVA; a terpolymer of AMPS, NNDMA, and acrylic acid; a terpolymer of AMPS, NNDMA, and acrylonitrile grafted to lignin; a terpolymer of AMPS, N-vinyl pyrrolidone, and acrylamide; tannin grafted AMPS with acrylamide and acrylic acid; and tannin grafted onto N-substituted acrylamide-based copolymers. Other additional fluid loss control materials include sulfonate polymers, such as polyvinyl aromatics such as sulfonated polystyrene (SPS), sulfonated polyvinyl toluene (SPVT); and mixtures of SPS, SPVT, and a styrene malic anhydride copolymer.

[0082] In some embodiments, the additional fluid loss control material is water-soluble and is formed from anionic monomers. The anionic monomers may include one or more of acrylic acid, sodium acrylate, methacrylic acid, sodium methacrylate, vinyl sulfonic acid, vinyl sulfonate, sodium vinyl sulfonate, vinyl toluene sulfonic acid, vinyl toluene sulfonic acid sodium salt, 2-acrylamido-2-methyl propane sulfonic acid (AMPS), 2-acrylamido-2-methyl propane sulfonic acid sodium salt, itaconic acid, sodium itaconate, maleic anhydride, other metallic salts of the acids.

[0083] In some embodiments, the additional fluid loss control material includes water-soluble cationic polymers, such as copolymers containing various quaternized ammonium or sulfonium monomers, such as alkyl ammoniumPATENTDocket No. IS24.1340-WOchloride, or sulfonium chloride containing monomers, dimethyl diallyl ammonium chloride DM-DAAC, Methacrylamidopropyltrimethyl ammonium chloride MAPTAC. The cationic polymers may be formed from cationic monomers, such as one or more of trimethylammonium ethyl acrylate, benzyl dimethylammonium ethyl acrylate, A / -vinylimidazolium salts, diallyldimethylammonium chloride DADMAC.

[0084] In some embodiments, the additional fluid loss material is formed from one or more nonionic water-soluble and water-dispersible monomers, such as one or more of N-vinylpyrrolidone, acrylamide, dimethyl’acrylamide, dimethylaminoethyl acrylate, ethylene glycol acrylate, diethyleneglycol acrylate, polyethylene glycol acrylate ethylene glycol methacrylate, diethyleneglycol methacrylate, polyethylene glycol methacrylate.

[0085] In some embodiments, the additional fluid loss material is formed from one or more zwitterionic water-soluble monomers, such as one or more of ammoniocarboxylates (betaines) and ammoniosulfates (sulfobetaines), such as methacrylates of ammoniosulfonates such as 2-[(Methacryloyloxy) ethyl] dimethyl-(3 sulfopropyl) ammonium hydroxide (DMAPS), 4-[[2-(Methacryloyloxy) ethyl] dimethylammonio] butane-1 -sulfonate 3-[[2-(Acryloyloxy) ethyl] dimethylammonio] propane-1 -sulfonate and 3-[(3-Acrylamidopropyl) dimethylammonio] propane-1 -sulfonate, 3-(2’-vinyl-pyridinio)propanesulfonate, A / -(2-methacryloyloxy)ethyl-A / , / \ / -dimethyl-ammonio propanesulfonate, / V-(3-methacryloylimino)propyl-A / , / \ / -dimethyl-ammonio propanesulfonate, 2- (methacryloyloxy)ethylphosphatidylcholine, and 3-(2’-vinyl-pyridinio)propanesulfonate.

[0086] The additional fluid loss control material may include cationic synthetic water-soluble polymers including quaternized ammonium and sulfonium monomers including alkyl ammonium chloride, sulfonium chloride containing monomers, dimethyl diallyl ammonium chloride (DM-DAAC), and methacrylamidopropyltrimethyl ammonium chloride (MAPTAC).

[0087] In some embodiments, the additional fluid loss control material includes one or more water insoluble materials, such as swellable or crosslinked polymers,PATENTDocket No. IS24.1340-WOwell dispersed nanosized inorganic materials such as fumed silica, and polymeric latexes, such as styrene-butadiene latexes, and the like, commonly known as gas block additives. The additional fluid loss control material may improve the gas blocking properties of the geopolymer slurry.

[0088] The additional fluid loss control material may be present in the geopolymer slurry at a concentration between 0.02 L / L and 0.3 L / L (1 gal / bbl and 15 gal / bbl), or between 0.05 L / L and 0.15 L / L.

[0089] The additional fluid loss control material may be present in the geopolymer composition at a weight percent within a range of from about 0.1 weight percent to about 10.0 weight percent by weight of the aluminosilicate, such as from about 1.0 weight percent to about 5.0 weight percent, about 5.0 weight percent to about 10.0 weight percent, about 1.0 weight percent to about 1.5 weight percent, from about 1.5 weight percent to about 2.0 weight percent, from about 2.0 weight percent to about 2.5 weight percent, from about 2.5 weight percent to about 3.0 weight percent, from about 3.0 weight percent to about 3.5 weight percent, from about 3.5 weight percent to about 4.0 weight percent, from about 4.0 weight percent to about 4.5 weight percent, or from about 4.5 weight percent to about 5.0 weight percent by weight of the aluminosilicate. In some embodiments, the additional fluid loss control material is present in the geopolymer composition at a weight percent within a range of from about 1.4 weight percent to about 2.0 weight percent by weight of the aluminosilicate.

[0090] The geopolymer composition may include a greater weight percent of the fluid loss control material than of the additional fluid loss control material. In other embodiments, the geopolymer composition includes a greater weight percent of the additional fluid loss control material than of the fluid loss control material. In some embodiments, a weight percent of the fluid loss control material may be about the same as the weight percent of the additional fluid loss control material in the geopolymer composition. In some embodiments, the additional fluid loss control material may be used alone as the only fluid loss control material.PATENTDocket No. IS24.1340-WO

[0091] As described above, the geopolymer composition may include one or more additives. The one or more additives may include one or more of an activator, a retarder, an accelerator, a binder, a density modifier, a viscosifier, a fluid loss agent, an extender, a dispersant, an antifoam agent, a defoamer, silica, an expanding agent, an anti-settling additive, a coagulant, or combinations thereof.

[0092] The activator may be present in the base composition or in the one or more additives. The activator may include an alkali activator, an alkali activator precursor, an alkali salt, or combinations thereof. Interaction of the activator and the aluminosilicate source may facilitate a polycondensation reaction between the aluminosilicate source and the activator to form a polymer including a crosslinked network, such as a three-dimensional aluminosilicate mineral polymer. The alkali activator may be an alkali metal hydroxide, an alkaline-earth metal hydroxide, an alkaline earth metal oxide, an alkaline earth metal peroxide, at least one alkali salt, cement, or combinations thereof. Alkali metal hydroxides may include one or more of lithium hydroxide, sodium hydroxide, cesium hydroxide, rubidium hydroxide, or potassium hydroxide. Alkaline earth metal hydroxides may include one or more of calcium hydroxide, magnesium hydroxide, strontium hydroxide, or barium hydroxide. The alkaline earth metal oxides may be one or more of calcium oxide (e.g., lime), magnesium oxide, strontium oxide, barium oxide, or combinations thereof. The alkaline earth metal peroxide may be one or more of calcium peroxide or magnesium peroxide. The at least one alkali salt may be one or more of a metal carbonate (e.g., M2CO3, such as sodium carbonate), a metal sulfate (e.g., M2SO4), a metal sulfite (e.g., M2SO3), a metal phosphate (e.g., M3PO4), a metal oxalate (e.g., M2C2O4), a metal silicate (e.g., M2xSiyO(2y+x), wherein x is 1, 2, or 3, and y is 1 or 2), a metal fluoride (e.g., MF), a metal hexafluoride (e.g., M2SiFe), a metal iodate (e.g., MIO3), a metal molybdate (e.g., M2MOO4), wherein M is a metal such as lithium, sodium, potassium, rubidium, and / or cesium in each of the above examples. In some embodiments, hardened polysialates and cements (e.g., Portland cement) can also be used as activators. The alkali activator may be added as a solid, an aqueous mixture, or an encapsulated liquid or solid material. In an encapsulated embodiment, the solid or liquid activator can be trapped in a capsulePATENTDocket No. IS24.1340-WOthat will break when subjected to, for example, mechanical stress on the capsule, or coating degradation from temperature, radiation, and / or chemical exposure. The capsule can also naturally degrade if made from a biodegradable or selfdestructive material. Furthermore, the alkali activator when in liquid state may be adsorbed into a porous material and may be released after a certain time or due to a predefined event. The alkali activator may be added to the geopolymer slurry at a concentration within a range of from about 1 M to about 10 M, such as from about 3 M to about 6 M.

[0093] In some embodiments, the aluminosilicate material is activated without a hydroxide. By way of non-limiting example, in some embodiments, the activator includes an alkali activator, such as sodium carbonate. In some such embodiments, the aluminosilicate starting material, such as GGBS, may be set with only the sodium carbonate and without a hydroxide activator.

[0094] In some embodiments, the activator includes a metal silicate, such as an alkali metal silicate, such as one or more of sodium silicate, sodium metasilicate (Na2SiO3), potassium silicate (e.g., potassium metasilicate (feSiOs)), calcium silicate (Ca2SiO4), calcium metasilicate (CaSiOs), sodium carbonate (Na2CO3), or combinations thereof. The activator may include silicates of lithium, sodium, potassium, rubidium, cesium, or combinations thereof.

[0095] In some embodiments, the activator includes a first activator and a second activator. For example, the activator may include a metal hydroxide (e.g., sodium hydroxide) and a metal silicate (e.g., sodium silicate).

[0096] In some embodiments, the activator raises the pH of a geopolymer slurry formed from the geopolymer composition upon the addition of water such that the aluminosilicates in the geopolymer composition dissolve and begin to react to form the geopolymer.

[0097] The activator may be present in the geopolymer composition at a concentration within a range of from about 4.0 weight percent to about 20.0 weight percent, such as from about 4.0 weight percent to about 6.0 weight percent, from about 6.0 weight percent to about 8.0 weight percent, from about 8.0 weightPATENTDocket No. IS24.1340-WOpercent to about 10.0 weight percent, from about 10.0 weight percent to about 12.0 weight percent, from about 12.0 weight percent to about 14.0 weight percent, from about 14.0 weight percent to about 16.0 weight percent, from about 16.0 weight percent to about 18.0 weight percent, or from about 18.0 weight percent to about 20.0 weight percent by weight of aluminosilicate. In some embodiments, the activator includes a first activator and a second activator. The weight percent of the second activator may be the same as the weight percent of the first activator in the geopolymer composition. In other embodiments, the weight percent of the first activator is different than the weight percent of the second activator in the geopolymer composition.

