AU2015362929B2

AU2015362929B2 - Hydraulic fracturing composition, method for making and use of same

Info

Publication number: AU2015362929B2
Application number: AU2015362929A
Authority: AU
Inventors: Leiming Li; Dong Shen; Hong Sun; Jia Zhou
Original assignee: Baker Hughes a GE Co LLC
Current assignee: Baker Hughes Holdings LLC
Priority date: 2014-12-15
Filing date: 2015-12-09
Publication date: 2018-02-01
Anticipated expiration: 2035-12-09
Also published as: BR112017011956A2; CA2970488C; WO2016100048A1; RU2679778C2; EP3234060A1; AU2015362929A1; NZ733169A; NO20171068A1; MX2017007128A; RU2017122066A; EP3234060A4; CN107207956A; CA2970488A1; RU2017122066A3

Abstract

A hydraulic fracturing composition includes: a superabsorbent polymer in an expanded state; a plurality of proppant particles disposed in the superabsorbent polymer; a well treatment agent, and a fluid to expand the superabsorbent polymer into the expanded state. A process for treating a well with well treatment agent includes disposing a hydraulic fracturing composition comprising the well treatment agent in a well. The well treatment agent can be a scale inhibitor, tracer, pH buffering agent, or a combination thereof.

Description

(71) Applicant(s)

Baker Hughes, a GE company, LLC (72) Inventor(s)

Shen, Dong;Li, Leiming;Zhou, Jia;Sun, Hong (74) Agent / Attorney

FPA Patent Attorneys Pty Ltd, L 43 101 Collins St, Melbourne, VIC, 3000, AU (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization

International Bureau (43) International Publication Date 23 June 2016 (23.06.2016)

WIPOIPCT (51) International Patent Classification:

C09K 8/03 (2006.01) C09K 8/035 (2006.01) (21) International Application Number:

PCT/US2015/064815 (22) International Filing Date:

December 2015 (09.12.2015) (25) Filing Language: English (26) Publication Language: English (30) Priority Data:

14/570,003 15 December2014(15.12.2014) US (71) Applicant: BAKER HUGHES INCORPORATED [US/US]; P.O. Box 4740, Houston, Texas 77210-4740 (US).

(72) Inventors: SHEN, Dong; 2929 Allen Parkway, Suite 2100, Houston, TX 77019-2118 (US). LI, Leiming; 2929 Allen Parkway, Suite 2100, Houston, TX 77019-2118 (US). ZHOU, Jia; 2929 Allen Parkway, Suite 2100, Houston, TX 77019-2118 (US). SUN, Hong; 2929 Allen Parkway, Suite 2100, Houston, TX 77019-2118 (US).

(81) Designated States (unless otherwise indicated, for every kind of national protection available)·. AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, (10) International Publication Number

WO 2016/100048 Al

DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG,

MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.

(84) Designated States (unless otherwise indicated, for every kind of regional protection available)·. ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,

LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG).

Declarations under Rule 4.17:

— as to applicant's entitlement to apply for and be granted a patent (Rule 4.17(H)) — as to the applicant's entitlement to claim the priority of the earlier application (Rule 4.17(iii))

Published:

— with international search report (Art. 21(3)) (54) Title: HYDRAULIC FRACTURING COMPOSITION, METHOD FOR MAKING AND USE OF SAME

FIG.1

WO 2016/100048 Al (57) Abstract: A hydraulic fracturing composition includes: a superabsorbent polymer in an expanded state; a plurality of proppant particles disposed in the superabsorbent polymer; a well treatment agent, and a fluid to expand the superabsorbent polymer into the expanded state. A process for treating a well with well treatment agent includes disposing a hydraulic fracturing composition comprising the well treatment agent in a well. The well treatment agent can be a scale inhibitor, tracer, pH buffering agent, or a combination thereof.

2015362929 21 Dec 2017

HYDRAULIC FRACTURING COMPOSITION, METHOD FOR MAKING AND USE OF

SAME

CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Application No. 14/570003, filed on December 15, 2014, which is incorporated herein by reference in its entirety.

BACKGROUND [0002] Hydraulic fracturing increases the flow of desirable fluids such as oil and gas from a subterranean formation and involves placing a fracturing fluid into a subterranean formation or zone at a rate and pressure sufficient to impart a stress in the formation or zone with attendant production of a fracture in the formation or zone. Some fracturing fluids contain a viscosifying or gelling agent such as a polysaccharide that breaks shortly before or after placement in the formation.

[0003] Beyond creating the fracture, the fracturing fluid also transports a proppant into the fracture. The proppant is supposed to keep the fracture open after release of the hydraulic pressure. Further, the proppant establishes conductive channels in which the desirable fluids flow to the borehole. Since the proppant provides a higher conductivity than the surrounding rock, the fracture has greater potential for production of hydrocarbons. However, some fracturing fluids break before the fracture closes, and the proppant separates from the fracturing fluid and settles at the bottom of the fracture. In this situation, the proppants settle and concentrate at the bottom of the fracture, and thus the geometry of the fracture and well productivity is impaired.

[0004] Accordingly, compositions and methods that provide relatively high permeability and that enhance the production of hydrocarbons from fractured formations are highly desired.

[0004A]Reference to any prior art in the specification is not an acknowledgment or suggestion that this prior art forms part of the common general knowledge in any jurisdiction or that this prior art could reasonably be expected to be combined with other pieces of prior art by a skilled person in the art.

2015362929 21 Dec 2017

BRIEF DESCRIPTION [0005]In an aspect, the present invention provides a process for disposing a plurality of proppant particles in a fracture, the process comprises: disposing a hydraulic fracturing composition in a downhole environment, the hydraulic fracturing composition comprising: a superabsorbent polymer in an expanded state and configured to break in response to a breaking condition, such that a decomposed polymer is formed from breaking the superabsorbent polymer, the superabsorbent polymer comprising particles having internal crosslinks derived from ethyleneglycol diacrylate, polyethyleneglycol diacrylate, trimethylopropane trimethacrylate, ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, or a combination comprising at least one of the foregoing but no intra-particle crosslinks and being present in a mass concentration from 5 ppt to 100 ppt, based on total volume of the composition, the superabsorbent polymer comprising a repeat unit derived from an acrylic acid, an acrylate, an acrylamide, a vinylpyrrolidone, a vinyl acetate, a 2-acrylamide-2-methylpropanesulfonic acid, a derivative thereof, or a combination thereof; and the superabsorbent polymer in the expanded state having a viscosity of about 1 centipoise to 300 centipoise as measured by Ofite M900 rheometer at a temperature of 180° F, a plurality of proppant particles disposed in a space between adjacent superabsorbent polymer particles prior to release of the plurality of proppant particles from the superabsorbent polymer particles in response to breaking the superabsorbent polymer; a well treatment agent comprising a scale inhibitor, a tracer, a buffering agent, or a combination thereof; and a fluid to expand the superabsorbent polymer into the expanded state; breaking the superabsorbent polymer with a breaker after closing of the fracture commences; and releasing the plurality of proppant particles from superabsorbent polymer to dispose the plurality of proppant particles in the fracture,wherein the hydraulic fracturing composition is free of gelling agents except for the superabsorbent polymer.

[0006] Disclosed herein is a hydraulic fracturing composition comprising: a superabsorbent polymer in an expanded state and configured to break in response to a breaking condition; a plurality of proppant particles disposed in the superabsorbent polymer prior to release of the plurality of proppant particles from the superabsorbent polymer in response to breaking the superabsorbent polymer; an well treatment agent comprising a scale inhibitor, a tracer, a buffering agent, or a combination thereof and a fluid to expand the superabsorbent polymer into the expanded state.

2015362929 21 Dec 2017

BRIEF DESCRIPTION OF THE DRAWINGS [0007] The following descriptions should not be considered limiting in any way.

With reference to the accompanying drawings, like elements are numbered alike:

[0008] FIG. 1 shows proppant particles disposed in a superabsorbent polymer in an expanded state according to an embodiment;

[0009] FIG. 2 shows proppant particles disposed in a superabsorbent polymer in an expanded state according to an embodiment;

[0010] FIG. 3 shows a superabsorbent polymer in an unexpanded state;

[0011] FIG. 4 shows a decomposed polymer and proppant particles;

[0012] FIG. 5 shows a hydraulic fracturing composition disposed in a fracture before a breaking condition;

[0013] FIG. 6 shows a response of the hydraulic fracturing composition of FIG. 5 to a breaking condition;

[0014] FIG. 7 shows a separated fluid and proppant particles disposed in a fracture before the fracture closes;

[0015] FIG. 8 shows an effect on fracture size for proppant particles that settle before the fracture closes;

2A

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PCT/US2015/064815 [0016] FIG. 9 shows proppant particles disposed in guar or a superabsorbent polymer as a function of time at 180°F;

[0017] FIG. 10 shows addition of a breaker to guar or a superabsorbent polymer at

180°F;

[0018] FIG. 11 shows a fracture cell during injection of a hydraulic fracturing composition;

[0019] FIG. 12 shows a fracture cell after injection of water into a hydraulic fracturing composition disposed in the fracture cell;

[0020] FIG. 13 shows the viscosity difference of a SPP fluid alone and a SPP fluid combined with linear gel systems;

[0021] FIG. 14A and FIG. 14B, collectively referred to as FIG. 14, shows the effect of SPP and a linear gel on the foam quality of a foam fracturing fluid;

[0022] FIG. 15 shows a fracture cell after alternating injection of a proppantcontaining fluid comprising SPP, proppant particles, a fluid to expand the SPP, and a proppant-free fluid comprising water and a lubricant; and [0023] FIG. 16 shows a fracture cell after alternating injection of a proppant-free fluid comprising SPP fluid and a proppant-containing fluid comprising water, a lubricant, and proppant particles.

[0024] FIG. 17 shows an effect of fluid pH on viscosity for a superabsorbent polymer.

DETAILED DESCRIPTION [0025] A detailed description of one or more embodiments is presented herein by way of exemplification and not limitation.

[0026] It has been found that a hydraulic fracturing composition described herein creates fractures in a formation and transports proppant particles into the fractures without changing the geometry of the fractures so that hydrocarbon transmission through the fractures and recovery are optimized. The proppant particles remain suspended in the hydraulic fracturing composition without settling to the bottom of the fractures, which enhances production from a well.

[0027] As shown in FIG. 1, the hydraulic fracturing composition 10 includes a superabsorbent polymer 12 (e.g., a plurality of superabsorbent polymer particles 12), a plurality of proppant particles 18 disposed in the superabsorbent polymer 12, and a fluid (not shown) to expand the superabsorbent polymer 12 into the expanded state. In the expanded

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PCT/US2015/064815 state, the superabsorbent polymer 12 is configured to break in response to a breaking condition, and a decomposed polymer is formed from breaking the superabsorbent polymer

12. Upon breaking of the superabsorbent polymer 12, the plurality of proppant particles 18 are released from the superabsorbent polymer 12.

[0028] The superabsorbent polymer 12 includes a plurality of polymer chains 13 having internal crosslinks 14 between the polymer chains 13 of the superabsorbent polymer

12. In an embodiment, the proppant particles 18 are included in a space 22 between adjacent superabsorbent polymer particles 12. In some embodiments, the proppant particles 18 are disposed in the space 22 and confined by intra-particle crosslinks 26 of the superabsorbent polymer particles 12. It is contemplated that the fluid surrounds an exterior 24 of the superabsorbent polymer 12, its interior space 22, inside the particles 12, or a combination thereof.

[0029] The superabsorbent polymer 12 is a crosslinked, neutralized or partially neutralized polymer that is capable of absorbing large amounts of aqueous liquids, such as water, brine, acid, or base, with swelling and the formation of a gel or viscous material, and retains the absorbed fluid under a certain pressure or temperature. The superabsorbent polymer has internal crosslinks, surface crosslinks, or a combination thereof. Superabsorbent polymer particles are particles of superabsorbent polymers or superabsorbent polymer compositions. The acronym SAP may be used in place of superabsorbent polymer, superabsorbent polymer composition, and particles or fibers (and the like) herein.

