# US 11,999,904 B2 · Reactive hydraulic fracturing fluid > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,999,904 B2 - Document ID: US11999904B2 - Status: Granted - Kind: B2 - Application number: 17/707,107 - Filed: 2022-03-29 - Published: 2022-07-14 - Granted: 2024-06-04 - Earliest claimed: 2019-12-31 - Assignees: Saudi Arabian Oil Company - Applicants: Saudi Arabian Oil Company - Inventors: Katherine Leigh Hull; Rajesh Kumar Saini; Younane N. Abousleiman; Desmond Schipper - Web page: https://patentgrep.com/patent/US11999904B2 ## CPC - C09K 8/665: {containing inorganic compounds (proppants C09K8/80)} - C09K 8/68: containing organic compounds - C09K 8/594: Compositions used in combination with injected gas {, e.g. CO2 orcarbonated gas}(C09K8/592 takes precedence) - C09K 8/64: Oil-based compositions - C09K 8/703: {Foams} - C09K 8/82: Oil-based compositions (C09K8/64 takes precedence) - C09K 8/845: {containing inorganic compounds} - C09K 8/94: Foams - E21B 43/26: by forming crevices or fractures - E21B 43/267: reinforcing fractures by propping - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS ## Abstract Hydraulic fracturing fluids and methods to hydraulically fracture a subterranean formation and oxidize organic material in the subterranean formation. The hydraulic fracturing fluid includes water, another fluid, and a surfactant. An inorganic oxidizer is included in the water. ## Claims ### Claim 1 A method of hydraulic fracturing, comprising: providing a hydraulic fracturing fluid through a wellbore into a subterranean formation, the hydraulic fracturing fluid comprising water, a nonpolar fluid, and a surfactant, wherein the hydraulic fracturing fluid comprises an inorganic oxidizer in the water and a reactive gas that is an oxidizer in the nonpolar fluid, wherein the nonpolar fluid is at least 50 vol % of the hydraulic fracturing fluid, and wherein the water is less than 50 vol % of the hydraulic fracturing fluid, wherein the hydraulic fracturing fluid comprises an aqueous phase and a non-aqueous phase, wherein the aqueous phase comprises the water and is a continuous phase of the hydraulic fracturing fluid, and wherein the non-aqueous phase comprises the nonpolar fluid and is not a continuous phase of the hydraulic fracturing fluid; hydraulically fracturing the subterranean formation with the hydraulic fracturing fluid; and oxidizing organic material in the subterranean formation with the hydraulic fracturing fluid. ### Claim 2 (depends on 1) The method of claim 1, wherein the nonpolar fluid comprises an inert gas. ### Claim 3 (depends on 2) The method of claim 2, wherein the hydraulic fracturing fluid comprises foam with the water as an external phase and the inert gas as an internal phase. ### Claim 4 (depends on 2) The method of claim 2, wherein the hydraulic fracturing fluid comprises a liquid-carrying gas with the inert gas as a continuous phase and the water as a dispersed phase. ### Claim 5 (depends on 2) The method of claim 2, comprising preparing the hydraulic fracturing fluid, wherein preparing comprises: mixing the water, the surfactant, and the inorganic oxidizer to give a first mixture; adding the reactive gas to the nonpolar fluid; and injecting the nonpolar fluid into the first mixture. ### Claim 6 (depends on 1) The method of claim 1, wherein the reactive gas that is the oxidizer comprises chlorine dioxide, bromine, ozone, or chlorine. ### Claim 7 (depends on 1) The method of claim 1, wherein the reactive gas that is the oxidizer comprises chlorine dioxide. ### Claim 8 (depends on 1) The method of claim 1, wherein concentration of the surfactant in the hydraulic fracturing fluid is less than 5 volume percent (vol %), wherein the surfactant comprises an interfacial surfactant that promotes the hydraulic fracturing fluid comprising two phases, and wherein the two phases comprise an aqueous phase and a nonpolar phase. ### Claim 9 (depends on 1) The method of claim 1, wherein the nonpolar fluid is at least 70 vol % of the hydraulic fracturing fluid, wherein the water is less than 30 vol % of the hydraulic fracturing fluid, wherein the hydraulic fracturing fluid comprises an aqueous phase and a non-aqueous phase, wherein the non-aqueous phase comprises the nonpolar fluid and is a continuous phase of the hydraulic fracturing fluid, and wherein the aqueous phase comprises the water and is not a continuous phase of the hydraulic fracturing fluid. ### Claim 10 (depends on 1) The method of claim 1, wherein the hydraulic fracturing fluid comprises an aqueous phase and a nonpolar phase, wherein the nonpolar phase is an external phase in the hydraulic fracturing fluid, and wherein the aqueous phase is an internal phase in the fracturing fluid. ### Claim 11 (depends on 1) The method of claim 1, wherein the hydraulic fracturing fluid comprises an aqueous phase and a nonpolar phase, wherein the aqueous phase is an external phase in the hydraulic fracturing fluid, and wherein the nonpolar phase is an internal phase in the fracturing fluid. ### Claim 12 (depends on 1) The method of claim 1, wherein concentration of the inorganic oxidizer in the water is in a range of 10 millimolar (mM) to 200 mM, and wherein the inorganic oxidizer comprises an anion that is bromate, chlorate, perchlorate, chlorite