[0098] In embodiments including a metal silicate, the metal silicate may be present in the geopolymer slurry at a concentration between 0.01 kg / L and 0.2 kg / L, or between 0.05 kg / L and 0.1 kg / L. The SiO2 / Na2O molar ratio may be less than or equal to 3.2. The SiCh / O molar ratio may be less than or equal to or less than 3.2. When mixed with the carrier fluid, the metal silicate may be present in the geopolymer composition at a concentration between about 0.1 M and 5 M, or between 0.5 M and 2 M. The metal silicates may be dry blended with the aluminosilicate source. Also, the metal silicate in another embodiment may be encapsulated.

[0099] The thickening time of geopolymer slurries formed from the geopolymer compositions described herein may be influenced by adding retarders and accelerators. The retarder may delay the setting and hardening of geopolymer slurries including the retarder. The retarder may include one or more of ferric sulfate (Fe2(SO4)3), sodium lignosulfonate (C2oH24Na20 S2), sodium pentaborate decahydrate, borax, boric acid, lignosulphonates, sodium gluconate, sodium glucoheptonate, tartaric acid, citric acid, sucrose, or phosphorus containing compounds such as phosphoric acid, salts thereof, or mixtures thereof. In some embodiments, the retarder includes ferric sulfate. The amount of retardation of the polymerization reaction, and the setting of the geopolymer slurry, may depend on the type of raw materials used for the geopolymer slurry and the type and relative quantity of the retarder in the geopolymer composition. A concentration of thePATENTDocket No. IS24.1340-WOretarder in the geopolymer composition may be within a range of from about 0.2 weight percent to about 3.0 weight percent, such as from about 0.2 weight percent to about 0.5 weight percent, from about 0.5 weight percent to about 1.0 weight percent, from about 1.0 weight percent to about 1.5 weight percent, from about 1.5 weight percent to about 2.0 weight percent, from about 2.0 weight percent to about 2.5 weight percent, or from about 2.5 weight percent to about 3.0 weight percent by weight of aluminosilicate. In some embodiments, the retarder is present in the geopolymer composition at a concentration within a range of from about 1.1 weight percent to about 2.3 weight percent.

[0100] In embodiments, the geopolymer slurry may include one or more fillers, which may include one or more density modifiers. The density modifier may include density increasing particles and density reducing particles. The fillers may be formulated and configured to reduce the density of the geopolymer slurry and the set geopolymer. In addition, the fillers may be configured to further improve the fluid loss of the geopolymer slurries. For example, the fillers may facilitate formation of a filter cake during cementing operations. The filter cake may reduce and / or prevent fluid loss. In some embodiments, the geopolymer slurry includes the fluid loss control material and one or more fillers. The combination of the fluid loss control material and one or more fillers in the geopolymer slurry may further reduce the fluid loss of the geopolymer slurry compared to embodiments not including the fillers.

[0101] In some embodiments, the fillers include density reducing particles, which may be included in the geopolymer composition to achieve lower geopolymer slurry densities for a given amount of water added, or density increasing particles may be added to achieve higher geopolymer slurry densities. The filler may include lightweight particles configured to lower the density of the geopolymer slurry. The filler may have a density lower than 2 g / cm3, or lower than 1.3 g / cm3In some embodiments, the filler includes surfactant stabilized gas bubbles, such as nitrogen or air gas bubbles in foams, or may include particles having a low specific gravity and having densities lower than 2 g / cm3, or lower than 1.3 g / cm3. Non-limiting examples of fillers for reducing the density of the geopolymer slurry include hollowPATENTDocket No. IS24.1340-WOglass beads or ceramic microspheres (cenospheres), elastomer, plastic particles such as polypropylene beads, rubber particles, uintaite (sold as GILSONITE™), vitrified shale, petroleum coke, coal, or combinations thereof. The density reducing particles may be present in the geopolymer slurry 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 density reducing particles may be between about 37 pm and 3,360 pm (6 mesh and 400 mesh).

[0102] In some embodiments, the geopolymer slurry includes fillers comprising density increasing particles configured to increase the density of the geopolymer slurry. The filler may include medium to heavy weight formulated and configured to increase the density of the geopolymer slurry. In some embodiments, the fillers have densities exceeding 2 g / cm3, or more than 3 g / cm3Density increasing particles may include cement, hematite, barite, ilmenite, silica (e.g., crystalline silica sand and silica flour), crushed granite, and manganese tetroxide commercially available under the trade names of MicroMax™ and MicroMax FF™, or combinations thereof (such as a combination of barite, silica, and hematite particles; barite and silica particles; and / or other combinations).

[0103] In embodiments, the geopolymer slurry may include a viscosifier. The viscosifier may include one or more of a polysaccharide (e.g., xanthan gum, diutan gum, welan gum), polyanionic cellulose (PAC), a carboxymethylcellulose (CMC), or another material. In some embodiments, the viscosifier includes diutan gum having a molecular weight higher than about 1 x 106. The viscosifier may be present in the geopolymer slurry at a concentration between 0.14 g / L and 1.4 g / L (0.05 Ib / bbl and 0.5 Ib / bbl). The molecular weight of the polysaccharides, which may be biopolymers, may be between 100,000 g / mol and 1,000,000 g / mol.

[0104] In embodiments, the geopolymer slurry may include an antifoam agent. The antifoam agent may include one or more of a propylene glycol, such as polypropylene glycol, a polyglycol ether, a silicone, or another material. The antifoam agent may be present in the geopolymer composition at a weight percent of from about 0.01 weight percent to about 0.05 weight percent by weight ofPATENTDocket No. IS24.1340-WOaluminosilicate, such as from about 0.01 weight percent to about 0.02 weight percent, from about 0.02 weight percent to about 0.03 weight percent, from about 0.03 weight percent to about 0.04 weight percent, or from about 0.04 weight percent to about 0.05 weight percent by weight of aluminosilicate. In some embodiments, the antifoam agent is present in the geopolymer composition at a weight percent of about 0.02 weight percent by weight of aluminosilicate.

[0105] In embodiments, the geopolymer slurry may include inorganic salt being added or pre-hydrated into the carrier fluid before adding the dry blend (the aluminosilicate composition) comprising of aluminosilicate silicate, alkali activator(s), fluid loss material and other additives for fine tuning properties of the geopolymer slurry to meet the wellbore requirements. The inorganic salts may include alkali metal and / or alkaline metal chlorides. Providing the inorganic salt in the carrier fluid rather than in the dry blend may facilitate temporary electrostatically binding between the cation of the inorganic salt and the anionic species of the fluid loss control material, preventing the polymers of the fluid loss control materials from hydrating and / or swelling. Accordingly, the surface viscosity of the geopolymer slurry is reduced, enhancing the flowability (pumpability) of the geopolymer slurry. For some high density geopolymers that include a relatively high concentration of the fluid loss control material, the inorganic salt in the carrier fluid may suppress the surface viscosity of the geopolymer slurry, enhancing the flowability of such geopolymer slurries.

[0106] In embodiments, the geopolymer slurry may include a dispersant. The dispersant may include a sulfonate-based material, carboxylic acids including gluconic acid and soluble salts thereof, glucoheptanonic 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, propionic 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, ethylenediamine tetraaceticPATENTDocket No. IS24.1340-WOacid (EDTA) and soluble salts thereof, phosphoric acid, or combinations thereof. By way of non-limiting example, the dispersant may include a sodium polynaphthalene (e.g., sodium polynaphthalene sulfonate), sodium lignosulfonate, calcium lignosulfonate, or combinations thereof.

[0107] The dispersant may be present in the geopolymer composition at a weight percent of from about 0.05 weight percent to about 0.50 weight percent by weight of aluminosilicate, such as from about 0.05 weight percent to about 0.10 weight percent, from about 0.10 weight percent to about 0.20 weight percent, from about 0.20 weight percent to about 0.30 weight percent, from about 0.30 weight percent to about 0.40 weight percent, or from about 0.40 weight percent to about 0.50 weight percent by weight of aluminosilicate.

[0108] The geopolymer composition may be mixed with a carrier fluid (e.g., water, brine, or another aqueous material) to form a geopolymer slurry including the geopolymer composition and the carrier fluid (e.g., water). The geopolymer slurry may be a pumpable composition. In use and operation, the geopolymer slurry may be pumped into the annular space between one or more sections of casing and the earth formation and / or between neighboring sections of casing. After setting, the geopolymer slurry may form the geopolymer.

[0109] A weight percent of the carrier fluid (e.g., water) in the geopolymer slurry may be within a range of from about 25.0 weight percent to about 35.0 weight percent, such as from about 25.0 weight percent to about 30.0 weight percent, or from about 30.0 weight percent to about 35.0 weight percent. However, the disclosure is not so limited, and the weight percent of water in the geopolymer slurry may be different than those described.

[0110] A density of the geopolymer slurry may be within a range of from about 800 kg / m3(about 6.69 pounds per gallon (Ib / gal) (ppg)) to about 2,900 kg / m3(about 24.2 ppg), such as from about 800 kg / m3(about 6.69 ppg) to about 1 ,000 kg / m3(about 8.35 ppg), from about 1,000 kg / m3(about 8.35 ppg) to about 1,200 kg / m3(about 10.0 ppg), from about 1,200 kg / m3(about 10.0 ppg) to about 1,400 kg / m3(about 11.7 ppg), from about 1,400 kg / m3(about 11.7 ppg) to about 1,600PATENTDocket No. IS24.1340-WOkg / m3(about 13.4 ppg), from about 1,600 kg / m3(about 13.4 ppg) to about 1,800 kg / m3(about 15.0 ppg), from about 1,800 kg / m3(about 15.0 ppg) to about 2,000 kg / m3(about 16.7 ppg), from about 2,000 kg / m3(about 16.7 ppg) to about 2,300 kg / m3(about 19.2 ppg), from about 2,300 kg / m3(about 19.2 ppg) to about 2,600 kg / m3(about 21.7 ppg), or from about 2,600 kg / m3(about 21.7 ppg) to about 2,900 kg / m3(about 24.2 ppg). In some embodiments, the density of the geopolymer slurry is about 1,800 kg / m3(about 15.0 ppg). However, the disclosure is not so limited, and the density of the geopolymer slurry may be different than those described. The density of the geopolymer slurry may be modified by incorporating one or more of the density reducing particles, density increasing particles, or by altering an amount of the aluminosilicate in the geopolymer composition.

[0111] A viscosity of the geopolymer slurry at about 20°C (about 68°F) may be less than about 400 centipoise (hereinafter “cP”), less than about 350 cP, or less than about 300 cP. A viscosity of the geopolymer slurry at about 48.9°C (about 120°F) may be less than about 200 cP, such as less than about 180 cP, less than about 160 cP, less than about 140 cP, less than about 120 cP, less than about 100 cP, or less than about 80 cP.