[0030] The SAP has a hydrophilic network that retains large amounts of aqueous liquid relative to the weight of the SAP. In an embodiment, the SAPs herein are a variety of organic polymers that react with or absorb water and swell when contacted with an aqueous fluid. Non-limiting examples of such SAPs are a polysaccharide material (that, e.g., in a dry state, absorbs and retains a weight amount of water equal to or greater than its own weight), poly 2-hydroxyethyl acrylate, polyalkyl acrylate, polyacrylamide, poly methacrylamide, poly vinylpyrrolidone, and poly vinyl acetate. In one embodiment, the SAP is a copolymer of acrylamide with, for example, maleic anhydride, vinyl acetate, ethylene oxide, ethylene glycol, acrylonitrile, or a combination thereof. Production of SAPs are, e.g., from acrylamide (AM) or acrylic acid and its salts.

[0031] In an embodiment, the SAP is polymerized from nonionic, anionic, cationic monomers, or a combination thereof. Polymerization to form the SAP can be via free-radical polymerization, solution polymerization, gel polymerization, emulsion polymerization,

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PCT/US2015/064815 dispersion polymerization, or suspension polymerization. Moreover, polymerization can be performed in an aqueous phase, in inverse emulsion, or in inverse suspension.

[0032] Examples of nonionic monomers for making the SAP include nonionic monomers such as acrylamide, methacrylamide, N,N-di(Ci-Cs alkyl)acrylamide such asN,Ndimethylacrylamide, vinyl alcohol, vinyl acetate, allyl alcohol, hydroxyethyl methacrylate, acrylonitrile, and derivatives thereof. Such derivatives include, for example, acrylamide derivatives, specifically alkyl-substituted acrylamides or aminoalkyl-substituted derivatives of acrylamide or methacrylamide, and are more specifically acrylamide, methacrylamide, Nmethylacrylamide, N-methylmethacrylamide, Ν,Ν-dimethylacrylamide, N-ethylacrylamide, Ν,Ν-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N,Ndimethylaminopropylacrylamide, Ν,Ν-dimethylaminoethylacrylamide, N-tert-butyl acrylamide, N-vinylformamide, N-vinylacetamide, acrylonitrile, methacrylonitrile, or a combination thereof.

[0033] Examples of anionic monomers for making the SAP include ethylenically unsaturated anionic monomers containing acidic groups including a carboxylic group, a sulfonic group, a phosphonic group, a salt thereof, a derivative thereof, or a combination thereof. In an embodiment, the anionic monomer is acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, oc-chloroacrylic acid, βcyanoacrylic acid, β-methylacrylic acid (crotonic acid), oc-phenylacrylic acid, βacryloyloxypropionic acid, sorbic acid, oc-chlorosorbic acid, 2’-methylisocrotonic acid, cinnamic acid, p-chlorocinnamic acid, β-stearyl acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, 2-acrylamido-2-methylpropane sulphonic acid, allyl sulphonic acid, vinyl sulphonic acid, allyl phosphonic acid, vinyl phosphonic acid, or a combination thereof.

[0034] Examples of cationic monomers for making the SAP include an Ν,Ν-di-Ci-Cs alkylamino-Ci-Cs alkylacrylate (e.g., Ν,Ν-dimethyl amino ethyl acrylate), Ν,Ν-di-Ci-Cs alkylamino-Ci-Cs alkylmethacrylate (e.g., Ν,Ν-dimethyl amino ethyl methacrylate), including a quaternary form (e.g., methyl chloride quaternary forms), diallyldimethyl ammonium chloride, Ν,Ν-di-Ci-Cs alkylamino-Ci-Cs alkylacrylamide, and a quaternary form thereof such as acrylamidopropyl trimethyl ammonium chloride.

[0035] In an embodiment, the SAP is an amphoteric SAP, containing both cationic substituents and anionic substituents. The cationic substituents and anionic substituents occur in various stoichiometric proportions, including one-to-one, or one substituent is present in a

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PCT/US2015/064815 greater stoichiometric amount than the other substituent. Representative amphoteric SAPs include terpolymers of nonionic monomers, anionic monomers and cationic monomers.

[0036] In an embodiment, the SAP includes a guar gum and carrageenan. Suitable materials include those disclosed in Japanese Patent Application No. P2003-154262A, the content of which is incorporated by reference herein in its entirety.

[0037] According to an embodiment, the guar gum used in the SAP includes natural guar gum as well as enzyme treated guar gum; the latter having been obtained by treating natural guar gum with galactosidase, mannosidase, or another enzyme. The guar gum may further be a galactomannan derivative prepared by treating natural guar gum with chemicals to introduce carboxyl groups, hydroxyl alkyl groups, sulfate groups, phosphate groups, and the like. In addition, in an embodiment, a natural polysaccharide, other than guar and carrageenan, is included. Exemplary natural polysaccharides include starch, cellulose, xanthan gum, agar, pectin, alginic acid, tragacanth gum, pluran, gellan gum, tamarind seed gum, cardlan, gum arabic, glucomannan, chitin, chitosan, hyaluronic acid, and the like.

[0038] Carrageenan is an ionic linear polysaccharide that includes repeating galactose units that individually may be sulfated or unsulfated. Specific carrageenan types include kappa, iota, lambda, and the like. In some embodiments, a mixture of carrageenan types is used. In a specific embodiment, a carrageenan or a carrageenan-like material that form a gel is used. In addition to natural carrageenan, suitable carrageenans include enzyme-treated substances of natural carrageenan or derivatized carrageenan, e.g., those prepared by treating natural carrageenan (e.g., with a chemical) to introduce a functional group (e.g., a carboxyl group, hydroxyl alkyl group, sulfate group, phosphate group, and the like).

[0039] The SAP includes a plurality of crosslinks among the polymer chains of the SAP. According to an embodiment, the crosslinks are covalent and result from crosslinking the SAP with a crosslinker. In an embodiment, the crosslinker is an ethylenically unsaturated monomer that contains, e.g., two sites of ethylenic unsaturation (i.e., two ethylenically unsaturated double bonds), an ethylenically unsaturated double bond and a functional group that is reactive toward a functional group (e.g., an amide group) of the polymer chains of the SAP, or several functional groups that are reactive toward functional groups of the polymer chains of the SAP. In an embodiment, the degree of crosslinking in the SAP herein is selected to control the amount of swelling (i.e., fluid absorption or volume expansion) of the SAP.

[0040] Exemplary crosslinkers include a diacrylamide or methacrylamide of a diamine such as a diacrylamide of piperazine; an acrylate or methacrylate ester of a di, tri,

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PCT/US2015/064815 tetrahydroxy compound including ethyleneglycol diacrylate, polyethyleneglycol diacrylate, trimethylopropane trimethacrylate, ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, and the like; a divinyl or diallyl compound separated by an azo group such as a diallylamide of 2,2’-azobis(isobutyric acid) or a vinyl or allyl ester of a di or tri functional acid. Additional crosslinkers include water-soluble diacrylates such as poly(ethylene glycol) diacrylate (e.g., PEG 200 diacrylate) or PEG 400 diacrylate and polyfunctional vinyl derivatives of a polyalcohol such as ethoxylated (9-20) trimethylol triacrylate. Further examples of the crosslinker include aliphatic unsaturated amides, such as methylenebisacrylamide or ethylenebisacrylamide; aliphatic esters of polyols or alkoxylated polyols with ethylenically unsaturated acids, such as di(meth)acrylates or tri(meth)acrylates of butanediol, ethylene glycol, polyglycols, trimethylolpropane; di- and triacrylate esters of trimethylolpropane (which is oxyalkylated (such as ethoxylated) with an alkylene oxide such ethylene oxide); acrylate and methacrylate esters of glycerol or pentaerythritol; acrylate and methacrylate esters of glycerol and pentaerythritol oxyethylated with, e.g., ethylene oxide; allyl compounds (such as allyl(meth)acrylate, alkoxylated allyl(meth)acrylate reacted with,

e.g., ethylene oxide, triallyl cyanurate, triallyl isocyanurate, maleic acid diallyl ester, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, diols, polyols, hydroxy allyl or acrylate compounds and allyl esters of phosphoric acid or phosphorous acid); or monomers that are capable of crosslinking, such as N-methylol compounds of unsaturated amides, such as of methacrylamide or acrylamide, and the ethers derived therefrom. A combination of the crosslinkers also can be employed.

[0041] In an embodiment, the SAP is a particle (or fiber or other format) that includes surface crosslinks, which occur external to the interior of the SAP. The surface crosslinks,

e.g., result from addition of a surface crosslinker to the SAP particle and heat-treatment. The surface crosslinks increase the crosslink density of the SAP near its surface with respect to the crosslinking density of the interior of the SAP. Some surface crosslinkers have a functional group that is reactive toward a group of the polymer chains of the SAP, e.g., an acid or amide group. The surface crosslinker are one of the previously mentioned crosslinkers and include a functional group such as an alcohol, amine, aldehyde, or carboxylate group. In an embodiment, surface crosslinkers have multiple different functional groups such as polyols, polyamines, polyaminoalcohols, and alkylene carbonates. Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, polyglycerol, propylene glycol, diethanolamine, triethanolamine, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, sorbitan fatty acid esters, ethoxylated sorbitan fatty

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PCT/US2015/064815 acid esters, trimethylolpropane, ethoxylated trimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, polyvinyl alcohol, sorbitol, ethylene carbonate, and propylene carbonate can be used. The surface crosslinkers also provide the SAP with a chemical property that the polymer chains of the SAP did not have before surface crosslinking and control chemical properties of the SAP, e.g., hydrophobicity, hydrophilicity, or adhesiveness of the SAP to other materials such as minerals (e.g., silicates) or other chemicals such as petroleum compounds (e.g., hydrocarbons, asphaltene, and the like). Other crosslinkers include borate, titanate, zirconate, aluminate, chromate, or a combination thereof. Boron crosslinkers include, e.g., boric acid, sodium tetraborate, encapsulated borates, and the like. In some embodiments, borate crosslinkers are used with buffering agents and pH control agents such as sodium hydroxide, magnesium oxide, sodium sesquicarbonate, and sodium carbonate, amines (such as hydroxyalkyl amines, anilines, pyridines, pyrimidines, quinolines, pyrrolidines, and carboxylates such as acetates and oxalates), delay agents such as sorbitol, aldehydes, sodium gluconate, and the like. Zirconium crosslinkers, e.g., zirconium lactates (e.g., sodium zirconium lactate), triethanolamines, 2,2’-iminodiethanol, or a combination thereof are used in certain embodiments. Titanates for crosslinking include, e.g., lactates and triethanolamines, and the like.

[0042] In an embodiment, the SAP includes a repeat unit that comprises an acrylate, an acrylamide, a vinylpyrrolidone, a vinyl ester (e.g., a vinyl acetate), a vinyl alcohol, a derivative thereof, or a combination thereof. According to an embodiment, the SAP is a polyacrylamide having crosslinks that are polyethylene glycol diacrylate. In some embodiments, the SAP is polyacrylic acid, wherein the crosslinks are vinyl ester oligomer. In an embodiment, the SAP is poly(acrylic acid) partial sodium salt graft poly(ethylene glycol), which is commercially available from Sigma Aldrich. Further, the SAP can be in a number of formats, including a particle (e.g., a powder), fiber, strand, braid, and the like, or a combination thereof. The size of the SAP is from 10 pm to 100,000 pm, specifically 50 pm to 10,000 pm, and more specifically 50 pm to 1,000 pm. As used herein, “size” refers to the largest linear dimension, e.g., a diameter in a spherical particle. Particles of the SAP are any shape including spherical, angular, and polyhedral. According to an embodiment, the SAP is a particle with pores or spaces between the polymer chains of the SAP that admits entrance of a fluid or proppant particle therein. The hydraulic fracturing composition includes a plurality of SAP particles (or other format such as fiber or braid) that coalesces together and form a single mass of SAP, herein also referred to as the superabsorbent polymer (SAP). Moreover, although FIG. 1 shows the SAP as a plurality of superabsorbent polymer particles 12, the

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PCT/US2015/064815

SAP is a plurality of superabsorbent polymer fibers 12 as shown in FIG. 2 in some embodiments. A combination of the various formats of the SAP is contemplated for some embodiments.