hypochlorite, persulfate, iodate, bromite, perborate, dichromate, permanganate, ferrate, percarbonate, nitrite, or nitrate. ### Claim 13 A method of hydraulic fracturing, comprising: providing a hydraulic fracturing fluid through a wellbore into a subterranean formation, the hydraulic fracturing fluid comprising an aqueous phase and a non-aqueous phase, the aqueous phase comprising water and an inorganic oxidizer in the water and is a continuous phase of the hydraulic fracturing fluid, wherein the water is less than 50 vol % of the hydraulic fracturing fluid, wherein a reactive gas that is an oxidizer is in the non-aqueous phase; hydraulically fracturing the subterranean formation with the hydraulic fracturing fluid; and oxidizing organic material in the subterranean formation with the hydraulic fracturing fluid, wherein oxidizing the organic material comprises degrading the organic material, and wherein the organic material comprises kerogen. ### Claim 14 (depends on 13) The method of claim 13, comprising specifying a concentration of the inorganic oxidizer in the water or in the hydraulic fracturing fluid based at least in part on an amount of kerogen in the subterranean formation, wherein a molality of the inorganic oxidizer in the water is in a range of 10 millimolar (mM) to 200 nM, and wherein the inorganic oxidizer comprises an anion comprising bromate, chlorate, perchlorate, chlorite hypochlorite, persulfate, iodate, bromite, perborate, dichromate, permanganate, ferrate, percarbonate, nitrite, or nitrate. ### Claim 15 (depends on 14) The method of claim 14, wherein the non-aqueous phase is an external phase of the hydraulic fracturing fluid, and wherein the aqueous phase in an internal phase of the hydraulic fracturing fluid. ### Claim 16 (depends on 14) The method of claim 14, wherein the non-aqueous phase is an internal phase of the hydraulic fracturing fluid, wherein the aqueous phase in an external phase of the hydraulic fracturing fluid, and wherein the fracturing fluid comprises a foam, an emulsion, or a foamed emulsion. ### Claim 17 (depends on 14) The method of claim 14, wherein the non-aqueous phase comprises an inert gas having the reactive gas that is the oxidizer. ### Claim 18 (depends on 17) The method of claim 17, wherein the inert gas comprises carbon dioxide (CO2), nitrogen (N2), ethane, propane, butane, or argon, or mixtures thereof. ### Claim 19 (depends on 17) The method of claim 17, wherein the hydraulic fracturing fluid comprises foam, wherein the non-aqueous phase is an internal phase of the hydraulic fracturing fluid, and wherein the concentration of the water in the hydraulic fracturing fluid is less than 50 volume percent (vol %). ### Claim 20 (depends on 17) The method of claim 17, wherein the non-aqueous phase is an external phase of the hydraulic fracturing fluid, wherein the aqueous phase is an internal phase of the hydraulic fracturing fluid, and wherein the concentration of the water in the hydraulic fracturing fluid is less than 30 vol %. ### Claim 21 (depends on 14) The method of claim 14, wherein the hydraulic fracturing fluid comprises a foamed emulsion, wherein the aqueous phase is an external phase of the hydraulic fracturing fluid, wherein the non-aqueous phase comprises a first non-aqueous phase and a second non-aqueous phase that are internal phases of the hydraulic fracturing fluid, the first non-aqueous phase comprising an inert gas having the reactive gas and the second non-aqueous phase comprising a nonpolar fluid. ### Claim 22 (depends on 21) The method of claim 21, wherein the nonpolar fluid comprises oil. ### Claim 23 (depends on 21) The method of claim 21, wherein the second non-aqueous phase comprises an organic oxidizer. ### Claim 24 (depends on 14) The method of claim 14, comprising adding proppant to the hydraulic fracturing fluid, wherein the hydraulic fracturing fluid comprises the proppant for at least a portion of time of providing the hydraulic fracturing fluid through the wellbore into the subterranean formation. ### Claim 25 (depends on 14) The method of claim 14, comprising providing a slickwater fracturing fluid through the wellbore into the subterranean formation before providing the hydraulic fracturing fluid through the wellbore into the subterranean formation. ### Claim 26 (depends on 25) The method of claim 25, wherein the slickwater fracturing fluid comprises an oxidizer, and wherein the hydraulic fracturing fluid comprises proppant. ### Claim 27 (depends on 14) The method of claim 14, comprising providing a CO2-based fracturing fluid through the wellbore into the subterranean formation before or after the providing the hydraulic fracturing fluid through the wellbore into the subterranean formation. ### Claim 28 (depends on 27) The method of claim 27, wherein the CO2-based fracturing fluid comprises an oxidizer that oxidizes the organic material. ### Claim 29 (depends on 14) The method of claim 14, wherein the non-aqueous phase is at least 45 volume percent (vol %) of the hydraulic fracturing fluid. ### Claim 30 (depends on 14) The method of claim 14, comprising: adding chlorine dioxide (ClO2) as the reactive gas to the hydraulic fracturing fluid from a ClO2 generator deployed at a well site of the wellbore; and incorporating at least a majority of the ClO2 into the non-aqueous phase as the reactive gas that is the oxidizer.