[0112] A solid volume fraction (SVF) (defined as the volumetric fraction of the geopolymer slurry comprised of solid particles) of the geopolymer slurry may be within a range of from about 25% to about 60%, such as from about 40% to about 55%. The carrier fluid (in which the solid materials of the geopolymer composition are dissolved) may constitute from about 40% to about 75% by volume of the geopolymer slurry and may be referred to as a liquid volume fraction (LVF). The carrier fluid may be present in the geopolymer slurry at a volume percent within a range of from about 40.0 volume percent to about 75.0 volume percent, such as from about 40.0 volume percent to about 50.0 volume percent, from about 50.0 volume percent to about 60.0 volume percent, from about 60.0 volume percent to about 70.0 volume percent, or from about 70.0 volume percent to about 75.0 volume percent. However, the disclosure is not so limited, and the SVF of the geopolymer composition may be different than those described.PATENTDocket No. IS24.1340-WO

[0113] A pH of the geopolymer slurry may be greater than about 11.0, such as greater than about 11.5, greater than about 12.0, greater than about 12.5, or greater than about 13.0. In some embodiments, the pH of the geopolymer slurry may be controlled by the alkali activator (e.g., the pH of the geopolymer slurry may be increased by increasing the amount of the alkali activator). The salt may not substantially affect the pH of the geopolymer slurry.

[0114] After setting, a density of the geopolymer formed from the geopolymer composition may be within a range of from about 800 kg / m3(about 6.68 ppg) to about 2,500 kg / m3(about 20.86 ppg), such as from about 800 kg / m3(about 6.68 ppg) to about 1 ,500 kg / m3(about 12.5 ppg), or from about 1 ,500 kg / m3(about 12.5 ppg) to about 2,500 kg / m3(about 20.86 ppg), however the disclosure is not so limited, and the density of the geopolymer may be different than those described.

[0115] Forming the geopolymer slurry from the geopolymer composition including the fluid loss control material may facilitate reducing the fluid loss of the geopolymer slurry during cementing operations in which the geopolymer slurry is pumped within a borehole and / or a wellbore and provided in an annulus between a casing or liner and surfaces of the earth formation defining a borehole. The geopolymer composition may form a filtercake on surfaces of the earth formation defining the borehole, and the fluid loss control material may reduce the amount of filtrate (of the geopolymer slurry) that filters through the filtercake. Accordingly, the presence of the fluid loss control material in the geopolymer slurry and / or in the filtercake may reduce the amount of fluid loss of the geopolymer slurry compared to geopolymer slurries that do not include the fluid loss control material.

[0116] FIG. 4 is a simplified flow chart illustrating a method 400 of performing a cementing operation, according to at least one embodiment of the present disclosure. The method 400 includes drilling at least a portion of an earth formation to form a borehole, as shown in act 402. A drilling fluid may be circulated through the borehole during drilling of the earth formation.

[0117] The method 400 further includes placing a section of casing within the borehole, as shown in act 404. Responsive to placing the section of casing withinPATENTDocket No. IS24.1340-WOthe borehole, the method 400 further includes circulating a geopolymer slurry through a drill string and to an annular space between the casing and the surfaces of the earth formation, as shown in act 406. The geopolymer slurry may include any of the geopolymer slurries formed from any of the geopolymer compositions described above. The geopolymer slurry may be formed from and include the aluminosilicate and the fluid loss control material. The geopolymer slurry may further include one or more of the additives described above.

[0118] Responsive to circulating the geopolymer slurry through the drill string and to an annular space between the casing and the surfaces of the earth formation, the geopolymer slurry may set to form a geopolymer including the fluid loss control material and the salt.

[0119] By way of comparison, some conventional fluid loss control materials, such as vinylidene chloride or polyvinyl acetate, are only suitable at temperatures below about 50°C (about 122°F). Such polymers are subject to degradation reactions, particularly in the moderate alkaline environment in cement slurries.

[0120] The fluid loss control material and / or the additional fluid loss control material may include water-soluble polymers and / or water-insoluble polymers. In some embodiments, fluid loss control materials for water-insoluble materials include but are not limited to polymer resins. Water-insoluble materials, including polymer resins, may act as permeability reducers in oil wells.

[0121] Both water-insoluble and soluble polymeric materials can be synthetic materials. The solubility of the fluid loss control material may affect the filter cake development in the wellbore. For example, filter cake development in the wellbore may be reduced when water-insoluble fluid loss control materials interact with the filter cake.

[0122] The fluid loss control material and / or the additional fluid loss control material can be synthesized using one or more of solution polymerization, precipitation polymerization, dispersion polymerization, partially non aqueous media solution polymerization, inverse emulsion polymerization, free radical polymerization, tempo mediated polymerization nitroxide-mediated polymerizationPATENTDocket No. IS24.1340-WO(NMP), atom transfer radical polymerization (ATRP) or transition metal-catalyzed living radical polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization, single electron transfer-living radical polymerization (SET-LRP), MADIX (macromolecular design via the interchange of xanthates), organoheteroatom-mediated living radical polymerization, and organometallic-mediated radical polymerization.

[0123] In some embodiments, the fluid loss control material and / or the additional fluid loss control material may be formed by one or more of emulsion polymerization, solution polymerization, or gel polymerization. By way of nonlimiting example, the fluid loss control material may be formed by emulsion polymerization and may include one or more of the polymers described above, such as polymers including one or more the monomers described above, one or more of the crosslinkers described above, and / or one or more of the anchoring materials described above.

[0124] In some embodiments, the fluid loss control material is formed by mixing acrylamide, AMPS, and / or NNDMA in water to form a solution. In some embodiments, crosslinkers, such as MBA and / or TAA are added to the solution. In some embodiments, the crosslinker includes NNDMA. An oleaginous phase and a surfactant may be added to the solution to form an emulsion. The oleaginous phase may include, for example, a hydrocarbon fluid, such as a hydrogenated oil. The surfactant may include one or more of the surfactants described above. In some embodiments, an anchoring agent, such as maleic anhydride and / or maleic acid is added to the emulsion. Nitrogen may be bubbled through the emulsion while the emulsion is cooled, such as in an ice bath. An initiator may be added to the emulsion to facilitate the polymerization reaction. The initiator may include a mixture of tert butyl hydroperoxide, sodium metabisulfite, azobis(2-methylpropionamidine)dihydrochloride, and combinations thereof. In some embodiments, the initiator includes about 0.02 weight percent tert butyl hydroperoxide, about 0.05 weight percent sodium metabisulfite, and about 0.05 weight percent azobis(2-methylpropionamidine)dihydrochloride. In some embodiments, the azobis(2-methylpropionamidine)dihydrochloride is added to thePATENTDocket No. IS24.1340-WOemulsion prior to the tert butyl hydroperoxide and sodium metabisulfite. Addition of the tert butyl hydroperoxide and sodium metabisulfite may increase the temperature of the emulsion. The emulsion mixture may be heated, such as to a temperature of about 65°C for a duration (e.g., about two hours) until the monomers are reacted.

[0125] In some embodiments, the fluid loss control material is formed by solution polymerization. By way of non-limiting example, the monomers (e.g., acrylamide, AMPS, and / or NNDMA) are dissolved in water to form a solution. After dissolving the monomers in the water, an initiator is added to the solution. The initiator may include a peroxide initiator, such as ammonium persulfate. The monomers may polymerize in the presence of the initiator when heated to a temperature, such as a temperature of about 65°C. In some embodiments, calcium hydroxide is added to the solution to neutralize the formed polymer. After the polymer is formed, the solution is dried (e.g., using a drum dryer or spray dryer) to obtain a powder comprising the polymer.

[0126] In some embodiments, fluid loss control materials and / or additional fluid loss control materials formed by emulsion polymerization may include polyvinylidene chloride, polyvinyl chloride, polytetrafluorethylene, polyvinylidene fluoride, polyvinyl acetate and derived copolymers, partially hydrolyzed polyvinyl acetate and derived copolymer of versatic acid vinyl esters (VEOVA), polyethylene, polyvinyl acetate ethylene copolymers, polypropylene, polybutylene, polystyrene, polybutadiene, polychloroprene, polyacrylic ester (where the ester radical is of methyl, ethyl, propyl, butyl, isobutyl, norbornyl, octadecyl, decil, hexadecyl, octyl, 2ethyl hexyl and the like), polymethacrylic ester (where the ester radical is of methyl, ethyl, propyl, butyl, isobutyl, norbornyl, octadecyl, decil, hexadecyl, octyl, 2ethyl hexyl and the like), polyacrylonitrile, polystyrene butadiene copolymer, polystyrene butadiene acrylonitrile terpolymer (ABS), polystyrene acrylonitrile copolymers, polyacrylonitrile butadiene copolymers, polystyrene butadiene copolymer, copolymers or polymers of one or more of the foregoing, polymers containing monomers selected from acrylic acid, methacrylic acid, acrylamide, acrylamide derived monomers, sulfonated monomers (styrene sulfonate, vinylPATENTDocket No. IS24.1340-WOsulfonate, AMPS), cationic monomers, polymerizable surfactant monomers, EO containing monomers, monomers capable of inducing a crosslinking in the polymer structure such as diacrylates, and divinyl benzene, diacrylamides, and the like, combinations thereof where the term copolymers in this list also includes terpolymers, tetrapolymers, and other polymers with a higher number of monomers in the composition.

[0127] As described above with reference to FIG. 4, geopolymer slurries formed from the geopolymer composition including the fluid loss control material may be used in oilfield operations and pumped downhole. Such geopolymer slurries may be disposed at a downhole location, typically in an annulus between a formation of interest and a casing, or in between two casings of different sizes (primary cementing).

[0128] To determine the effectiveness of the geopolymer composition for such cementing operations, multiple properties may be measured as per API RP 10B, including but not limited to the method of mixing, time and temperature of conditioning, viscosity at various speeds, gel time, degree of gelation, time to reach a certain consistency, transit time of an ultrasound wave (commonly reported as ultrasonic cement compressive strength in psi during setting), set cement mechanical properties (young’s modulus, compressive strength, tensile strength, poisson’s ratio, etc.), porosity and permeability, CO2 resistance, brine resistance, acid resistance, durability, grade of expansion or contraction, and / or other properties.

[0129] Another property of a geopolymer slurry is the filtration properties of the geopolymer slurry before setting. This property, commonly known as fluid loss volume, is determined in an experimental test whereby the geopolymer slurry is pressurized against a metallic porous filtration element, of known mesh, typically 44 microns (325 mesh screen). This test simulates the tendency of the geopolymer slurry to be lost through filtration of the interstitial fluid onto the formation when the geopolymer slurry is pumped downhole, and values as low as possible are desirable. One typical acceptable value of this parameter is when the volume ofPATENTDocket No. IS24.1340-WOfiltrate volume, as determined at the required temperature conditions in the API standardized test, is below 50 ml, and in some cases, below 100 ml.