[0043] The SAP with crosslinks is useful as a carrier for a fluid or proppant particles. In a fracturing operation (e.g., hydraulic fracturing), the proppant particles disposed in the SAP remain in the fracture and prop open the fracture when pressure used to form the fracture is released as SAPs are broken in response to the breaking condition. The proppant particles have a size from 1 pm to 2000 pm, specifically 10 pm to 1000 pm, and more specifically 10 pm to 500 pm. Further, the proppant particles have any shape including spherical, angular, and polyhedral and are monodisperse or polydisperse with an average particle size distribution that is unimodal or multimodal, e.g., bimodal.

[0044] In an embodiment, due to the relative size of the SAP and the proppant particles, the proppant particles are disposed between neighboring SAP particles (FIG. 1 item) 12 or fibers (FIG. 2 item 12), e.g., in pores or channels formed by voids or spaces 22 between such adjacent SAP particles or fibers or are disposed within individual SAP particles or fibers in the expanded state of the SAP.

[0045] The proppant particles include a ceramic, sand, a mineral, a nutshell, gravel, glass, resinous particles, polymeric particles, or a combination thereof. In an embodiment, the proppant particles are selected depending on the particular application of the hydraulic fracturing composition. Examples of the ceramic include an oxide-based ceramic, nitridebased ceramic, carbide-based ceramic, boride-based ceramic, silicide-based ceramic, or a combination thereof. In an embodiment, the oxide-based ceramic is silica (SiO₂), titania (TiO₂), aluminum oxide, boron oxide, potassium oxide, zirconium oxide, magnesium oxide, calcium oxide, lithium oxide, phosphorous oxide, and/or titanium oxide, or a combination thereof. The oxide-based ceramic, nitride-based ceramic, carbide-based ceramic, boridebased ceramic, or silicide-based ceramic contain a nonmetal (e.g., oxygen, nitrogen, boron, carbon, or silicon, and the like), metal (e.g., aluminum, lead, bismuth, and the like), transition metal (e.g., niobium, tungsten, titanium, zirconium, hafnium, yttrium, and the like), alkali metal (e.g., lithium, potassium, and the like), alkaline earth metal (e.g., calcium, magnesium, strontium, and the like), rare earth (e.g., lanthanum, cerium, and the like), or halogen (e.g., fluorine, chlorine, and the like). Exemplary ceramics include zirconia, stabilized zirconia, mullite, zirconia toughened alumina, spinel, aluminosilicates (e.g., mullite, cordierite), perovskite, silicon carbide, silicon nitride, titanium carbide, titanium nitride, aluminum carbide, aluminum nitride, zirconium carbide, zirconium nitride, iron carbide, aluminum

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PCT/US2015/064815 oxynitride, silicon aluminum oxynitride, aluminum titanate, tungsten carbide, tungsten nitride, steatite, and the like, or a combination thereof.

[0046] Examples of suitable sands for the proppant particles include, but are not limited to, Arizona sand, Wisconsin sand, Badger sand, Brady sand, and Ottawa sand. In an embodiment, the proppant particles made of a mineral such as bauxite are sintered to obtain a hard material. In an embodiment, the bauxite or sintered bauxite has a relatively high permeability such as the bauxite material disclosed in US Patent No. 4,713,203, the content of which is incorporated by reference herein in its entirety.

[0047] Naturally occurring proppant particles include nut shells such as walnut, coconut, pecan, almond, ivory nut, brazil nut, and the like; seed shells of fruits such as plum, olive, peach, cherry, apricot, and the like; seed shells of other plants such as maize (e.g., corn cobs or corn kernels); wood materials such as those derived from oak, hickory, walnut, poplar, mahogany, and the like. Such materials are particles formed by crushing, grinding, cutting, chipping, and the like.

[0048] In an embodiment, the proppant particles are coated, e.g., with a resin. That is, individual proppant particles have a coating applied thereto. In this manner, if the proppant particles are compressed during or subsequent to, e.g., fracturing, at a pressure great enough to produce fine particles therefrom, the fine particles remain consolidated within the coating so they are not released into the formation. It is contemplated that fine particles decrease conduction of hydrocarbons (or other fluid) through fractures or pores in the fractures and are avoided by coating the proppant particles. Coating for the proppant particles include cured, partially cured, or uncured coatings of, e.g., a thermoset or thermoplastic resin. Curing the coating on the proppant particles occurs before or after disposal of the proppant particles in the SAP or before or after disposal of the hydraulic fracturing composition downhole, for example.

[0049] In an embodiment, the coating is an organic compound that includes epoxy, phenolic, polyurethane, polycarbodiimide, polyamide, polyamide imide, furan resins, or a combination thereof. The phenolic resin is, e.g., a phenol formaldehyde resin obtained by the reaction of phenol, bisphenol, or derivatives thereof with formaldehyde. Exemplary thermoplastics include polyethylene, acrylonitrile-butadiene styrene, polystyrene, polyvinyl chloride, fluoroplastics, polysulfide, polypropylene, styrene acrylonitrile, nylon, and phenylene oxide. Exemplary thermosets include epoxy, phenolic (a true thermosetting resin such as resole or a thermoplastic resin that is rendered thermosetting by a hardening agent), polyester resin, polyurethanes, epoxy-modified phenolic resin, and derivatives thereof.

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PCT/US2015/064815 [0050] In an embodiment, the curing agent for the coating is nitrogen-containing compounds such as amines and their derivatives; oxygen-containing compounds such as carboxylic acid terminated polyesters, anhydrides, phenol-formaldehyde resins, aminoformaldehyde resins, phenol, bisphenol A and cresol novolacs, phenolic-terminated epoxy resins; sulfur-containing compounds such as polysulfides, polymercaptans; and catalytic curing agents such as tertiary amines, Lewis acids, Lewis bases; or a combination thereof.

[0051] In an embodiment, the proppant particles include a crosslinked coating. The crosslinked coating typically provides crush strength, or resistance, for the proppant particles and prevents agglomeration of the proppant particles even under high pressure and temperature conditions. In some embodiments, the proppant particles have a curable coating, which cure subsurface, e.g. downhole or in a fracture. The curable coating cures under the high pressure and temperature conditions in the subsurface reservoir. Thus, the proppant particles having the curable coating are used for high pressure and temperature conditions.

[0052] According to an embodiment, the coating is disposed on the proppant particles by mixing in a vessel, e.g., a reactor. Individual components, e.g., the proppant particles and resin materials (e.g., reactive monomers used to form, e.g., an epoxy or polyamide coating) are combined in the vessel to form a reaction mixture and are agitated to mix the components. Further, the reaction mixture is heated at a temperature or at a pressure commensurate with forming the coating. In another embodiment, the coating is disposed on the particle via spraying such as by contacting the proppant particles with a spray of the coating material.

The coated proppant particles are heated to induce crosslinking of the coating.

[0053] In addition to the proppant particles and the SAP, the hydraulic fracturing composition includes a breaker in some embodiments. The breaker contacts the SAP to break the SAP. In an embodiment, the breaker contacts the SAP and breaks a bond in the backbone of the polymer chains of the SAP, a bond in the crosslinker, a bond between the crosslinker and a polymer chain of the SAP, or a combination thereof. That is, breaking the SAP includes disintegrating, decomposing, or dissociating the SAP such as by breaking bonds in the backbone of the SAP, breaking crosslinks among chains of the SAP, changing a geometrical conformation of the superabsorbent polymer, or a combination thereof. In this way, the viscosity of the hydraulic fracturing composition decreases. In some embodiments, the breaker breaks the SAP to form a decomposed polymer such as a plurality of fragments that have a lower molecular weight than the SAP. After breaking the SAP, the plurality of proppant particles is released from the SAP.

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PCT/US2015/064815 [0054] According to an embodiment, the breaker includes an oxidizer such as a peroxide, a persulfate, a perphosphate, a perborate, a percarbonate, a persilicate, an oxyacid of a halogen, an oxyanion of halogen, a peracid, a derivative thereof, or a combination thereof.

[0055] In one embodiment, the breaker is persulfate, such as sodium persulfate, ammonium persulfate, potassium persulfate, potassium peroxymonosulfate (Caro’s acid), or a combination thereof. The breaker is, e.g., an oxyacid or oxyanion of halogen, for instance, hypochlorous acid, a hypochlorite, chlorous acid and chlorites, chloric acid and chlorates, perchloric acid and perchlorate, a derivative thereof, or a combination thereof.

[0056] In an embodiment, a peroxide breaker has oxygen-oxygen single bonds in its molecular structure. The peroxide breaker is hydrogen peroxide or another material to provide peroxide or hydrogen peroxide for breaking the SAP. Metal peroxides such as sodium peroxide, calcium peroxide, zinc peroxide, magnesium peroxide, or other peroxides such as superoxides, organic peroxides, and the like can be used.

[0057] Additionally, in an embodiment, the peroxide breaker is a stabilized peroxide breaker with the hydrogen peroxide bound, inhibited, or the like by another compound or molecule prior to contact with, e.g., an aqueous fluid such as water such that it forms or releases hydrogen peroxide when contacted by the aqueous fluid. Exemplary stabilized peroxide breakers include an adduct of hydrogen peroxide with another molecule and include carbamide peroxide or urea peroxide (C(=O)(NH₂)₂ H₂O₂), a percarbonate (e.g., sodium percarbonate (2Na₂CO₃ 3H₂O₂), potassium percarbonate, ammonium percarbonate, and the like), and the like. The stabilized peroxide breakers also include compounds that undergo hydrolysis in water to release hydrogen peroxide, e.g., sodium perborate. In an embodiment, hydrogen peroxide stabilized with appropriate surfactants also is used as the stabilized peroxide breaker.

[0058] According to an embodiment, the breaker is the peracid, e.g., peracetic acid, perbenzoic acid, a derivative thereof, or a combination thereof. Additionally, a variety of peroxycarboxylic acids is employed as the peracid breaker. The peroxycarboxylic acid includes an ester peroxycarboxylic acid, an alkyl ester peroxycarboxylic acid, a sulfoperoxycarboxylic acid, or a combination thereof. Peroxycarboxylic acid (or percarboxylic acid) are acids having a general formula R(CO₃H)_n. In an embodiment,, the R group is saturated or unsaturated as well as substituted or unsubstituted. As described herein, R is an alkyl, alkenyl, arylalkyl, arylalkenyl, cycloalkyl, cycloalkenyl, aromatic, heterocyclic, or ester group, or a combination thereof (e.g., an alkyl ester group), with n being 1, 2, or 3.

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Exemplary ester groups include aliphatic ester groups, such as RJOQOjR², where R¹ and R² independently are a group (e.g., an alkyl group) described above for R such that R¹ and R² are, e.g., independently small carbon chain alkyl groups, such as a C1-C5 alkyl group.

[0059] One skilled in the art will appreciate that peroxycarboxylic acids may not be as stable as carboxylic acids, and their stability may increase with increasing molecular weight. Thermal decomposition of the peracids proceeds by, e.g., free radical and nonradical paths, by photodecomposition or radical-induced decomposition, or by the action of metal ions or complexes. In an embodiment, the percarboxylic acid peracids are made by direct, acid catalyzed equilibrium action of hydrogen peroxide with a carboxylic acid, by autoxidation of aldehydes, or from acid chlorides, and hydrides, or carboxylic anhydrides with hydrogen or sodium peroxide.

[0060] Exemplary peroxycarboxylic acids include peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, peroxylactic, peroxycitric, peroxymaleic, peroxyascorbic, peroxyhydroxyacetic (peroxyglycolic), peroxyoxalic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic, peroxysuberic, peroxysebacic acid, and the like.

[0061] In an embodiment, the peracid includes a combination of several peroxycarboxylic acids. According to one embodiment, the composition includes a C2-C4 peroxycarboxylic acid, a C+-C12 peroxycarboxylic acid, an ester peroxycarboxylic acid, an alkyl ester peroxycarboxylic acids, or a mono- or di-peroxycarboxylic acid having up to 12 carbon atoms, and more specifically 2 to 12 carbon atoms. In an embodiment, the peroxycarboxylic acid includes peroxyacetic acid (POAA) (i.e., peracetic acid having the formula CH3COOOH) or peroxyoctanoic acid (POOA) (i.e., peroctanoic acid having the formula, e.g., of n-peroxyoctanoic acid: CH3(CH₂)6COOOH).

[0062] In an embodiment, the peracid is an ester peroxycarboxylic acid. As used herein, ester peroxycarboxylic acid refers to a molecule having the formula:

0

R²-O-C-R¹-C-O-OH wherein R¹ and R² are independently an organic group (e.g., alkyl, linear or cyclic, aromatic or saturated) or a substituted organic group (e.g., with a heteroatom or organic group). In an embodiment, the ester peroxycarboxylic acid is made by employing methods used for making

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PCT/US2015/064815 peroxycarboxylic acid such as combining the corresponding ester carboxylic acid with an oxidizing agent, e.g., hydrogen peroxide.

[0063] Exemplary alkyl esterperoxycarboxylic acids include monomethyl monoperoxyglutaric acid, monomethyl monoperoxyadipic acid, monomethyl monoperoxyoxalie acid, monomethyl monoperoxymalonic acid, monomethyl monoperoxysuccinic acid, monomethyl monoperoxypimelic acid, monomethyl monoperoxysuberic acid, and monomethyl monoperoxysebacic acid; mono ethyl monoperoxyoxalie acid, monoethyl monoperoxymalonic acid, monoethyl monoperoxysuccinic acid, monoethyl monoperoxyglutaric acid, monoethyl monoperoxyadipic acid, monoethyl monoperoxypimelic acid, monoethyl monoperoxysuberic acid, and monoethyl monoperoxysebacic acid; monopropyl monoperoxyoxalie acid, monopropyl monoperoxymalonic acid, monopropyl monoperoxysuccinic acid, monopropyl monoperoxyglutaric acid, monopropyl monoperoxyadipic acid, monopropyl monoperoxypimelic acid, monopropyl monoperoxysuberic acid, monopropyl monoperoxysebacic acid, in which propyl is n- or isopropyl; monobutyl monoperoxyoxalie acid, monobutyl monoperoxymalonic acid, monobutyl monoperoxysuccinic acid, monobutyl monoperoxyglutaric acid, monobutyl monoperoxyadipic acid, monobutyl monoperoxypimelic acid, monobutyl monoperoxysuberic acid, monobutyl monoperoxysebacic acid, in which butyl is η-, iso-, or t-butyl; and the like.

[0064] In some embodiments, the peracid breaker is a sulfoperoxycarboxylic acid. Sulfoperoxycarboxylic acids, which also are referred to as sulfonated peracids, include the peroxycarboxylic acid form of a sulfonated carboxylic acid. In some embodiments, the sulfonated peracid is a mid-chain sulfonated peracid, i.e., a peracid that includes a sulfonate group attached to a carbon that is at least one carbon (e.g., at least the three position) from the carbon of the percarboxylic acid group in the carbon backbone of the percarboxylic acid chain, wherein the at least one carbon is not in the terminal position. As used herein, the term “terminal position” refers to the carbon on the carbon backbone chain of a percarboxylic acid that is furthest from the percarboxyl group. Thus, in an embodiment, sulfoperoxycarboxylic acid has the following formula:

SO₃X⁺ O

R³-C-R⁴-C-O-OH

H

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PCT/US2015/064815 wherein R³ is hydrogen or a substituted or unsubstituted alkyl group; R⁴ is a substituted or unsubstituted alkyl group; X is hydrogen, a cationic group, or an ester forming moiety; or salts or esters thereof.

[0065] In some embodiments, R³ is a substituted or unsubstituted Cm alkyl group; X is hydrogen, a cationic group, or an ester forming moiety; R⁴ is a substituted or unsubstituted Cn alkyl group; m=l to 10; n=l to 10; and m+n is less than 18; or salts, esters, or a combination thereof. In some embodiments, R³ is hydrogen. In other embodiments, R³ is a substituted or unsubstituted alkyl group. In some embodiments, R³ is a substituted or unsubstituted alkyl group that does not include a cycloalkyl group. In some embodiments, R³ is a substituted alkyl group. In some embodiments, R³ is an unsubstituted C1-C9 alkyl group. In some embodiments, R³ is an unsubstituted C7 or Cx alkyl. In other embodiments, R³ is a substituted Cg-Cio alkyl group. In some embodiments, R³ is a substituted Cg-Cio alkyl group and is substituted with at least 1, or at least 2 hydroxyl groups. In still yet other embodiments, R³is a substituted C1-C9 alkyl group. In some embodiments, R³i is a substituted C1-C9 substituted alkyl group and is substituted with an -SO3H group. In other embodiments, R³ is a C9-C10 substituted alkyl group. In some embodiments, R³ is a substituted C9-C10 alkyl group wherein at least two of the carbons on the carbon backbone form a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group.

[0066] In an embodiment, R⁴ is a substituted C1-C10 alkyl group. In some embodiments, R⁴ is a substituted Cg-Cio alkyl. In some embodiments, R⁴ is an unsubstituted C6-C9 alkyl. In other embodiments, R⁴ is a Cs-Cio alkyl group substituted with at least one hydroxyl group. In some embodiments, R⁴ is a C10 alkyl group substituted with at least two hydroxyl groups. In other embodiments, R⁴ is a Cx alkyl group substituted with at least one -SO3H group. In some embodiments, R⁴ is a substituted C9 group, wherein at least two of the carbons on the carbon backbone form a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group. In some, embodiments, R⁴is a Cs-Cg substituted or unsubstituted alkyl, and R⁴ is a C7-C8 substituted or unsubstituted alkyl.

[0067] According to an embodiment, in the hydraulic fracturing composition, the breaker is encapsulated in an encapsulating material to prevent the breaker from contacting the SAP. The encapsulating material is configured to release the breaker in response to the breaking condition. The breaker is a solid or liquid. As a solid, the breaker is, e.g., a crystalline or granular material. In an embodiment, the solid is encapsulated or provided with a coating to delay its release or contact with the SAP. Encapsulating materials are the same or different as the coating material noted above with regard to the proppant particles.

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Methods of disposing the encapsulating material on the breaker are the same or different as for disposing the coating on the proppant particles. In an embodiment, a liquid breaker is dissolved in an aqueous solution or another suitable solvent.

[0068] In an embodiment, the encapsulation material is a polymer that releases the breaker in a controllable way, e.g., at a controlled rate or concentration. Such material is a polymer that degrades over a period of time to release the breaker and is chosen depending on the release rate desired. Degradation of the polymer of the encapsulation material polymer occurs, e.g., by hydrolysis, solvolysis, melting, and the like. In an embodiment, the polymer of the encapsulation material is a homopolymer or copolymer of glycolate and lactate, a polycarbonate, a polyanhydride, a polyorthoester, a polyphosphazene, or a combination thereof.

[0069] According to an embodiment, the encapsulated breaker is an encapsulated hydrogen peroxide, encapsulated metal peroxides (e.g., sodium peroxide, calcium peroxide, zinc peroxide, and the like) or any of the peracids or other breaker herein.

[0070] In the hydraulic fracturing composition, the fluid is included to contact and expand the SAP into the expanded state. The fluid is an aqueous fluid that includes water, brine, an acid such as a mineral acid or an organic acid, or a base. The brine is, for example, seawater, produced water, completion brine, or a combination thereof. The properties of the brine can depend on the identity and components of the brine. Seawater, as an example, contains numerous constituents such as sulfate, bromine, and trace metals, beyond typical halide-containing salts. In some embodiments, produced water is water extracted from a production reservoir (e.g., hydrocarbon reservoir) or produced from the ground. Produced water also is referred to as reservoir brine and contains components such as barium, strontium, and heavy metals. In addition to the naturally occurring brines (seawater and produced water), completion brine is synthesized from fresh water by addition of various salts such as KC1, NaCI, ZnCfr, MgCfr, or CaCl₂ to increase the density of the brine, such as

10.6 pounds per gallon of CaCl₂ brine. Completion brines typically provide a hydrostatic pressure optimized to counter the reservoir pressures downhole. In an embodiment, the above brines are modified to include an additional salt. In an embodiment, the additional salt included in the brine is NaCI, KC1, NaBr, MgCl₂, CaCl₂, CaBr₂, ZnBr₂, NH4CI, sodium formate, cesium formate, and the like. The salt is present in the brine in an amount from about 0.5 weight percent (wt%) to about 50 wt%, specifically about 1 wt% to about 40 wt%, and more specifically about 1 wt% to about 25 wt%, based on the weight of the fluid.

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PCT/US2015/064815 [0071] According to an embodiment, the fluid is a mineral acid that includes hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, or a combination thereof. In some embodiments, the fluid is an organic acid that includes a carboxylic acid, sulfonic acid, or a combination thereof. Exemplary carboxylic acids include formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, propionic acid, butyric acid, oxalic acid, benzoic acid, phthalic acid (including ortho-, meta- and para-isomers), and the like. Exemplary sulfonic acids include alkyl sulfonic acid or aryl sulfonic acid. Alkyl sulfonic acids include, e.g., methane sulfonic acid. Aryl sulfonic acids include, e.g., benzene sulfonic acid or toluene sulfonic acid. In one embodiment, the alkyl group may be branched or unbranched and contains from one to about 20 carbon atoms and is substituted or unsubstituted. In an embodiment, the aryl group is alkyl-substituted, i.e., is an alkylaryl group, or is attached to the sulfonic acid moiety via an alkylene group (i.e., an arylalkyl group). In an embodiment, the aryl group is substituted with a heteroatom. The aryl group has from 3 carbon atoms to 20 carbon atoms and includes, e.g., a polycyclic ring structure.

[0072] In an embodiment, the hydraulic fracturing composition further includes a well treatment agent for flow assurance, performance enhancement, and fluid stability. Suitable well treatment agents include those that can adress undesired effects caused by scale formation, salt formation, paraffin deposition, asphaltene deposition, foaming agent deposition, emulsification, gas hydrate formation, corrosion, foaming agents, oxygen scavengers, H₂S scavengers, biocides, surfactants, or a combination thereof. Specific well treatment agents include a scale inhibitor, a tracer, a pH-buffering agent, or a combination thereof.

[0073] The well treatment agents can be used in liquid or solid form, as-is or in the form of a salt or other complex. The well treatment agent can be coated, encapsulated, incorporated into a binder, adsorbed onto a matrix, or absorbed into a matrix. Suitable coatings include the thermoplastic, thermosetting, and crosslinked coatings described above for use with proppants. Suitable encapsulants include those described above for use with breakers. The same thermoplastic, thermosetting, and crosslinked materials that can be used as a coating or an encapsulant are also suitable for use as a binder, or a matrix for adsorption of the well treatment agents. Matrices for absorption of the well treatment materials are porous, preferably microporous, and can be organic (e.g., an open-celled polymer foam such as a polyurethane foam) or inorganic (e.g., zeolites, metal silicates, and aluminophosphates).