[0130] Another property considered in several primary cement applications is the gas permeation through the set cement or set geopolymer, commonly known as the gas block (or blocking) properties of the fluid.

[0131] The fluid loss volume and gas blocking properties are typically only achieved as per industry requirements with the addition of chemical additives, typically known as fluid loss additives.

[0132] When primary cementing is performed using Portland cement, and / or pozzolan cement-based slurries, and other similar slurries, the fluid loss and gas blocking properties of the cement slurry are higher than desired in most applications irrespective of the solid volume fraction of the cement, the concentration of viscosifiers, the type of fillers, and the retarders, or dispersants used.

[0133] The study of the behavior of the fluid loss control materials and / or the additional fluid loss control materials (e.g., water-soluble fluid loss control materials) disclosed herein, such as low molecular weight linear and crosslinked polymers such as vinyl acetal polymers; polyvinyl pyrrolidone; synthetic linear or crosslinked copolymers of AMPS and acrylamide; other polyelectrolyte copolymers, which according to IUPAC are polymers composed of macromolecules in which a substantial portion of the constitutional units contains ionic or ionizable groups or both; and fluid loss control materials which are effective in reducing the fluid loss of Portland cement-based slurries, and substantially nonreacting aluminosilicate slurries, can be simulated using proxy aqueous solutions, for instance with small concentrations of Ca(OH)2. Measurements of physicochemical parameters of such additives in the aqueous solution, such as static light scattering, multiangle light scattering, and dynamic light scattering, to determine the molecular weight, molecule configuration, radius of gyration, hydrodynamic radius, intrinsic viscosity, polymer diffusion coefficient, turbidity, onset of precipitation, and solution viscosity are critical to determine that suchPATENTDocket No. IS24.1340-WOadditives will perform their functionalities in the cement slurry. In addition, adsorption tests to determine the adsorption effectiveness of the water-soluble additives onto the solids through adsorption isotherms are also of interest.

[0134] The study of the behavior of the additional fluid loss control materials disclosed herein, such as swellable or crosslinked polymers, well-dispersed nanosized inorganic materials such as fumed silica, and polymeric latexes, such as styrene-butadiene latexes, and the like, commonly known as gas block additives which are effective in reducing the fluid loss of pumpable Portland cement based slurries, and pumpable substantially non-reacting aluminosilicate slurries can also be simulated using proxy aqueous solutions, for instance with small concentrations of Ca(OH)2. Measurements of physicochemical parameters of such additives in the aqueous solution, such as dynamic light scattering or laser diffraction to determine the particle size, particle size distribution, zeta potential, turbidity, onset of precipitation, and emulsion stability, may be used to determine that such additional fluid loss control materials will perform their functionalities in the pumpable cement slurry. In addition, adsorption tests to determine the adsorption effectiveness of the water insoluble additives onto the solids through adsorption isotherms are also of interest.

[0135] It has been found that when pumpable substantially non-reacting slurries of aluminosilicates (e.g., not including alkali activators), such as those prepared to pump in oil and gas wellbores, or geopolymer slurries in the absence of alkaline activators such as sodium hydroxide, potassium hydroxide, lime, calcium hydroxide, sodium silicate, potassium silicate, calcium silicate, cement, sodium carbonate, sodium phosphate, and other compounds with similar net effect of increasing the hydroxyl concentration of the interstitial fluid, are formulated without fluid loss control materials and gas blocking additives, such slurries exhibit poor fluid loss properties and poor gas blocking properties in the absence of such fluid loss control materials and gas block additives, similar to Portland cement slurries.

[0136] On the other hand, when pumpable substantially non-reacting slurries of aluminosilicates (e.g., not including alkali activators), such as those prepared toPATENTDocket No. IS24.1340-WOpump in oil and gas wellbores, or geopolymer slurries in the absence of alkaline activators such as sodium hydroxide, potassium hydroxide, lime, calcium hydroxide, sodium silicate, potassium silicate, calcium silicate, cement, sodium carbonate, sodium phosphate, and other compounds with similar net effect of increasing the hydroxyl concentration of the interstitial fluid, the addition in adequate concentrations of additional fluid loss control materials such as low molecular weight linear and crosslinked polymer such as vinyl acetal polymers, polyvinyl pyrrolidone, synthetic linear or crosslinked copolymers of AMPS (2-Acrylamido-2-methylpropane sulfonic acid) and acrylamide, are effective in reducing the fluid loss of non-reacting slurries of aluminosilicates (e.g., substantially reducing the fluid loss volume).

[0137] In addition, it is observed that when pumpable non-reacting slurries of aluminosilicates (e.g., not including alkali activators) such as those prepared to pump in oil and gas wellbores, or geopolymer slurries in the absence of alkaline activators such as sodium hydroxide, potassium hydroxide, lime, calcium hydroxide, sodium silicate, potassium silicate, calcium silicate, cement, sodium carbonate, sodium phosphate, and other compounds with similar net effect of increasing the hydroxyl concentration of the interstitial fluid, the addition in adequate concentrations of additional fluid loss control materials such as swellable or crosslinked polymers, well dispersed nanosized inorganic materials such as fumed silica, and polymeric latexes, such as styrene butadiene latexes, commonly known as gas block additives, are effective in reducing the fluid loss of non-reacting slurries of aluminosilicates, and often are effective in improving the gas block properties of non-reacting slurries of aluminosilicates.

[0138] Such pumpable non-reacting slurries of aluminosilicates may exhibit interstitial fluids with low levels of salinity and ionic strength and moderate concentrations of hydroxyl ions that do not accurately represent the dynamic reactive environment in the aqueous phase present in the interstitial space between solid particles of the geopolymer slurries of the disclosure, which may include and be referred to as a “colloidally active and chemically react-able and filtrate-able aqueous liquid”, where the use of alkali activated materials and / orPATENTDocket No. IS24.1340-WOgeopolymer alkaline activators such as sodium hydroxide, potassium hydroxide, lime, calcium hydroxide, sodium silicate, potassium silicate, calcium silicate, cement, sodium carbonate, sodium phosphate, and other compounds with a similar net effect of substantially increasing the hydroxyl concentration of the interstitial fluid are used.

[0139] It has also been found that when substantially activated pumpable reacting slurries of aluminosilicates (including alkali activated slurries or geopolymer slurries) are formulated with working substantial concentrations of alkaline activators such as sodium hydroxide, potassium hydroxide, lime, calcium hydroxide, sodium silicate, potassium silicate, calcium silicate, cement, sodium carbonate, sodium phosphate, and other compounds with a similar net effect of increasing the hydroxyl concentration of the interstitial fluid, are formulated without fluid loss control materials and gas migration additives, these slurries exhibit poor fluid loss properties and poor gas block properties in the absence of such fluid loss additives and gas block additives.

[0140] On the other hand, it has been surprisingly observed that when such substantially activated pumpable reacting slurries of aluminosilicates (including alkali activated slurries or geopolymer slurries) are formulated with working substantial concentrations of alkaline activators such as sodium hydroxide, potassium hydroxide, lime, calcium hydroxide, sodium silicate, potassium silicate, calcium silicate, cement, sodium carbonate, sodium phosphate, and other compounds with similar net effect of increasing the hydroxyl concentration of the interstitial fluid, the addition of water-soluble fluid loss control materials, according to embodiments of the disclosure substantially reduce the fluid loss and increase the gas blocking properties of the geopolymer slurries, as described below with reference to FIG. 11 through FIG. 13.

[0141] Accordingly, while some fluid loss control materials may be effective at reducing the fluid loss and / or increasing gas blocking of cement slurries, such fluid loss control materials may not be effective at reducing the fluid loss and / or increasing gas blocking of activated (e.g., alkali activated) geopolymer slurries.PATENTDocket No. IS24.1340-WO

[0142] The geopolymer slurries of the disclosure may comprise react-able geopolymer slurries including interstitial fluids with high levels of salinity and ionic strength and very high concentrations of hydroxyl ions and may comprise a colloidally active chemically react-able filtrate-able aqueous liquid. It is in the best interest of the product developer and formulator to have fast screening methods that can aid in identifying suitable fluid loss control materials that can properly perform their function in such pumpable reacting slurries of aluminosilicates. Suitable screening methods can be developed by performing comparative tests between the physicochemical behavior of the fluid loss control materials in aqueous solutions in water compared to a proxy fluid such as, for instance, 3 molar Na OH, (in short 3M NaOH). Measurements of physicochemical parameters, such as static light scattering, multiangle light scattering, dynamic light scattering to determine the molecular weight, molecule configuration, radius of gyration, hydrodynamic radius, intrinsic viscosity, polymer diffusion coefficient, turbidity, onset of precipitation, and solution viscosity, are suitable parameters for rapid screening of water-soluble fluid loss control materials. In contrast, measurements of physicochemical parameters, such as dynamic light scattering or laser diffraction to determine the particle size and particle size distribution, turbidity, zeta potential, onset of precipitation, and emulsion stability, are suitable parameters for rapid screening of water-insoluble fluid loss control materials.

[0143] It is expected that the results of the ratios of the properties of interest for each type of fluid loss control material (soluble or insoluble) will be correlated with the polymer configuration for the polymer (e.g., water-soluble or water-insoluble) fluid loss control materials and with the colloidal stability of the dispersed solid additives, in the conditions of use, for instance in the geopolymer slurry (the colloidally active chemically react-able filtrate-able aqueous liquid) or its proxy 3M NaOH.

[0144] Fast screening of fluid loss control materials may facilitate improving the fluid loss of geopolymer slurries by selecting optimal soluble geopolymers based on their interaction with the colloidally active chemically react-able filtrate-able aqueous liquid or a proxy solution such as 3M NaOH aqueous solution.PATENTDocket No. IS24.1340-WO

[0145] For water-soluble polymers, the conformation of polyelectrolyte polymers may affect the adsorption of the polymer onto the geopolymer slurry particles and, therefore, affect (e.g., dictate) the rate and mechanism of packing and agglomeration of particles during a filtration experiment, and thus the ultimate fluid loss volume of the geopolymer slurry including the water-soluble polymers. This conformation may be affected by several factors, notably the polymer architecture and solvent affinity, with overall charge also having a significant effect. Whereas an uncharged linear polymer chain and slightly crosslinked and crosslinked polymers may be in a random conformation in solution, the charges on a linear polyelectrolyte chain and slightly crosslinked and crosslinked polyelectrolyte polymers may repel each other via double layer forces, which may cause the chain to adopt a more expanded, rigid-rod-like configuration. The charges will be screened if the solution contains more than a predetermined concentration or amount of added salt or, as in the application, a high concentration of hydroxyl ions. Consequently, the polyelectrolyte chain will collapse to a more conventional conformation (essentially identical to a neutral chain in good solvent). In addition to adsorption behavior onto particles, polymer conformation affects many bulk properties (such as viscosity, turbidity, solubility, precipitation, etc.). Techniques such as static light scattering and multiangle light scattering can be used to study polyelectrolyte conformation and conformational changes, determining parameters such as the molecular weight, the hydrodynamic radius, the radius of gyration, and the ratio of the radius of gyration over the hydrodynamic radius.