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PCT/US2015/064815 [0074] Scale inhibitors can be used to control or prevent scale formation in the well, among other functions. Scale inhibitors can be a carboxylic, sulfonic, or phosphonic acidcontaining compound, a carboxylic, sulfonic, or phosphonic group-containing polymer, or a combination thereof, for example amino trimethylene phosphonic acid, 1-hydroxy ethylidene-l,l-diphosphonic acid, 2-phosphonobutane-l,2,4-tricarboxylic acid, 2hydroxyethyl-amino-bis(methylenephosphonic acid), ethylenediamine tetrakis(methylene phosphonic acid), tetramethylenediamine tetrakis(methylene phosphonic acid), hexamethylenediamine tetrakis(methylene phosphonic acid), 2-hydroxy phosphonoacetic acid, diethylene triamine penta(methylene phosphonic acid), bis(hexamethylenetriamine penta(methylene phosphonic acid)), polyaminopolyether methylenephosphonate or a salt thereof, phosphino-polycarboxylate, polyacrylic acid, polymaleic acid, acrylic acid copolymers, sulfonated polyacrylate copolymers, polyvinyl sulfonate, carboxymethyl inulin, polyaspartate, or a combination thereof.

[0075] The scale inhibitor is present in the hydraulic fracturing composition in an amount effective to inhibit scale to the desired degree, which can be, for example, about 0.001 wt% to about 10 wt%, or about 0.01 wt% to about 10 wt%, or about 0.01 wt% to about 5 wt%, preferably about 0.1 wt% to about 2 wt%, each based on total weight of the composition.

[0076] A tracer can be used to later detect or infer information about the well, borehole or the drilled formations. Tracers used during drilling can be mud tracers and filtrate tracers. Tracers can be oil- or water-soluble. Examples of tracers include a fluorinated benzoic acid, perfluorinated hydrocarbon, alcohol, ketone, organic acid, halogenated compound, or a combination thereof.

[0077] Exemplary perfluorinated hydrocarbons are perfluorinated Ci-Cig hydrocarbons, for example, tetrafluoromethane, tetrafluoroethane, tetrafluoropropane, and the like.

[0078] Examples of alcohols include C1-C24 monofunctional and polyfunctional alcohols such as methanol, ethanol, glycol, propanol, propanediol, butanol, pentanol, pentaerythritol, hexanol, octanol, decanol, dodecanol, and the like. Preferred alcohols are C10-C24 monofunctional alcohols.

[0079] Exemplary ketones are C1-C18 ketones and diketones such as acetone, cyclopropanone, methyl ethyl ketone, cyclohexanone, acetyl acetone, benzophenone, and the like.

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PCT/US2015/064815 [0080] Exemplary organic acids include Ci-Cig mono-, di and tricarboxylic acids.

Examples of organic acids are acetic acid, propanoic acid, butanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, citric acid, and the like.

[0081] The halogenated compounds can be mono, di, tri and tetrachlorinated C1-C12 hydrocarbons. Examples include methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, hexachlorocyclohexane, benzyl chloride, benzal chloride, benzotrichloride, and the like.

[0082] The tracer is present in the hydraulic fracturing composition in an amount effective to trace the desired fluid or composition, which can be, for example, about 0.001 wt% to about 10 wt%, or about 0.001 wt% to about 5 wt%, or about 0.01 wt% to about 5 wt%, preferably about 0.01 wt% to about 1 wt%, each based on total weight of the composition.

[0083] A buffering agent can be a weak acid or base used to maintain the pH of a solution near a chosen value after the addition of another acid or base. The function of a buffering agent is to prevent a rapid change in pH when acids or bases are added to the solution. For buffers in acid regions, the pH is adjusted to a desired value by adding a strong acid such as HCI to the buffering agent. For alkaline buffers, a strong base such as NaOH is added. Alternatively, a buffer combination can be made from a combination, e.g., a mixture, of an acid and its conjugate base. For example, an acetate buffer can be made from a mixture of acetic acid and sodium acetate. Similarly, an alkaline buffer can be made from a mixture of the base and its conjugate acid. pH-Buffering agents differ from pH-adjusting agents in that a buffering agent maintains the pH of the fluid in a desired range, for example a pH from about 6 to about 9, preferably a pH from about 6.5 to about 8.5, most preferably a pH of about 7 to about 8 at a downhole temperature of a subterranean well. Examples of buffering agents include alkali and alkaline earth salts of carbonates, bicarbonate, acetate, citrate, gluconate, phosphate, borate, or tartrate, for example sodium carbonate and potassium carbonate, CaCCE, sodium sesquicarbonate, and potassium sesquicarbonate, oxides of alkaline earth metals such as MgO and CaO, an organic polyelectrolytes, or a combination thereof.

[0084] The buffering agent is present in the hydraulic fracturing composition in an amount effective to buffer the composition, which can be, for example, about 0.005 wt% to about 10 wt%, or about 0.01 wt% to about 10 wt%, or about 0.01 wt% to about 5 wt%, or about 0.1 wt% to about 2 wt%, each based on total weight of the composition.

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PCT/US2015/064815 [0085] The buffering agent can optionally be used in combination with a slow-release breaking agent, for example, a slow release acid. The acid can be glyoxal, a solid acid, an encapsulated acid, a coated acid, or a combination thereof. Glyoxal is a dialdehyde that can slowly release acids. Slow release of acids can overcome the buffering agent, and result in gradual reduction of the fluid pH until a selected pH value is attained that is suitable for breaking the SAP.

[0086] When used, the foregoing well treatment agents can be continuously injected through a downhole injection point in the completion, or periodic squeeze treatments can be undertaken to place the additive in the reservoir matrix for subsequent commingling with produced fluids.

[0087] Besides the SAP, the hydraulic fracturing composition includes a viscous polymer in in some embodiments. The viscous polymer includes guar gums, high-molecular weight polysaccharides composed of mannose and galactose sugars, xanthan gum, guar, or starch or guar derivatives such as hydropropyl guar (HPG), carboxymethyl guar (CMG), and carboxymethylhydroxypropyl guar (CMHPG), galactomannan gums, glucomannan gums, guars, derived guars, cellulose derivatives, or a combination thereof. Cellulose derivatives such as hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), hydroxypropylcellulose (HPC), and carboxymethylhydroxyethylcellulose (CMHEC); hydropropyl starch; or lignosulfonate also is used.

[0088] According to an embodiment, the viscous polymer is includes a repeat unit that comprises an acrylate, an acrylamide, a vinylpyrrolidone, a vinyl ester (e.g., a vinyl acetate), a vinyl alcohol, a 2-acrylamide-2-methylpropanesulfonic acid, a derivative thereof, or a combination thereof. In some embodiments, the viscous polymer is polyacrylic acid.

[0089] In an exemplary embodiment, the viscous polymer comprises a linear polymer such as a polyacrylamide, a guar, a guar derivative, glycerol, a polysaccharide such as cellulose and starch, or a combination thereof. Without wishing to be bound by theory, it is believed that the presence of a viscous polymer in the hydraulic fracturing composition increases the viscosity, thus the proppant-suspension ability of the composition. The presence of the viscous polymer also helps to reduce the friction pressure. When the hydraulic fracturing composition is a foam fluid, the viscous polymer further stabilizes the foam fluid by improving the foam quality and foam half-life.

[0090] The viscous polymer forms a viscous gel due to contact with the fluid of the hydraulic fracturing composition (or another fluid such as water, brine, or other downhole fluid). When the viscous polymer comprises glycerol, a linear polymer such as linear

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PCT/US2015/064815 polyacrylamide, a guar, a guar derivative, a polysaccharide such as cellulose and starch, or a combination thereof, the formed viscous gel can be referred to as a linear gel. In some embodiments, a combination of fluids is used, a first fluid to expand the SAP and a second fluid to gel the viscose polymer. Without wishing to be bound by theory, it is believed that the viscous polymer has increased viscosity due to long polymer chains that becomes entangled. Entangled polymer chains of the viscous polymer creates networks, giving complex viscosity behavior. In an embodiment, the viscous polymer is a copolymer that contains two or more different monomers that are arranged randomly or in blocks. Moreover, the viscosity of the viscous polymer is increased by crosslinking the polymer chains of the viscose polymer. Crosslinkers for the viscous polymer include borate, titanate, zirconate, aluminate, chromate, or a combination thereof. Boron crosslinked viscose polymers include, e.g., guar and substituted guars crosslinked with boric acid, sodium tetraborate, or encapsulated borates; borate crosslinkers may be used with buffering agents and pH control agents such as sodium hydroxide, magnesium oxide, sodium sesquicarbonate, and sodium carbonate, amines (such as hydroxyalkyl amines, anilines, pyridines, pyrimidines, quinolines, and pyrrolidines, and carboxylates such as acetates and oxalates) and with delay agents such as sorbitol, aldehydes, and sodium gluconate. Zirconium crosslinked viscose polymers include, e.g., those crosslinked by zirconium lactates (e.g., sodium zirconium lactate), triethanolamines, 2,2’-iminodiethanol, or a combination thereof. Titanates for crosslinking include, e.g., lactates and triethanolamines, and the like.

[0091] In an embodiment, the hydraulic fracturing composition includes an SAP, for example an SAP having crosslinked polymer particles such as a polyacrylic acid, polyacrylamide, a polysaccharide, or a combination thereof; a plurality of proppant particles; a fluid to expand the SAP, and a viscose polymer. Once the SAP is combined with the fluid, it expands while maintaining its shape. The viscous polymer is a linear polymer that hydrates in the fluid and has a viscosity determined by entanglement of the hydrated linear polymer. It is contemplated that the entangled linear polymers can be crosslinked in-situ to form a crosslinked gel. Thus, the hydraulic fracturing composition has beneficial rheological properties including tunable viscosity and breaking properties.

[0092] The hydraulic fracturing composition can also comprise a surfactant. Useful surfactants include fatty acids of up to 22 carbon atoms such as stearic acids and esters and polyesters thereof, poly(alkylene glycols) such as poly(ethylene oxide), polypropylene oxide), and block and random poly(ethylene oxide-propylene oxide) copolymers such as those marketed under the trademark PLURONIC by BASF. Other surfactants include

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PCT/US2015/064815 polysiloxanes, such as homopolymers or copolymers of poly(dimethylsiloxane), including those having functionalized end groups, and the like. Other useful surfactants include those having a polymeric dispersant having poly(alkylene glycol) side chains, fatty acids, or fluorinated groups such as perfluorinated Cw sulfonic acids grafted to the polymer backbone. Polymer backbones include those based on a polyester, a poly(meth)acrylate, a polystyrene, a poly(styrene-(meth)acrylate), a polycarbonate, a polyamide, a polyimide, a polyurethane, a polyvinyl alcohol, or a copolymer comprising at least one of these polymeric backbones. Additionally, the surfactant is anionic, cationic, zwitterionic, or non-ionic.

[0093] Exemplary cationic surfactants include but are not limited to alkyl primary, secondary, and tertiary amines, alkanolamides, quaternary ammonium salts, alkylated imidazolium, and pyridinium salts. Additional examples of the cationic surfactant include primary to tertiary alkylamine salts such as, e.g., monostearylammonium chloride^ distearylammonium chloride, tristearylammonium chloride; quaternary alkylammonium salts such as, e.g., monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, monostearylbis(polyethoxy)methylammonium chloride; alkylpyridinium salts such as, e.g., Ncetylpyridinium chloride, N-stearylpyridinium chloride; Ν,Ν-dialkylmorpholinium salts; fatty acid amide salts such as, e.g., polyethylene polyamine; and the like.

[0094] Exemplary anionic surfactants include alkyl sulfates, alkyl sulfonates, fatty acids, sulfosuccinates, and phosphates. Examples of an anionic surfactant include anionic surfactants having a carboxyl group such as sodium salt of alkylcarboxylic acid, potassium salt of alkylcarboxylic acid, ammonium salt of alkylcarboxylic acid, sodium salt of alkylbenzenecarboxylic acid, potassium salt of alkylbenzenecarboxylic acid, ammonium salt of alkylbenzenecarboxylic acid, sodium salt of polyoxyalkylene alkyl ether carboxylic acid, potassium salt of polyoxyalkylene alkyl ether carboxylic acid, ammonium salt of polyoxyalkylene alkyl ether carboxylic acid, sodium salt of N-acylsarcosine acid, potassium salt of N-acylsarcosine acid, ammonium salt of N-acylsarcosine acid, sodium salt of Nacylglutamic acid, potassium salt of N-acylglutamic acid, ammonium salt of N-acylglutamic acid; anionic surfactants having a sulfonic acid group; anionic surfactants having a phosphonic acid; and the like.

[0095] In an embodiment, the nonionic surfactant is, e.g., an ethoxylated fatty alcohols, alkyl phenol polyethoxylates, fatty acid esters, glycerol esters, glycol esters, polyethers, alkyl polyglycosides, amineoxides, or a combination thereof. Exemplary nonionic surfactants include fatty alcohols (e.g., cetyl alcohol, stearyl alcohol, cetostearyl

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PCT/US2015/064815 alcohol, oleyl alcohol, and the like); polyoxyethylene glycol alkyl ethers (e.g., octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, and the like); polyoxypropylene glycol alkyl ethers (e.g., butapropylene glycol monononyl ethers); glucoside alkyl ethers (e.g., decyl glucoside, lauryl glucoside, octyl glucoside); polyoxyethylene glycol octylphenol ethers (e.g., Triton X-100 (octyl phenol ethoxylate)); polyoxyethylene glycol alkylphenol ethers (e.g., nonoxynol-9); glycerol alkyl esters (e.g., glyceryl laurate); polyoxyethylene glycol sorbitan alkyl esters (e.g., polysorbates such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, and the like); sorbitan alkyl esters (e.g., polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like); cocamide ethanolamines (e.g., cocamide monoethanolamine, cocamide diethanolamine, and the like); amine oxides (e.g., dodecyldimethylamine oxide, tetradecyldimethylamine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide, and the like); block copolymers of polyethylene glycol and polypropylene glycol (e.g., poloxamers available under the trade name Pluronics, available from BASF);polyethoxylated amines (e.g., polyethoxylated tallow amine); polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether; polyoxyethylene alkylene ethers such as polyoxyethylene oleyl ether; polyoxyalkylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyalkylene glycols such as polyoxypropylene polyoxyethylene glycol; polyoxyethylene monoalkylates such as polyoxyethylene monostearate; bispolyoxyethylene alkylamines such as bispolyoxyethylene stearylamine; bispolyoxyethylene alkylamides such as bispolyoxyethylene stearylamide; alkylamine oxides such as Ν,Ν-dimethylalkylamine oxide; and the like.

[0096] Zwitterionic surfactants (which include a cationic and anionic functional group on the same molecule) include, e.g., betaines, such as alkyl ammonium carboxylates (e.g., [(CFF^iSr-CH(R)COO'] or sulfonates (sulfo-betaines) such as [RN⁺(CH3)2(CH2)3SO3-], where R is an alkyl group). Examples include n-dodecyl-N-benzyl-N-methylglycine [Ci2H25N⁺(CH2C6H5)(CH3)CH2COO'], N-allyl N-benzyl N-methyltaurines [C„H_2n+iN⁺(CH₂C₆H₅)(CH3)CH₂CH₂SO3].

[0097] In an embodiment, the surfactant is a viscoelastic surfactant. The surfactant is viscoelastic because, unlike numerous surfactants, which form Newtonian solutions with a viscosity slightly higher than water even at high concentrations, it is capable of forming viscoelastic fluids at a lower concentration. This specific rheological behavior is mainly due to the types of surfactant aggregates that are present in the fluids. In low viscosity fluids, the

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PCT/US2015/064815 surfactant molecules aggregate in spherical micelles whereas, in viscoelastic fluids, long micelles, which can be described as worm-like, thread-like or rod-like micelles, are present and entangle.

[0098] The viscoelastic surfactant of the invention is usually ionic. It may be cationic, anionic or zwitterionic depending on the charge of its head group. When the surfactant is cationic, it is associated with a negative counterion, which can be an inorganic anion such as a sulfate, a nitrate, a perchlorate or a halide such as Cl, Br or with an aromatic organic anion such as salicylate, naphthalene sulfonate, p and m chlorobenzoates, 3,5 and 3,4 and 2,4dichlorobenzoates, t-butyl and ethyl phenate, 2,6 and 2,5-dichlorophenates, 2,4,5trichlorophenate, 2,3,5,6-tetrachlorophenate, p-methyl phenate, m-chlorophenate, 3,5,6trichloropicolinate, 4-amino-3,5,6-trichlorpicolinate, 2,4-dichlorophenoxyacetate. When the surfactant is anionic, it is associated with a positive counterion, for example, Na+ or K+. When it is zwitternionic, it is associated with both negative and positive counterions, for example, Cl and Na+ or K+. Other viscoelastic surfactant has been described in US Patent Numbers 7,081,439 and 7,279,446.

[0099] The hydraulic fracturing composition can be a liquid or a foam. A liquid includes a surfactant based fluid, a linear gel fluid, or a crosslinked gel fluid. A surfactantbased fluid can refer to the hydraulic fracturing composition comprising a viscoelastic surfactant. A linear gel fluid can refer to the hydraulic fracturing composition comprising a linear gel. Similarly, a crosslinked gel fluid refers to the hydraulic fracturing composition comprising a crosslinked gel.

[0100] A foam fluid is a stable mixture of gas and liquid. It is generally described by its foam quality, i.e. the ratio of gas volume to the foam volume. The foam half-life is another important parameter to evaluate the stability of foam fluids. The half-life of a foam fluid is the time necessary for one-half of the liquid used to generate the foam to break out of the foam under atmospheric conditions. A foam system is mainly used in fracturing low pressure or water sensitive formations.

[0101] Water-soluble polymers, such as guar gums, high-molecular weight polysaccharides composed of mannose and galactose sugars, or guar derivatives such as hydropropyl guar (HPG), carboxymethylhydropropyl guar (CMHPG), can be used to prepare the liquid phase of the foam fluids. Crosslinking agents based on boron, titanium, zirconium or aluminum complexes can be used to increase the effective molecular weight of the polymer and make them better suited for use in high-temperature wells.

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PCT/US2015/064815 [0102] Polymer-free, liquid phase of foam fluids can be obtained using viscoelastic surfactants. These fluids are normally prepared by mixing in appropriate amounts suitable surfactants such as anionic, cationic, nonionic and zwitterionic surfactants in aqueous solutions. The viscosity of viscoelastic surfactant fluids is attributed to the three dimensional structure formed by the components in the fluids. When the concentration of surfactants in a viscoelastic fluid significantly exceeds a critical concentration, and in most cases in the presence of an electrolyte, surfactant molecules aggregate into species such as micelles, which can interact to form a network exhibiting viscosity and elastic behavior to further stabilize the foamed systems. Meanwhile, the surfactant also acts as foaming agent to create the stable dispersion of gas in viscous liquid.

[0103] In an embodiment, various additional additives are included in the hydraulic fracturing composition. Exemplary additional additives include a lubricant, a non-emulsifier, a clay stabilizer, a biocide, an acid, a corrosion inhibitor, a pH-adjusting agent, or a combination thereof.

[0104] In an embodiment, the non-emulsifier of the additional additive is a combination of the above surfactants or a combination of surfactant with a short chain alcohol or polyol such as lauryl sulfate with isopropanol or ethylene glycol. The nonemulsifier prevents formation of emulsions in the hydraulic fracturing composition.

[0105] In an embodiment, the additional additive is the lubricant such as a polyacrylamide, petroleum distillate, hydrotreated light petroleum distillate, a short chain alcohol (e.g., methanol), or polyol (e.g., ethylene glycol or glycerol). Such lubricants minimize friction and include, e.g., a polymer such as polyacrylamide, polyisobutyl methacrylate, polymethyl methacrylate, or polyisobutylene as well as water-soluble lubricants such as guar, guar derivatives, polyacrylamide, and polyethylene oxide. In an embodiment, the lubricant comprises a guar, a guar derivative, glycerol, polyacrylamide, a polysaccharide such as cellulose and starch, or a combination thereof.

[0106] The clay stabilizer of the additional additive prevents the clay downhole from swelling under contact with the hydraulic fracturing composition or applied fracturing pressure. In an embodiment, the clay stabilizer includes a quaternary amine, a brine (e.g., KC1 brine), choline chloride, tetramethyl ammonium chloride, and the like.

[0107] According to an embodiment, the additional additive is the pH-adjusting agent, which adjusts pH of the hydraulic fracturing composition. The pH-adjusting agent is an organic or inorganic base, organic or inorganic acid, or a buffering agent, which is any appropriate combination of acid and conjugate base. Exemplary inorganic bases include

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PCT/US2015/064815 those represented by MOH, where M is a metal from group 1 or 2 of the periodic table, a transition metal, or a metal or metalloid from group 13, 14, or 15; carbonate salt; bicarbonate salt; or a combination thereof. Exemplary inorganic acids include HC1, HBr, fluoroboric acid, sulfuric acid, nitric acid, acetic acid, formic acid, methanesulfonic acid, propionic acid, chloroacetic or dichloroacetic acid, citric acid, glycolic acid, lactic acid, or a combination thereof. In an embodiment, the pH-adjusting agent is selected to avoid imparting favorable characteristics to the hydraulic fracturing composition. In an embodiment, the pH-adjusting agent is selected to avoid damage to the surface equipment containing the hydraulic fracturing composition or to avoid damaging the wellbore or subterranean formation.

[0108] In an embodiment, the additional additive to the hydraulic fracturing composition is the biocide that prevents injection of a microbe (e.g., bacteria) downhole. The biocide kills, eliminates, or reduces bacteria in the hydraulic fracturing composition such as water (e.g., when using river water as the fluid). In this way, introduction of live bacteria into the formation is prevented, thus reducing production of, e.g., sour gas.

[0109] According to an embodiment, the biocide does not interfere with the other components of the hydraulic fracturing composition and is not a health risk. In an embodiment, the biocide is an aldehyde such as glutaraldehyde. Examples of the biocide include non-oxidizing and oxidizing biocides. Exemplary oxidizing biocides include hypochlorite bleach (e.g., calcium hypochlorite and lithium hypochlorite), peracetic acid, potassium monopersulfate, potassium peroxymonosulfate, bromochlorodimethylhydantoin, dichloroethylmethylhydantoin, chloroisocyanurate, trichloroisocyanuric acids, dichloroisocyanuric acids, chlorinated hydantoins, and the like. Additional oxidizing biocides include, e.g., bromine products such as stabilized sodium hypobromite, activated sodium bromide, or brominated hydantoins. Other oxidizing biocides include chlorine dioxide, ozone, inorganic persulfates such as ammonium persulfate, or peroxides, such as hydrogen peroxide and organic peroxides.