[0146] Low molecular weight (below 2 million Dalton, and often below 500,000 Dalton), negatively charged polymers such as those described as water-soluble additives (such as AMPS acrylamide copolymers and AMPS acrylamide copolymer with partially hydrolyzed acrylamide copolymers, or AMPS acrylamide and acrylic acid containing copolymers, and their partially crosslinked counterparts, which are polymers with charges of a single type (negative such as sulfonate, phosphonate or carboxylate)) where the polymer has a substantial number of negative charges per polymer chain (at least 1 negative charge every 2 monomeric units or at least 1 negative charge every 5 monomeric units, or at least 1 negative charge every 10PATENTDocket No. IS24.1340-WOmonomeric units) may be referred to herein as “strongly anionic polyelectrolytes.” The ratio of a property such as the hydrodynamic radius in 3M NaOH over that in a reference water is expected to be substantially lower than 1 (i.e., the value of the property in 3M NaOH divided by the value of the property in a reference water is lower than 1). It is expected that the ratio of a property such as the radius of gyration in 3M NaOH over that in a reference water will be substantially lower than 1 (i.e., the value of the property in 3M NaOH divided by the value of the property in a reference water is lower than 1 ). Without being bound by any particular theory, it is believed that the ratio is related to the ionic strength of the medium where higher ionic strength corresponds to lower the resulting radius.

[0147] Low molecular weight (below 2 million Dalton, and often below 500,000 Dalton), positively charged polymers such as polycationic polyacrylamides, polydiallyldimethylammonium chloride, or polyDADMAC, and the like where the polymer has a substantial number of positive charges per polymer chain (at least 1 positive charge every 2 monomeric units or at least 1 positive charge every 5 monomeric units, or at least 1 positive charge every 10 monomeric units) may be referred to herein as “strongly cationic polyelectrolytes.”

[0148] Even though colloidal stability such as zeta potential, electrostatic potential, electrostatic stabilization, and steric stabilization, are only scientifically relevant in colloids, the colloidal stability of the fluid loss control materials may be used to determine the compatibility of the fluid loss control materials with the aggressive aqueous fluids used in pumpable alkali activated material slurries and pumpable geopolymer slurries for dispersed materials, and for soluble polymers. The use of a mildly charged fluid loss control material (or combination of fluid loss control materials) with sufficient nonionic stabilization (whether in the interface or the polymer structure of the fluid loss control material) facilitates the fluid loss control material exhibiting a resistance against the ionic strength and high hydroxyl content of the colloidally active chemically react-able filtrate-able aqueous liquid present in the interstitial space of the slurry during mixing, pumping, and testing, notably during fluid loss testing, regardless of the water-solubility of the fluid loss control material. Without being bound by any particular theory, it is believed that aPATENTDocket No. IS24.1340-WOsufficiently mild ionic charge (not strong charges) compensates for the ionic strength and, most preferably, substantial nonionic stabilization for the fluid loss control material to perform effectively as a fluid loss control material in geopolymer slurries.

[0149] The fluid in the interstitial space of the geopolymer slurry is considered colloidally active because it may contain colloids dispersed in the fluid either by the designed addition of latex or a nano solid, by the dissolution of silica and alumina, and / or precipitation of silica, alumina, carbonates, etc. More importantly, it can affect the colloidal stability and / or the solution stability of the additives.

[0150] Without being bound by any particular theory, it is believed that the fluid in the interstitial space of the slurry is chemically react-able because it participates in the aluminum and silica dissolution precipitation processes, carries the activating hydroxyl ions, and alters the chemical stability of the fluid loss control materials, by hydrolysis for instance, of esters and amides, such as acrylamide.

[0151] In addition, and without being bound by any particular theory, the fluid in the interstitial space of the slurry is considered filtrate-able due to migrating through the slurried particles across the filter cake and the permeable barrier during the fluid loss testing and during application during cementing operations when the geopolymer slurry forms a filter cake on surfaces of the earth formation. In addition, the fluid in the interstitial space of the slurry is considered aqueous liquid because, besides the hydroxyl ion and the ions resulting in a high ionic strength, the primary liquid solvent is water.

[0152] According to embodiments described herein, a methodology of fluid evaluation, where “proxy interstitial fluids” are proposed for some of the tests to optimize the chemical nature and concentrations of the fluid loss control material in a geopolymer slurry to achieve the desired properties regarding overall fluid viscosity, dispersion, and notable filtration performance, is commonly known in the fluid as fluid loss determination.

[0153] Measurements of physicochemical parameters of fluid loss control materials soluble in the aqueous solution, such as gel permeation chromatography,PATENTDocket No. IS24.1340-WOstatic light scattering, multiangle light scattering, dynamic light scattering to determine the molecular weight, molecule configuration, radius of gyration, hydrodynamic radius, intrinsic viscosity, polymer diffusion coefficient, turbidity, onset of precipitation, and solution viscosity may be used to determine that such fluid loss control materials will perform their functionalities in the geopolymer slurry. In addition, adsorption tests to determine the adsorption effectiveness of the water-soluble fluid loss control materials onto the solids through adsorption isotherms may also be of interest.

[0154] Measurements of physicochemical parameters of particulate and / or insoluble additives in the aqueous solution, such as dynamic light scattering or laser diffraction, to determine the particle size, particle size distribution, zeta potential, turbidity, onset of precipitation, and emulsion stability, may be used to determine that such fluid loss control materials will perform their functionalities in the pumpable geopolymer slurry. In addition, adsorption tests to determine the adsorption effectiveness of water-insoluble fluid loss control materials onto the solids through adsorption isotherms are also of interest. In addition, dynamic scanning calorimetry and related mechanical characterization methods may be used to determine the glass transition temperature and other thermal or mechanical properties.

[0155] Methods of rapid screening of fluid loss control materials may include estimating the ratio Rproperty(i) of the value of a property of interest i (Property(i)3M NaOH) in, for instance, a proxy fluid 3 M NaOH water solution over the value of the same property of interest (Property(i)water) in reference water such as deionized or potable water, or saturated Ca(OH)2 solution, wherein:

[0156] Rproperty(i)=PrOperty(i)3M NaOH I Property(i)water

[0157] In the equation above, the ratio may be equal to the value of the property in the proxy fluid divided by the value of the property in the reference water. Proxy fluids can be any high salinity high hydroxyl content tailored aqueous fluid effectively simulating the compatibility of the fluid loss control material with the colloidally active chemically react-able filtrate-able aqueous liquid. For soluble fluidPATENTDocket No. IS24.1340-WOloss control materials, where one such property of interest i is the hydrodynamic radius measured by static or multiangle light scattering, most additives at most concentrations will typically exhibit results such as Property(i)3M NaOH < Property(i)water with values of Property(i)3M NaOH decreasing as the fluid compatibility with the proxy fluid decreases.

[0158] For soluble fluid loss control materials, where one such property of interest i is the radius of gyration measured by static or multiangle light scattering, most additives at most concentrations will typically exhibit results such as Property(i)3M NaOH < Property(i)water, wherein lower values of Property(i)3M NaOH correspond to lower compatibility of the fluid loss control material with the proxy fluid (and a geopolymer slurry).

[0159] For soluble fluid loss control materials, one other such property of interest i is the interstitial fluid viscosity measured by a capillary viscometer or other suitable viscosity testing method, which will also typically exhibit results such as Property(i)3M NaOH < Property(i)water, wherein lower values of Property(i)3M NaOH correspond to lower compatibility of the fluid loss control material with the proxy fluid (and a geopolymer slurry).

[0160] Whereas for insoluble fluid loss control materials, where a property of interest i is the mean particle size diameter typically measured by laser diffraction, the insoluble fluid loss control materials may exhibit results such as Property(i)3M NaOH > Property(i)water, wherein higher values of Property(i)3M NaOH correspond to lower compatibility of the fluid loss control material with the proxy fluid (and a geopolymer composition).

[0161] Without being bound by any particular theory, for some properties such as the hydrodynamic radius, it is expected that the ratio (the value of Rproperty(i)) will decrease when exposing the fluid to the 3M NaOH solution, and it is speculated that suitable candidates for the fluid loss control material will be those with ratio values between 0.1 and 1, and most suitable candidates will be those with ratio values between 0.5 and 1 , whereas unsuitable candidates may have ratio values between 0.001 and 0.1. For other properties such as the radius of gyration, it isPATENTDocket No. IS24.1340-WOspeculated that suitable candidates will also be those with ratio values between 0.1 and 1 , and most suitable candidates will be those with ratio values between 0.5 and 1, whereas unsuitable candidates may exhibit ratio values between 0.001 and 0.1 . For other properties such as the mean particle size, it is expected that the ratio will increase when exposing the fluid to the 3M NaOH solution, and it is speculated that suitable candidates will also be those with ratio values between 1 and 10, and most suitable candidates will be those with ratio values between 1 and 2, whereas unsuitable candidates may exhibit ratio values between 10 and 1000.

[0162] Without being limited to any particular theory, it is expected that most suitable fluid loss control materials will be those with values of several properties of interest closest to 1, whereas most unsuitable candidates will be those with values of several properties either well below 1 (such as 0.2, 0.1 , or lower) when the Property(i)3MNaOH < Property(i)water or well above 1 (such 5.0, or 10.0 or higher). Without being bound by any particular theory, it is believed that the difference in performance between the additives in 3M NaOH and reference water may be used to determine if such fluid loss control materials will perform their functionalities in the pumpable react -able aluminosilicate slurry.

[0163] During selection of the fluid loss control material, one may consider additional properties of the fluid loss control material, such as the physical state, concentration, durability, chemical stability, field usability, degradation, ecotoxicity, HSE, cost, availability, and impact on other properties such as acceleration, retardation, or gelation.