[0110] Exemplary non-oxidizing biocides include dibromonitfdopropionamide, thiocyanomethylthiobenzothlazole, methyldithiocarbamate, tetrahydrodimethylthladiazonethione, tributyltin oxide, bromonitropropanediol, bromonitrostyrene, methylene bisthiocyanate, chloromethylisothlazolone, methylisothiazolone, benzisothlazolone, dodecylguanidine hydrochloride, polyhexamethylene biguanide, tetrakis(hydroxymethyl) phosphonium sulfate, glutaraldehyde, alkyldimethylbenzyl ammonium chloride, didecyldimethylammonium chloride, poly[oxyethylene-(dimethyliminio) ethylene (dimethyliminio) ethylene dichloride],

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PCT/US2015/064815 decylthioethanamine, terbutylazine, and the like. Additional non-oxidizing biocides are quaternary ammonium salts, aldehydes and quaternary phosphonium salts. In an embodiment, quaternary biocides have a fatty alkyl group and three methyl groups, but in the phosphonium salts, the methyl groups, e.g., are substituted by hydroxymethyl groups without substantially affecting the biocidal activity. In an embodiment, they also are substituted with an aryl group. Examples include formaldehyde, glyoxal, furfural, acrolein, methacrolein, propionaldehyde, acetaldehyde, crotonaldehyde, pyridinium biocides, benzalkonium chloride, ceramide, cetyl trimethyl ammonium chloride, benzethonium chloride, cetylpyridinium chloride, chlorphenoctium amsonate, dequalinium acetate, dequalinium chloride, domiphen bromide, laurolinium acetate, methylbenzethonium chloride, myristyl-gamma-picolinium chloride, ortaphonium chloride, triclobisonium chloride, alkyl dimethyl benzyl ammonium chloride, cocodiamine, dazomet, l-(3-chloroallyl)-chloride.3,5,7-triaza-l-azoniaadamantane, or a combination thereof.

[0111] In an embodiment, the biocide is encapsulated or coated as discussed above with regard to the proppant particles or breaker. In an embodiment, the biocide is encapsulated or coated by any suitable encapsulation method using any suitable encapsulation material. The encapsulation material is any material that does not adversely interact or chemically react with the biocide to destroy its utility. In an embodiment, the biocide is released from the coating at a selected time.

[0112] In the hydraulic fracturing composition, the proppant particles are present in an amount effective to prop open the fracture without the geometry of the fracture being altered during settling of the formation when the proppant is released from the SAP. In a particular embodiment, the proppant particles are present in a mass concentration from 0.1 pounds per gallon (lb/gal) to 20 lb/gal, specifically 0.25 lb/gal to 16 lb/gal, and more specifically 0.25 lb/gal to 12 lb/gal, based on the total volume of the composition. In an embodiment, the SAP is present in a mass concentration from 1 pound of SAP per one thousand gallons of fluid (ppt) to 200 ppt, specifically 5 ppt to 100 ppt, and more specifically 15 ppt to 50 ppt, based on the total volume of the composition. In the hydraulic fracturing composition, any ratio of the amount of the proppant particles to the amount of the SAP is applicable as long as the proppant particles are suspended in the gel formed by the SAP.

[0113] In an embodiment, the breaker is present in the hydraulic fracturing composition in a mass concentration from 0 ppt to 20 ppt, specifically 0 ppt to 15 ppt, and more specifically, 0 ppt to 10 ppt, based on the total volume of the composition. In some embodiments, the biocide is present in an amount from 10 parts per million (ppm) to 2000

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PCT/US2015/064815 ppm, specifically 50 ppm to 1500 ppm, and more specifically 50 ppm to 1000 ppm. An amount of the viscose polymer, if present, is from 0.25 gallons of viscose polymer per 1000 gallons of fluid (gpt) to 10 gpt, specifically 0.5 gpt to 8 gpt, and more specifically 0.5 gpt to 4 gpt, based on the total hydraulic fracturing composition volume.

[0114] The hydraulic fracturing composition can be made in a variety of ways. According to an embodiment, a process for making the hydraulic fracturing composition includes contacting a superabsorbent polymer with a fluid to expand the superabsorbent polymer into an expanded state and disposing a plurality of proppant particles in the superabsorbent polymer to make the hydraulic fracturing composition. As shown in FIG. 3, the SAP (e.g., particle 12 or fiber 50) is in an unexpanded state 20 with internal crosslinks 14 and has a diameter of D2 prior to contact with the fluid (not shown). As indicated in FIGs. 1 and 2, once contacted with the fluid, the SAP (12 or 50) expands to diameter Dt (where Dt is greater than D2) as the fluid is absorbed into the SAP (12 or 50). Additionally, in the case of an SAP fiber 50 or an SAP that has a major axis, the length of the SAP 50 can lengthen upon expansion caused by absorption of the fluid. It should be noted that the crosslinks 14 limit the volumetric expansion and the ultimate size of the SAP 12. In the expanded state (FIG. 1 or FIG. 2), the proppant particles 18 are disposed in the SAP (12 or 50). The SAPs (12 or 50) shown in FIG. 1, FIG. 2, and FIG. 3 represent a single particle, fiber, etc. of the SAP 12 or a plurality of such items as well as agglomerates of polymer chains that make the SAP (12 or 50).

[0115] The additive including the scale inhibitor, tracer, buffering agent, or a combination thereof, can be added to the fluid before or after disposing the SAP (12 or 50) and the proppant particles 18. Optionally, the additive is added to the SAP and proppant particles. According to an embodiment, the breaker is added to the fluid before or after disposing the SAP (12 or 50) and the proppant particles 18. Optionally, the breaker is added to the SAP and proppant particles.

[0116] In an embodiment, combining the components of the hydraulic fracturing composition is accomplished in a vessel such as a mixer, blender, and the like. In some embodiments, the hydraulic fracturing composition is injected without mixing, e.g. it is injected “on the fly”. The components are mixed, agitated, stirred, and the like. In an embodiment, the components are combined as the hydraulic fracturing composition is being disposed downhole.

[0117] The hydraulic fracturing composition herein has advantageous properties that include suspending the proppant particles in the SAP for an extended period of time or at an

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PCT/US2015/064815 elevated temperature or pressure. The length of time, temperature, or pressure under which the proppant particles remain suspended in the SAP is determined by the polymer chains that make up the SAP as well as the crosslinker compound, degree of crosslinking, amount of proppant particles present, concentration of the SAP, and identity of the fluid.

[0118] Accordingly, the hydraulic fracturing composition includes a highly crosslinked SAP, lightly crosslinked SAP, or a combination thereof. In the hydraulic fracturing composition, the SAP is configured to be broken and to release the proppant particles in response to the breaking condition. The breaking condition includes a temperature, pH, contact between the breaker and the SAP, a time lapse between the SAP being in the expanded state and breaking the superab sorbent polymer. In an embodiment, the time the proppant particles are disposed in the SAP prior to release from the SAP is greater than or equal to 48 hours at a temperature greater than or equal to 150°F, specifically greater than or equal to 36 hours, more specifically greater than or equal to 24 hours, even more specifically greater than or equal to 18 hours, and yet more specifically greater than or equal to 20 minutes, preferably from 10 minutes to 18 hours.

[0119] In an embodiment, the pH for breaking the SAP is a pH effective to break bonds in the SAP, crosslinker, between the SAP and crosslinker, or a combination thereof. Likewise, in an embodiment, the pH causes dissociation between particles of SAP so that the proppant particles are released therefrom. In an embodiment, the pH is acidic or basic so that ionic groups of the polymer chains in the SAP are neutralized, which affects the amount of fluid present in the SAP and causes contraction of the SAP and expulsion of the proppant particles. According to an embodiment, the pH is from 1 to 12, specifically 3 to 12, and more specifically 5 to 11.5.

[0120] In an embodiment, the SAP breaks due to the breaking condition even in the absence of the breaker. Thus, in an embodiment, the SAP is broken at a temperature, pH, time lapse, and the like without contact with the breaker.

[0121] In an embodiment, the viscosity of the SAP in the expanded state is from 1 centipoise (cP) to 1000 cP, and specifically 1 cP to 300 cP, as measured by Ofite M900 rheometer for less than 100 cP viscosity or Grace M5500 rheometer for more than 100 cP viscosity at a temperature of 180°F.

[0122] The hydraulic fracturing composition is useful e.g., to transport and dispose proppant particles in a fracture without the SAP being broken until after disposal of the proppant particles to prevent proppant particles from settling and therefore increase overall fractured surface area. According to an embodiment, the hydraulic fracturing composition is

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PCT/US2015/064815 used to form the fracture. In an embodiment, a process for disposing a plurality of proppant particles in a fracture includes disposing a hydraulic fracturing composition in a downhole environment. The hydraulic fracturing composition includes an SAP in an expanded state and configured to break in response to a breaking condition, such that a decomposed polymer is formed from the superabsorbent polymer. The hydraulic fracturing composition also includes a plurality of proppant particles disposed in the SAP prior to release of the plurality of proppant particles from the SAP in response to breaking the SAP, an additive comprising a scale inhibitor, tracer, buffer, or combination thereof, and a fluid to expand the SAP into the expanded state. In this method, forming a fracture in the downhole environment is accomplished by applying hydraulic force on the downhole environment from the hydraulic fracturing composition, disposing the hydraulic fracturing composition in the fracture, breaking the superabsorbent polymer after forming the fracture, and releasing the plurality of proppant particles from superabsorbent polymer to dispose the plurality of proppant particles in the fracture. In this manner, the proppant particles do not settle to the bottom of the fracture. The downhole environment is, e.g., a reservoir temperature, formation water, formation rock, sand, and the like, which contains, e.g., pores or veins of various sizes in such rock, sand, and the like.

[0123] As shown in FIG. 4, after the breaking condition occurs, the SAP is in a broken state 30 such that the SAP forms, e.g., a decomposed polymer 32 with the proppant particles 18 released from the SAP. Although the decomposed polymer 32 is shown as being separated fragments (e.g., polymers, oligomers, monomers, molecules, atoms, and the like, which are charged or charge neutral), in an embodiment, the decomposed polymer is formed from the SAP by breaking all or some of the crosslinks so that the polymer chains of the SAP remain intact. It is contemplated that conformational changes in the SAP release the proppant particles from the SAP and ensure good conductivity.

[0124] In an embodiment, the crosslinks or the SAP are degraded by certain conditions such as heat or pH. Degradation reduces the degree of crosslinking in the SAP by breaking a bond in the crosslinker or a bond between the crosslinker and polymer chains of the SAP. Generally, decreasing the degree of crosslinking of the SAP increases the amount of fluid that is absorbed by the SAP or increases the volumetric increase of the SAP due to fluid absorption. In an embodiment, the aforementioned conditions cleave bonds in the crosslinks without substantially degrading the polymer backbone of the SAP. In some embodiments, these conditions also degrade the polymer backbone of the SAP.

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PCT/US2015/064815 [0125] In addition to disposing the hydraulic fracturing composition in the downhole environment for hydraulically fracturing the formation, the method also includes disposal of other elements such as water, a downhole fluid (e.g., brine or other above-mentioned fluids), a viscose polymer, or a combination thereof. Thus, in an embodiment, the method further includes disposing water, a viscose polymer, or a combination thereof in the downhole environment and forming the fracture with the hydraulic fracturing composition, water, the viscose polymer, or a combination thereof. The order of addition can be varied and the time of injecting each is the same or different. According to an embodiment, for hydraulically fracturing a formation, a proppant-free fluid and a proppant-containing fluid are injected in an alternating order into a subterranean formation. The proppant-free fluid can be injected first followed by the proppant-containing fluid. Alternatively, the proppant-containing fluid is injected first followed by the proppant-free fluid.

[0126] In an exemplary embodiment, the proppant-free fluid comprises an aqueous carrier comprising water, brine, an acid, or a base and a lubricant. The lubricant can comprise a polyacrylamide, a guar, a guar derivative, glycerol, a polysaccharide such as cellulose and starch, or a combination thereof. When the lubricant comprises a polyacrylamide, e.g. MaxPerm 20A, MaxPerm 20A is present in an amount of 0.25 to 15 gallons per one thousand gallons of the proppant-free fluid. When the lubricant comprises a guar, the lubricant is present in an amount of 1 to 50 pounds per one thousand gallons of the proppant-free fluid. The proppant-containing fluid comprises SPP, a plurality of proppant particles disposed in SPP, a fluid to expand the SPP into the expanded state, and optionally a linear gel or a viscous polymer comprising a guar, a guar derivative, a polyacrylamide, glycerol, a polysaccharide, or a combination thereof. The proppant-containing fluid can be the hydraulic fracturing composition disclosed herein. By using the method, high conductivity channels are created within the proppant pack. The effects are illustrated in FIG. 15.

[0127] In another exemplified embodiment, the proppant-free fluid comprises SPP, a fluid to expand the SPP, and optionally a viscous polymer comprising a guar, a guar derivative, a polyacrylamide, glycerol, a polysaccharide, or a combination thereof. For proppant free fluid, 20-60 pounds SPPs are normally prepared in one thousand gallons of proppant-free fluids. Proppant containing fluids comprises an aqueous carrier comprising water, brine, an acid, or a base, proppants, and a lubricant. The lubricant can comprise a polyacrylamide, a guar, a guar derivative, glycerol, a polysaccharide, or a combination thereof. When the lubricant comprises a polyacrylamide, e.g. MaxPerm 20A, MaxPerm 20A

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PCT/US2015/064815 is present in an amount of 0.25 to 15 gallons per one thousand gallons of the proppant-free fluid. When the lubricant comprises a guar, the polymer is present in an amount of 1 to 50 pounds per one thousand gallons of the proppant-containing fluid. Heterogeneous proppant distribution can be achieved by this method. The beneficial effects are illustrated in FIG. 16.

[0128] In an embodiment, the initial injection of water (or brine) and the viscous polymer is, e.g., 15 minutes each although the length of injection times is different in some embodiments. The injection time for the hydraulic fracturing composition is the same or different as the water or viscose polymer, e.g., having a duration of two hours. It is contemplated that the injection time varies and is selected based on conditions of the formation and the properties of the hydraulic fracturing composition, other fluids (e.g., brine), viscose polymer, and the like.

[0129] A benefit of the hydraulic fracturing composition is that the proppant particles remain disposed in the SAP until the breaking condition causes the SAP to break. As shown in FIG. 5, a formation 100 is traversed by a tubular 104 disposed in casing 102 although only the casing 102 or only the tubular 104 is present in some embodiments. The hydraulic fracturing composition 120 is transferred from an interior of the tubular 104 to contact the formation 100 through an aperture (not shown) in the tubular 104. The hydraulic fracturing composition 120 (which is similar to or identical to that of FIG. 1 or FIG. 2) fractures the formation 100 to create a fracture 106. The proppant particles 18 are disposed in the SAP 12 until the breaking condition occurs at which point the SAP 12 breaks to form a decomposed polymer 122 and releases the proppant particles 18 as shown in FIG. 6. Here, the SAP 12 is not broken nor are the proppant particles 18 released from the SAP 12 before closing of the fracture 106. Therefore, the proppant particles 18 do not settle to the bottom of the fracture 106 before the fracture 106 closes so that the geometry of the fracture 106 is not affected negatively by breaking the SAP 12. That is, before the fracture 106 closes, it has a height Hl. After closing, the fracture has a height H2. After closing of the fracture commences, the SAP 12 is broken, and the decomposed polymer 122 is formed. Due to the high degree of suspension of the proppant particles 18 in the SAP 12, the height H2 of the fracture 106 does not vary significantly from the original, pre-closing height Hl, such that the height H2 (postclosing) is nearly the same size as the original height Hl (pre-closing).

[0130] During the breaking of SAP 12, the formation pressure squeezes the proppant particles in-situ from settling to the bottom of the fracture by the broken fluids leaking off. In this manner, the hydraulic fracturing composition accomplishes enhanced proppant particles transport and vertical distribution in the fracture. Consequently, the conduction of

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PCT/US2015/064815 hydrocarbons or other fluids from the formation 100, through the fracture 106, into the tubular 104 (or a space between the tubular 104 and casing 102) is increased relative to incomplete or imperfect disposal of the proppant particles 18, which is shown in FIGs. 7 and

8. Therefore, the hydraulic fracturing composition 120 transports and disposes the proppant particles 18 to ensure that the proppant particles 18 prop open the fracture 106 in the same or substantially the same geometry as the fracture 106 is initially formed and thus provides more fractured surface area than if the proppant particles settle to the bottom of the fracture as shown in the FIGs. 7 and 8. In this manner, a high conduction pathway for transmission of hydrocarbons and other fluids between the formation and the borehole occurs when using the hydraulic fracturing composition herein.

[0131] With regard to FIG. 7 and FIG. 8, when using certain fracturing systems that do not contain the hydraulic fracturing composition herein, such as proppant particles 130 suspended in a fluid 132 without the benefit of the SAP to suspend the proppant particles 130, the proppant particles 130 settle from the fluid 132 and collect on the bottom of the fracture 106 before the fracture 106 closes (FIG. 7). Even though the fracture 106 has an original height H2 before closing (FIG. 7), the height H2 is reduced to a diminished height H4 after closing because the proppant particles 130 settle to the bottom of the fracture 106 before the fracture 106 closed.

[0132] The hydraulic fracturing composition and processes herein are illustrated further by the following non-limiting example.

[0133] Superabsorbent polymer (SAP) (QX-A1051; Nippon Shokubai) was mixed with tap water at a concentration of 40 parts per thousand (ppt) (w/v). The pH of the mixture was determined to be about 7. The pH was adjusted to greater than 7 using the buffer BF10L (from Baker Hughes) and a pH of less than 7 using the buffer BF-9L from Baker Hughes. The viscosity of the mixtures at different pH’s was recorded using a Chandler M5550 instrument according to the API RP 39 standard at 20 °C and under atmospheric pressure. FIG. 17 is a plot showing the effect of pH on viscosity for this example. As shown in FIG. 17, a maximum viscosity was recorded at a fluid pH about 7 to about 8.

[0134] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. The ranges are continuous and thus contain every value and subset thereof in the range. Unless otherwise stated or contextually inapplicable, all percentages, when expressing a quantity, are weight percentages. As used herein, “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. Further As used herein, “a combination thereof’ refers to a combination comprising at least

WO 2016/100048

PCT/US2015/064815 one of the named constituents, components, compounds, or elements, optionally together with one or more like constituents, components, compounds, or elements not named. The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and/or.” The conjunction “or” is used to link objects of a list or alternatives and is not disjunctive; rather the elements can be used separately or can be combined together under appropriate circumstances.

[0135] It should further be noted that the terms “first,” “second,” “primary,” “secondary,” and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the particular quantity). All references are incorporated herein by reference.

[0136] While one or more embodiments have been shown and described, modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustrations and not limitation. Embodiments herein can be used independently or can be combined.

2015362929 21 Dec 2017

Claims

1 hour at 180°F 24 hours at 180°F

FIG.9

Time = 0, Room temperature

FIG.10

WO 2016/100048

PCT/US2015/064815

6/9

200 212

FIG. 12

WO 2016/100048

PCT/US2015/064815

7/9

Time (min)

FIG.13

Left: sample K; Right: sample L

Time = 0, Room Temperature

FIG.14A

WO 2016/100048

PCT/US2015/064815

8/9

Left: sample K; Right: sample L Time = 24 hours, Room Temperature

FIG.14B

FIG.15

FIG.16

WO 2016/100048

PCT/US2015/064815

9/9

Viscosity (cP) at 100/s shear rate

1600

1400

1200

1000

800

600

400

200

1. A.process for disposing a plurality of proppant particles in a fracture, the process comprising:

disposing a hydraulic fracturing composition in a fracture in a downhole environment, the hydraulic fracturing composition comprising:

a superabsorbent polymer in an expanded state and configured to break in response to a breaking condition, such that a decomposed polymer is formed from the superabsorbent polymer, the superabsorbent polymer comprising particles having internal crosslinks derived from ethyleneglycol diacrylate, polyethyleneglycol diacrylate, trimethylopropane trimethacrylate, ethoxylated trimethylol triacrylate, ethoxylated pentaerythritol tetracrylate, or a combination comprising at least one of the foregoing but no intra-particle crosslinks and being present in a mass concentration from 5 ppt to 100 ppt, based on total volume of the composition, the superabsorbent polymer comprising a repeat unit derived from an acrylic acid, an acrylate, an acrylamide, a vinylpyrrolidone, a vinyl acetate, a 2-acrylamide-2methylpropanesulfonic acid, a derivative thereof, or a combination thereof; and the superabsorbent polymer in the expanded state having a viscosity of about 1 centipoise to 300 centipoise as measured by Ofite M900 rheometer at a temperature of 180° F, a plurality of proppant particles disposed in a space between adjacent superabsorbent polymer particles prior to release of the plurality of proppant particles from the superabsorbent polymer particles in response to breaking the superabsorbent polymer, a well treatment agent comprising a scale inhibitor, a tracer, a pH buffering agent, or a combination thereof, and a fluid to expand the superabsorbent polymer into the expanded state; and breaking the superabsorbent polymer with a breaker after closing of the fracture commences; and releasing the plurality of proppant particles from the superabsorbent polymer to dispose the plurality of proppant particles in the fracture, wherein the hydraulic fracturing composition is free of gelling agents except for the superabsorbent polymer.

2/9

WO 2016/100048

PCT/US2015/064815

FIG.4

WO 2016/100048

PCT/US2015/064815

2. The process of claim 1, further comprising decreasing undesired effects caused by scale formation, salt formation, paraffin deposition, asphaltene deposition, foaming agent deposition, emulsification, gas hydrate formation, corrosion, foaming agents, oxygen scavengers, H₂S scavengers, biocides, surfactants, or a combination thereof, compared to a composition without the well treatment agent.

2015362929 21 Dec 2017

3/9

FIG.5

FIG.6

WO 2016/100048

PCT/US2015/064815

4/9

FIG.7

FIG.8

106

WO 2016/100048

PCT/US2015/064815

5/9

Time = 0, Room temperature 15 min at 180°F

3. The process of claim 2, wherein the hydraulic fracturing composition comprises the pH buffering agent and a slow-release acid, and the process further comprises lowering the pH of the hydraulic fracturing composition past the buffering range of the buffering agent before the breaking of the superabsorbent polymer.

4. The process of claim 1, wherein the hydraulic fracturing composition comprises about 0.01 to about 10 wt % of the pH buffering agent, based on the total weight of the hydraulic fracturing composition.

5. The process of claim 4, wherein the pH buffering agent maintains the pH of the hydraulic fracturing composition at about 6 to about 9.

6. The process of claim 4, wherein the pH buffering agent maintains the pH of the hydraulic fracturing composition at about 7 to about 8.

7. The process of claim 4, wherein the pH buffering agent is alkali or alkaline earth salt of a carbonate, a citrate, a gluconate, a phosphate or a tartrate, an oxide of an alkaline earth metal, an organic polyelectrolyte, or a combination thereof.

8. The process of claim 1, wherein the hydraulic fracturing composition comprises the pH buffering agent and further comprises a slow-release acid.

9. The process of claim 8, wherein the slow-release acid comprises glyoxal, an encapsulated acid, a coated acid, or a combination thereof.

10. The process of claim 1, wherein the breaker comprises a peroxide, a persulfate, a peracid, or a combination thereof.

11. The process of claim 10, wherein the breaker is encapsulated in an encapsulating material to prevent the breaker from contacting the superabsorbent polymer, and the encapsulating material is configured to release the breaker.

12. The process of claim 10, wherein the plurality of proppant particles is present in a mass concentration from 0.1 lb/gal to 12 lb/gal, based on the total volume of the

2015362929 21 Dec 2017 composition, and the breaker is present in a mass concentration from greater than 0 ppt to 20 ppt, based on the total volume of the composition.

13. The process of claim 1, wherein the superabsorbent polymer comprises the repeat unit derived from an acrylic acid and its salts.

14. The process of claim 13, wherein the superabsorbent polymer comprises the internal crosslinks derived from polyethylene glycol diacrylate.

15. The process of claim 1, wherein the breaker comprises a persulfate.

16. The process of claim 1, wherein the superabsorbent polymer particles have a size of 10 microns to 1,000 microns.

2015362929 21 Dec 2017 ι /9

M...

«->U

VMS' ✓* ^Ά, ’* ·”* V ,fe/«

14'

4 5 6 7 8 9 1

Fluid pH

FIG. 17