[0164] FIG. 5 is a simple flow chart illustrating a method 500 for rapid screening of a fluid loss control material, according to at least one embodiment of the disclosure. The fluid loss control material may include a water-soluble copolymer of a low to intermediate molecular weight (in between 10,000 Dalton and 5,000,000 Dalton, such as between 100,000 Dalton and 4,000,000 Dalton, between 200,000 Dalton and 3,000,000 Dalton, between 300,000 Dalton and 3 ,000,000 Dalton, or between about 300,000 Dalton and 2,000,000 Dalton.PATENTDocket No. IS24.1340-WO

[0165] The fluid loss control material may include polymers that are sterically or quasi-neutrally electrostatically stabilized negatively charged polyelectrolytes and may exhibit at least one property with a ratio close to one, preferably this property being selected from the hydrodynamic radius or the radius of gyration, with a different chemical composition than those currently in use in oil well cementing, where the chemical composition of the polymer may be selected by introducing the polymer structure features such as: i) the concentration of negative charges is reduced to no more than 1 every 11 monomeric units (mild anionic polyelectrolytes; ii) the concentration of positive charges is reduced to no more than 1 every 11 monomeric units (mild cationic polyelectrolytes); iii) additional nonionic monomers with substantial steric stabilization of the charge polymer are introduced; iv) polyampholytes, or polyelectrolytes, are composed of macromolecules containing cationic and anionic or corresponding ionizable groups. In this case, additional monomers with opposite charges are introduced in the same polymeric chain, resulting in a nearly neutral charge balance having about an equal number of monomeric units with negative charges and positive charges with a charge difference of no more than 20% excess of negative charges quasi-neutrally electrostatically stabilized negatively charged polyelectrolytes or no more than a 20% excess of positive charges quasi-neutrally electrostatically stabilized positively charged polyelectrolytes; v) additional zwitterionic monomers with both positive and negative charges in one monomeric unit.

[0166] In some embodiments, mild anionic polyelectrolytes, mild cationic polyelectrolytes, quasi-neutrally electrostatically stabilized negatively charged polyelectrolytes, quasi-neutrally electrostatically stabilized positively charged polyelectrolytes, polyampholytes and / or polyzwitterionic polymers may provide enhanced fluid loss performance in the pumpable activated, react-able aluminosilicate slurries, as for these polyelectrolytes that bear both cationic and anionic groups the competition between the acid-base equilibria of these groups may lead to only dissolving when sufficient added salt screens the interactions between oppositely charged segments. It is speculated that the closer to one the ratio of the hydrodynamic radius of the polymer dissolved in 3M NaOH over thePATENTDocket No. IS24.1340-WOhydrodynamic radius of the polymer dissolved in water, the more likely the chance of achieving good fluid loss. Improving fluid loss of slurries may be evaluated by selecting optimal soluble fluid loss control materials based on their interaction with the colloidally active chemically react-able filtrate-able aqueous liquid or a proxy solution such as 3M NaOH aqueous solution.

[0167] With reference to FIG. 5, the method 500 may include selecting an aqueous fluid comprising a reference formulation comprising an alkyl activated material or a geopolymer material, the reference formulation comprising at least aluminosilicate, an activator, and water, as shown in act 502. The method 500 may further include identifying properties of the aqueous fluid in the reference formulation with respect to hydroxyl ion content and ionic strength, as shown in act 504.

[0168] The method 500 may further include identifying a proxy aqueous fluid composition that simulates the aqueous fluid in the reference formation, as shown in act 506. In addition, the method 500 may include identifying a reference water composition, as shown in act 508. The method 500 may further include identifying a fluid loss control material (also referred to as a “fluid loss additive” (FLA)) composition of interest, FLA(J), as shown in act 510.

[0169] Responsive to identifying a fluid loss control material, the method 500 may further include synthesizing and / or sourcing the fluid loss control material of interest FLA(J), as shown in act 512. A sample of the fluid loss control material FLA(J) may be prepared in the proxy aqueous fluid (the proxy brine), and in reference water, as shown in act 514 and act 516, respectively.

[0170] Responsive to identifying the fluid loss control material FLA(J) of interest, the method 500 may further include selecting at least one physiochemical parameter of interest for the fluid loss control material FLA(J) of interest (property(i)), as shown in act 518. The physiochemical parameter of interest may be determined in the proxy aqueous fluid (the proxy brine) (property(i)proxy brine), as shown in act 520; and the physiochemical parameter of interest may be determined in the reference water (property(i)reference water), as shown in act 522.PATENTDocket No. IS24.1340-WO

[0171] The method 500 may further include comparing the physicochemical parameter of interest in the proxy aqueous fluid to the physicochemical parameter of interest in the reference water for the fluid loss control material FLA(J) of interest, as shown in act 524. The comparison may include determining the ratio of the properties, according to the following equation: Rproperty(i) = Property(i)proxy brine / Property(i)reference water.

[0172] The method 500 may further include determining whether the fluid loss control material FLA(J) of interest passes the screening criteria, as shown in act 526. For example, the water-soluble polymer synthetized with a composition using the monomers included herein may be evaluated and selected according to the rapid screening process described herein, such as by determining a ratio of a physicochemical property of interest such as the hydrodynamic volume Rproperty(i) = Property(i)Proxy brine / Property(i)water (e.g., close to 1 , or an acceptable value), by having obtained a ratio of a physicochemical property of interest such as the radius of gyration Rproperty(i) = Property(i)Proxy brine / Property(i)water (e.g., close to 1, or an acceptable value). In other words, fluid loss control materials FLA(J) of interest having a ratio of Rproperty(i) close to 1 or greater may pass screening criteria, while fluid loss control materials FLA(J) of interest having a ratio below 1 (e.g., lower than about 0.75 or about 0.50) may not be suitable fluid loss control materials of interest. Responsive to determining that the fluid loss control material FLA(J) of interest is not suitable, the method 500 includes identifying learnings and continuing to search for a suitable fluid loss control material FLA(J+1), as shown in acts 528 and 530.

[0173] Responsive to determining that the fluid loss control material FLA(J) of interest is suitable, the method 500 includes performing cementing testing or other performance testing (e.g., API testing) of the fluid loss control material FLA(J) of interest, as shown in act 532. The method 500 may include determining whether the fluid loss control material FLA(J) of interest passes cementing criteria, as shown in act 534. Fluid loss control materials FLA(J) of interest passing cementing criteria may be proposed for use, as shown in act 536; whereas fluid loss control material FLA(J) of interest not passing cementing criteria may be used to identifyPATENTDocket No. IS24.1340-WOlearnings and continue searching for a suitable fluid loss control material FLA(J+1 ), as shown in acts 538 and 540, respectively.

[0174] Accordingly, in some embodiments, the fluid loss of slurries may be improved by evaluating and selecting optimal soluble fluid loss control materials and / or insoluble fluid loss control materials based on their interaction with the colloidally active chemically react-able filtrate-able aqueous liquid or a proxy solution, such as 3M NaOH aqueous solution.

[0175] While FIG. 5 describes a method 500 for selecting a fluid loss control material, the fluid loss control material may be selected according to different criteria. In addition, while the fluid loss control material has been described as exhibiting certain properties (e.g., Rproperty(i) = Property(i)Proxy brine / Property(i)water having a value of 1 or close to about 1), the disclosure is not so limited, and the fluid loss control material may exhibit different properties than those described.

[0176] Herein we disclose a particulate additive for use in alkali activated pumpable slurries or pumpable geopolymer slurries comprising latex, comprising: i) a continuous external aqueous phase, ii) a stabilizing package partially dissolved in the aqueous phase and partially adsorbed onto the surface of the dispersed phase comprising one or more stabilizing agents selected from an anionic surfactant, a non-ionic surfactant and / or a partially water soluble nonionic polymer selected from a protective colloid, HEC, PVA, guar, polyethylene glycol, HPGuar, starch, their derivatives, and the like, where the polymer may be partially degraded and partially grafted a discontinuous internal; and iii) a dispersed quasi-spherical selected from either an oil phase or an emulsion polymerization polymer (produced via a known polymerization initiation and propagation method in dispersed media as per above), or a emulsified, dispersed polymer.

[0177] In some embodiments, the fluid loss control material can be selected according to the process described herein, by having obtained a ratio of a physicochemical property of interest such as the mean particle diameter Rproperty(i) = Property(i)Proxy brine / Property(i)water close to 1 , or an acceptable value.PATENTDocket No. IS24.1340-WO

[0178] The colloidally active chemically react-able filtrate-able aqueous liquid may be considered an interstitial fluid, as it primarily resides in the space between the react-able solids, including the contact surface between solid and liquid phase upon mixing of the slurry.

[0179] The colloidally active chemically react-able filtrate-able aqueous liquid may comprise at least one type of water selected from freshwater, rainwater, river water, potable water, sea water, deionized, brackish, briny water, produced water, distilled water, filtrated water, reverse osmosis water, desalinated water, and mixtures thereof etc. The aqueous liquid may include one or more monovalent, divalent, trivalent, tetravalent, pentavalent, or hexavalent metallic cations selected from Li+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Fe2+, Mn2+, Zn2+, Co2+, Ti2+, B3+, Al3+, Fe3+, Mn3+, Co3+, Ni3+, Ti3+, U3+, Ti4+,Zr4+, Mn4+, Ce4+, U4+, Th4+, U5+, U6+, in hydrated form, or in the form of aqueous complexes derived thereof, and organic cations selected from quaternary ammonium comprising alkyl ammonium, or aryl ammonium, and mixtures thereof, and alkyl phosphonium, aryl phosphonium, and mixtures thereof.

[0180] The aqueous liquid may include one or more monovalent, divalent, or trivalent inorganic anions, selected from F-, Cl’, Br, I-, S2-, NOs-, SO42-, SO32COs2-, B(OH)4‘, AI(OH)4’, PO43', SiO44, TiO42’, TiOa’, ZrOa2’, VO43in equilibrium with a concentration of protons, or hydronium ions, resulting from the presence in the water of hydroxyl ions in a concentration exceeding 1M, 2M, 2.5M, and 2.90 M, where the hydroxyl ions can be the result of the addition of monovalent cation hydroxides, carbonates, bicarbonates, and or phosphates, and / or divalent oxides to the water, followed by precipitation of lower solubility hydroxides, oxides, carbonates, sulfates, sulfides, and / or phosphates of other cations present in the fluid while maintaining charge neutrality in the fluid.

[0181] In some embodiments, the colloidally active chemically react-able filtrateable aqueous liquid includes dispersed, dissolved partially dissolved or colloidal salts derived from supersaturation and or precipitation of such hydroxides, oxides, carbonates, sulfates, sulfides, and / or phosphates, potentially other inorganicPATENTDocket No. IS24.1340-WOpolymeric species resulting from the dissolution precipitation of aluminosilicates. For this disclosure the properties of interest of such colloidally active chemically react-able filtrate-able aqueous liquid may include: a high hydroxyl ion activity (*), presence of reacting anions including at least one of aluminates, silicates, sialites, phosphates, carbonates, in monomeric and oligomeric state, electrical neutrality, through the presence of cations, serving as counterions, and high overall ionic strength, which can be defined as a measure of the concentration of ions in that solution.

[0182] One parameter of relevance in the disclosed slurries is the slurry viscosity, and in particular the relative viscosity of the aqueous fluid. For the slurries of interest, the estimated relative viscosity hr can be hr >1.01, defined as the ratio between the colloidally active chemically react-able filtrate-able aqueous liquid viscosity hiiquid resulting from the interaction between the water and the ions, the temperature at which the fluid is prepared, and the additional viscosity resulting from the dissolution of organic materials such as foamers, retarders, accelerants, polymeric materials incorporated into the fluid, such as viscosifiers, dispersants, flocculants, precipitants, and the viscosity of deionized water hw at the same temperature as the fluid, where hr = hiiquid / hw.

[0183] This relative viscosity hr measurement could be performed with capillary viscometers, automated liquid viscometers such as those used in size exclusion chromatography, for instance the “viscotek” detector, or advanced rheometers with suitable sensitivity, (contravis, paar, haake, etc.), upon separation of the “colloidally active chemically react-able filtrate-able aqueous liquid” from the reactable solid phase by, for instance, filtration of the slurry.

[0184] The measurement of slurry viscosity hsiurry, which is typically performed with an industry viscometer following API 10B as the measurement of choice to predict slurry pumpability, does consider the additional viscosifying effect of dispersed particulates hsoiids. The overall slurry viscosity could be considered as:hfluid — hw * hsoiidsPATENTDocket No. IS24.1340-WOAnd thus, the contribution of the solids can be derived from the overall viscosity as:hsolids=hfluid / hwFor reference many models have been described to introduce the contribution of the solid to the viscosity, starting with the simplest model of monodisperse spheres by Einstein wherehsolids — hfluid * [1 + (5 / 2) * Fparticles]Where Fparticles is the volume fraction of monodispersed particles in the fluid, an equation that effective describes the contribution of solids in small concentrations. Other empirical models such as the Batchelor Model incorporate higher exponent polynomial contributions of the volume fraction of monodispersed particles as permore realistic models for higher volume fractions of monodispersed particles are used in the industry, such as the Krieger-Dogherty equation (I. M. Krieger and T. J. Dougherty, Trans. Soc. Rheol. 3, 137-152 (1959).)where fmax is the theoretical maximum packing density of those monodispersed spheres, which can be 0.52 or 0.74 depending on the sphere packing scheme, with a well-established value of 0.64 considered for the random close packing of spheres. Other models may take into consideration the polydispersity of the spherical particles, such as those proposed by R. Sudduth (A generalized model to predict the viscosity of solutions with suspended particles. I Richard D. Sudduth Journal of Applied Polymer Science Volume 48, Issuel Pages 25-36), where fmax is calculated as a function of the polydispersity of the particle size distribution. Other empirical and geometrical considerations are to be considered when non-idealized particles are considered, non-spherical, and non-round.

[0185] Such relative viscosity hr estimated from the “colloidally active chemically react-able filtrate-able aqueous liquid” viscosity hiiquid and the viscosity of deionized water hw is considered as a time dependent parameter, as the chemical reactions and colloidal effects in the fluid are very dynamic and cannot be frozen in place for a time independent effective measurement of the viscosity.PATENTDocket No. IS24.1340-WOEXAMPLESExample 1

[0186] The fluid loss of geopolymer slurries formed from a geopolymer composition including aluminosilicate and a fluid loss control material was measured.

[0187] The examples below demonstrate the impact of ionic strength in the fluid loss control material. The detailed slurry recipe is presented in Table 2.Table 2Table 2 shows a basic composition of the Geopolymer Slurry with variation of the activator package and inorganic salts to demonstrate the impact of the system’s ionic strength.

[0188] FIG. 6 illustrates fluid loss in non-activated systems at 36°C. The example in FIG. 6 is a non-activated system with slag, fly ash C, and cement with the same fluid loss control material where the fluid loss of the slurry was controlled. After increasing the ionic strength of the system with the use of inorganic salts, the control of the fluid loss decreased. FIG. 6 demonstrates how the ionic strength can influence the fluid loss control independent of the geopolymer without an activator package. (Figure 2: BHCT=36 degC | SVF=40% | No activators | 1% BWOC FLAC based AMPS / Acrylamide copolymer).

[0189] FIG. 6 illustrates the system's results at 36°C, while FIG. 7 illustrates the results at 66°C. This comparison aims to confirm whether the hypothesis holds true at different temperature levels. FIG. 7 illustrates fluid loss in non-activatedPATENTDocket No. IS24.1340-WOsystems at 66°. (FIG. 7: BHCT=66 degC | SVF=40% | No activators | 1% BWOC FLAC based AMPS / Acrylamide copolymer).Example 2

[0190] FIG. 8 illustrates fluid loss in alkali activated systems and illustrates a system with various activation packages compared to systems that have not been activated, highlighting the impact of ionic strength on these systems. FIG. 8 shows that when the activator is included in the system, sodium carbonate, sodium metasilicate, or the package with sodium carbonate + calcium hydroxide increases the ionic strength and consequently increases the fluid loss independent of the raw material (Fly Ash C or Slag). (FIG. 4. BHCT=36 degC | 14.8 ppg (neat) | 1% BW0C FLAC based AMPS / Acrylamide copolymer).Example 3

[0191] FIG. 9 illustrates the effect of the activator’s chemistry on fluid loss performance. FIG. 9 compares the systems with slag, base raw material, and the result of fluid loss control when utilized with higher ionic strength activators or activator packages as sodium carbonate, sodium metasilicate or the packages with sodium carbonate and calcium hydroxide, with activator packages with lower ionic strength, as example calcium hydroxide, strontium hydroxide, barium hydroxide or cement in 5% by weight of slag. (Figure 5. BHCT=36 degC | 14.8 ppg (neat) | 0-5% of Activator | 1% BWOC FLAC based AMPS / Acrylamide copolymer).Example 4

[0192] FIG. 10 illustrates fluid loss value of slag geopolymer slurries activated by sodium carbonate (6% BWOC) and calcium hydroxide (5% BWOC). Fluid loss additives used are 1% AMPS / AA copolymer and 1 gal / sack PVA / PVP.Example 5

[0193] The fluid loss of different geopolymer compositions including different fluid loss control materials was tested. FIG. 11 is a graph illustrating the measured fluid loss value of 15.8 ppg geopolymer slurries including different fluid loss control materials versus a control slurry without a fluid loss control material. ThePATENTDocket No. IS24.1340-WOgeopolymer slurries that were tested included a geopolymer slurry without fluid loss control materials (fluid 1); a geopolymer slurry including a fluid loss control material including styrene butadiene (fluid 2); a geopolymer slurry including a fluid loss control material including crosslinked polyvinyl acetate crosslinked with pentaerythritol allyl ether (fluid 3); a geopolymer slurry including a fluid loss control material including a crosslinked copolymer of AMPS (about 5.1 mole percent) and N,N-diethylacrylamide (about 92.8 mole percent) and including a crosslinker comprising methylene bisacrylamide (about 2.10 mole percent) (fluid 4); a geopolymer slurry including a fluid loss control material including a crosslinked polymer of acrylamide (about 25.22 mole percent), AMPS (about 25.04 mole percent), and N,N-diethylacrylamide (about 47.74 mole percent), and including a crosslinker comprising methylene bisacrylamide (about 2.02 mole percent) (fluid 5); a geopolymer slurry including a fluid loss control material including a copolymer of AMPS (about 7.11 mole percent) and acrylamide (about 86.37 mole percent), crosslinked with methylene bisacrylamide (about 0.51 mole percent), and including an anchoring material including triallyl amine (about 6.0 mole percent) (fluid 6); and a geopolymer slurry including a fluid loss control material including a copolymer of AMPS (about 60.32 mole percent) and acrylamide (about 33.65 mole percent), crosslinked with methylene bisacrylamide (about 2.02 mole percent), and including an anchoring material including maleic anhydride (about 4.01 mole percent) (fluid 7). Each of the fluids including fluid loss control materials included about 1.0 gallon per sack of the fluid loss control material. With reference to FIG. 11, fluid 6 and fluid 7 including the copolymers exhibited a fluid loss about as low as or lower than fluid 2, which included a synthetic material (styrene butadiene).

[0194] Table 3 below compares the thickening time of fluid 2 and fluid 7. With reference to Table 3, fluid 7 reached 70 Bearden units (Be) and 100 Be faster than fluid 2, indicating that the fluid loss control material in fluid 7 was not non-retarding, or did not delay the setting of the geopolymer slurry. The geopolymer slurries had a density of about 15.8 pounds per gallon.PATENTDocket No. IS24.1340-WOTable 3Example 6

[0195] The fluid loss of geopolymer compositions including no fluid loss control material, fluid 2, and fluid 7 were compared in a high ionic strength environment. To confirm the fluid loss control performance of the fluid loss material in fluid 7 (that was a 15.8 ppg slurry), a different slurry density and geopolymer design was tested. FIG. 12 is a graph illustrating the measured fluid loss value of the different geopolymer slurries at 11.4 ppg slurry density. The data presents the fluid loss value of the lightweight geopolymer slurries having two different fluid loss control materials versus a control slurry without a fluid loss control polymer. With reference to FIG. 12, fluid 7 had a fluid loss material synthesized from AMPS, acrylamide, methylene bisacrylamide, and maleic anhydride, and exhibited a substantially lower fluid loss than the base fluid (the control slurry, or fluid 1) and a lower fluid loss than fluid 2 that had styrene butadiene as a fluid loss control material to represent a benchmark fluid loss control material. To illustrate the dependence of the fluid loss control material on the concentration of the fluid loss control material, FIG. 13 is a graph illustrating the fluid loss control performance of the same fluid loss control material (fluid 7 in FIG. 11 and FIG. 12) at different concentrations. As shown in FIG. 13, the fluid loss value reduces with increasing concentration of the fluid loss material in the geopolymer slurry.

[0196] One or more specific embodiments of the present disclosure are described herein. These described embodiments are examples of the presently disclosed techniques. Additionally, in an effort to provide a concise description of these embodiments, not all features of an actual embodiment may be described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerousPATENTDocket No. IS24.1340-WOembodiment-specific decisions will be made to achieve the developers’ specific goals, such as compliance with system-related and business-related constraints, which may vary from one embodiment to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.

[0197] The articles “a,” “an,” and “the” are intended to mean that there are one or more of the elements in the preceding descriptions. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements. Additionally, it should be understood that references to “one embodiment” or “an embodiment” of the present disclosure are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features. For example, any element described in relation to an embodiment herein may be combinable with any element of any other embodiment described herein. Numbers, percentages, ratios, or other values stated herein are intended to include that value, and also other values that are “about” or “approximately” the stated value, as would be appreciated by one of ordinary skill in the art encompassed by embodiments of the present disclosure. A stated value should therefore be interpreted broadly enough to encompass values that are at least close enough to the stated value to perform a desired function or achieve a desired result. The stated values include at least the variation to be expected in a suitable manufacturing or production process, and may include values that are within 5%, within 1%, within 0.1%, or within 0.01% of a stated value.

[0198] A person having ordinary skill in the art should realize in view of the present disclosure that equivalent constructions do not depart from the spirit and scope of the present disclosure, and that various changes, substitutions, and alterations may be made to embodiments disclosed herein without departing from the spirit and scope of the present disclosure. Equivalent constructions, including functional “means-plus-function” clauses are intended to cover the structures described herein as performing the recited function, including both structuralPATENTDocket No. IS24.1340-WOequivalents that operate in the same manner, and equivalent structures that provide the same function. It is the express intention of the applicant not to invoke means-plus-function or other functional claiming for any claim except for those in which the words ‘means for’ appear together with an associated function. Each addition, deletion, and modification to the embodiments that falls within the meaning and scope of the claims is to be embraced by the claims.

[0199] The terms “approximately,” “about,” and “substantially” as used herein represent an amount close to the stated amount that still performs a desired function or achieves a desired result. For example, the terms “approximately,” “about,” and “substantially” may refer to an amount that is within less than 5% of, within less than 1% of, within less than 0.1% of, and within less than 0.01% of a stated amount. Further, it should be understood that any directions or reference frames in the preceding description are merely relative directions or movements. For example, any references to “up” and “down” or “above” or “below” are merely descriptive of the relative position or movement of the related elements.

[0200] The present disclosure may be embodied in other specific forms without departing from its spirit or characteristics. The described embodiments are to be considered as illustrative and not restrictive. The scope of the disclosure is, therefore, indicated by the appended claims rather than by the foregoing description. Changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims

PATENTDocket No. IS24.1340-WOCLAIMSWhat is claimed is:

1. A geopolymer slurry, comprising:at least one aluminosilicate source including an amorphous aluminosilicate material;an activator;a fluid loss control material including a crosslinked polymer including a reaction product of:one or more monomers including one or more of acrylamide, 2-acrylamido- 2-methyl propane sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, vinyl acetate, an N-substituted acrylamide, methacrylamide, an N-substituted methacrylamide, an acrylate, a methacrylate, acrylic acid, methacrylic acid, an N-vinylamide, an N- allylamide, vinyl alcohol, a vinyl ether, a vinyl ester, allyl alcohol, an allyl ether, an allyl ester, vinylpyridine, a vinyl sulfonate, vinyl sulfonic acid, styrene sulfonate, an allyl sulfonate, vinylimidazole, allylimidazole, or diallyldimethylammonium chloride; and a crosslinker including one or more of methylene bisacrylamide, triallyl amine, pentaerythritol allyl ether, triallyl-triazine-trione, divinyl ether, diallyl ether, a vinyl or allyl ether of polyglycols, a vinyl or allyl ether of polyols, divinylbenzene, 1 ,3-divinylimidazolidin-2-one, divinyltetrahydropyrimidin-2(1H)-one, a diene, an allyl amine, N- vinyl-3(E)-ethylidene pyrrolidone, or ethylidene bis(N- vinylpyrrolidone); andan aqueous base fluid.

2. The geopolymer slurry of claim 1, wherein the fluid loss control material includes a reaction product of an anchoring material including one or more of maleic anhydride, carbonyl phosphonicacid, vinyl phosphonic acid, and itaconic acid.PATENTDocket No. IS24.1340-WO3. The geopolymer slurry of claim 1, wherein the fluid loss control material includes greater than about 50.0 mole percent 2-acrylamido-2-methyl propane sulfonic acid.

4. The geopolymer slurry of claim 1, wherein the fluid loss control material includes from about 20.0 mole percent to about 90.0 mole percent acrylamide.

5. The geopolymer slurry of claim 1, wherein the fluid loss control material includes a reaction product of 2-acrylamido-2-methyl propane sulfonic acid, methylene bisacrylamide, and at least one of N,N-dimethylacrylamide or N,N-diethylacrylamide.

6. The geopolymer slurry of claim 1, wherein the fluid loss control material includes a reaction product of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, and methylene bisacrylamide.

7. The geopolymer slurry of claim 6, wherein the fluid loss control material includes a reaction product of the acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, and methylene bisacrylamide with one or both of N,N-dimethylacrylamide or N,N-diethylacrylamide.

8. The geopolymer slurry of claim 6, wherein the fluid loss control material includes a reaction product of the acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, and methylene bisacrylamide with an anchoring material.

9. The geopolymer slurry of claim 8, wherein the anchoring material includes triallyl amine or maleic anhydride.PATENTDocket No. IS24.1340-WO10. The geopolymer slurry of claim 1, wherein the fluid loss control material includes crosslinked polyvinyl acetate crosslinked with pentaerythritol allyl ether.

11. The geopolymer slurry of claim 1, wherein the crosslinked polymer includes tannin grafted onto an N-substituted acrylamide-based copolymer.

12. The geopolymer slurry of claim 11 , wherein:the N-substituted acrylamide-based copolymer includes the reaction product of acrylamide and 2-acrylamido-2-methyl propane sulfonic acid; and the crosslinker includes methylene bisacrylamide.

13. The geopolymer slurry of claim 1, wherein the fluid loss control material includes an emulsion.

14. The geopolymer slurry of claim 1, wherein the fluid loss control material constitutes from about 0.1 weight percent to about 10.0 weight percent by weight of the amorphous aluminosilicate material.

15. The geopolymer slurry of claim 1, further comprising one or more fillers comprising density reducing particles having a density less than 2 g / cm3and including one or more of hollow glass beads or ceramic microspheres (cenospheres), elastomer, plastic particles such as polypropylene beads, rubber particles, uintaite, vitrified shale, petroleum coke, coal, or combinations thereof.

16. The geopolymer slurry of claim 1, further comprising one or more fillers comprising density increasing particles having a density greater than 2 g / cm3and including one or more of cement, hematite, barite, ilmenite, crystalline silica sand, silica flour, crushed granite, or manganese tetroxide.PATENTDocket No. IS24.1340-WO17. The geopolymer slurry of claim 1, wherein the activator includes at least one alkali activator.

18. The geopolymer slurry of claim 17, wherein the at least one alkali activator includes one or more of:an alkali metal hydroxide comprising one or more of lithium hydroxide, sodium hydroxide, or potassium hydroxide;an alkaline-earth metal hydroxide comprising one or more of calcium hydroxide, magnesium hydroxide, strontium hydroxide, or barium hydroxide; an alkaline earth metal oxide comprising one or more of calcium oxide, magnesium oxide, strontium oxide, or barium oxide;an alkaline earth metal peroxide comprising one or more of calcium peroxide or magnesium peroxide; orone or more of an alkali salt comprising one or more of a metal carbonate, a metal sulfate, a metal sulfite, a metal phosphate, metal oxalate, a metal silicate, a metal fluoride, a metal hexafluoride, a metal iodate, or a metal molybdate.

19. The geopolymer slurry of claim 17, wherein the at least one alkali activator includes one or more of sodium silicate, sodium metasilicate, potassium silicate, calcium silicate, calcium metasilicate, or sodium carbonate.

20. A geopolymer composition, comprising:at least one aluminosilicate source including an amorphous aluminosilicate material;an activator; anda fluid loss control material including a crosslinked polymer including a reaction product of:PATENTDocket No. IS24.1340-WOone or more monomers including one or more of acrylamide, 2-acrylamido- 2-methyl propane sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, vinyl acetate, an N-substituted acrylamide, methacrylamide, an N-substituted methacrylamide, an acrylate, a methacrylate, acrylic acid, methacrylic acid, an N-vinylamide, an N- allylamide, vinyl alcohol, a vinyl ether, a vinyl ester, allyl alcohol, an allyl ether, an allyl ester, vinylpyridine, a vinyl sulfonate, vinyl sulfonic acid, styrene sulfonate, an allyl sulfonate, vinylimidazole, allylimidazole, or diallyldimethylammonium chloride; and a crosslinker including one or more of methylene bisacrylamide, triallyl amine, pentaerythritol allyl ether, triallyl-triazine-trione, divinyl ether, diallyl ether, a vinyl or allyl ether of polyglycols, a vinyl or allyl ether of polyols, divinylbenzene, 1 ,3-divinylimidazolidin-2-one, divinyltetrahydropyrimidin-2(1H)-one, a diene, an allyl amine, N~ vinyl-3(E)-ethylidene pyrrolidone, or ethylidene bis(N~ vinylpyrrolidone).

21. The geopolymer composition of claim 20, wherein the fluid loss control material includes a reaction product of the one or more monomers, the crosslinker, and an anchoring material including one or more of maleic anhydride, maleic acid, carbonyl phosphonic acid, vinyl phosphonic acid, or itaconic acid.

22. A method of cementing a subterranean borehole, the method comprising:mixing water with a geopolymer composition to form a geopolymer slurry, the geopolymer composition including:at least one aluminosilicate source including an amorphous aluminosilicate material;an activator; anda fluid loss control material including a crosslinked polymer including a reaction product of:PATENTDocket No. IS24.1340-WOone or more monomers including one or more of acrylamide, 2- acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, N,N-diethylacrylamide, vinyl acetate, an N-substituted acrylamide, methacrylamide, an N- substituted methacrylamide, an acrylate, a methacrylate, acrylic acid, methacrylic acid, an N-vinylamide, an N- allylamide, vinyl alcohol, a vinyl ether, a vinyl ester, allyl alcohol, an allyl ether, an allyl ester, vinylpyridine, a vinyl sulfonate, vinyl sulfonic acid, styrene sulfonate, an allyl sulfonate, vinylimidazole, allylimidazole, or diallyldimethylammonium chloride; anda crosslinker including one or more of methylene bisacrylamide, triallyl amine, pentaerythritol allyl ether, triallyl-triazine-trione, divinyl ether, diallyl ether, a vinyl or allyl ether of polyglycols, a vinyl or allyl ether of polyols, divinylbenzene, 1,3- divinylimidazolidin-2-one. divinyltetrahydropyrimidin-2(1 H)- one, a diene, an allyl amine, N-vinyl~3(E)~ethylidene pyrrolidone, or ethylidene bis(N-vinylpyrrolidone); and pumping the geopolymer slurry into an annular space between a casing and a subterranean formation defining the subterranean borehole.

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