# US 8,739,876 B2 · Nanohybrid-stabilized emulsions and methods of use in oil field applications > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,739,876 B2 - Document ID: US8739876B2 - Status: Granted - Kind: B2 - Application number: 13/005,861 - Filed: 2011-01-13 - Published: 2012-07-19 - Granted: 2014-06-03 - Earliest claimed: 2011-01-13 - Assignees: Halliburton Energy Services, Inc. - Applicants: Rajesh K. Saini; Lewis R. Norman - Inventors: Rajesh K. Saini; Lewis R. Norman - Web page: https://patentgrep.com/patent/US8739876B2 ## CPC - C09K 8/36: Water-in-oil emulsions - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - C04B 40/0633: {Chemical separation of ingredients, e.g. slowly soluble activator} - C09K 8/265: {containing inorganic additives} - C09K 8/467: containing additives for specific purposes - C09K 8/62: Compositions for forming crevices or fractures - C09K 8/74: combined with additives added for specific purposes - C09K 2208/14: Double emulsions, i.e. oil-in-water-in-oil emulsions or water-in-oil-in-water emulsions - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE ## Abstract Methods of using nanohybrid-stabilized emulsions in a well are provided that include the steps of: (a) forming an emulsion comprising: (i) a nanohybrid; (ii) water or an aqueous solution; and (iii) a water-immiscible liquid; (b) introducing a well fluid comprising the emulsion into a well; and (c) after the step of introducing, modifying the nanohybrid to break the emulsion in the well. The methods can be used in various applications, such as in drilling, completion, or intervention operations. ## Claims ### Claim 1 A method of using a nanohybrid-stabilized emulsion in a well, wherein the method comprises the steps of: (a) forming an emulsion comprising: (i) a nanohybrid comprising a carbon nanotube attached to a hydrophilic inorganic second component; (ii) water or an aqueous solution; and (iii) a water-immiscible liquid; (b) introducing a well fluid comprising the emulsion into the well; and (c) after the step of introducing, modifying the nanohybrid to break the emulsion in the well. ### Claim 2 (depends on 1) The method according to claim 1, wherein the nanohybrid has a hydrophilic-lipophilic balance adapted to forming an oil-in-water emulsion. ### Claim 3 (depends on 1) The method according to claim 1, wherein the nanohybrid has a hydrophilic-lipophilic balance adapted to forming a water-in-oil emulsion. ### Claim 4 (depends on 1) The method according to claim 1, wherein the emulsion further comprises a polymer or other particles to help stabilize the emulsion. ### Claim 5 (depends on 1) The method according to claim 1, wherein the water-immiscible liquid is water insoluble. ### Claim 6 (depends on 1) The method according to claim 1, wherein the emulsion is stable at 77° F. for 10 days. ### Claim 7 (depends on 1) The method according to claim 1, wherein the emulsion is stable to high-dilution conditions when tested at 77° F. ### Claim 8 (depends on 1) The method according to claim 1, wherein the well fluid introduced into the well is the emulsion. ### Claim 9 (depends on 1) The method according to claim 1, wherein the well fluid is introduced into the well at a rate and pressure and directed to a subterranean formation at a rate and pressure that is at least sufficient to create at least one fracture in the subterranean formation of the well. ### Claim 10 (depends on 1) The method according to claim 1, wherein the well fluid further comprises a proppant. ### Claim 11 (depends on 1) The method according to claim 1, wherein the well fluid is selected from the group consisting of a drilling fluid, a cementing composition, a fluid-loss control pill, an acidizing fluid, a viscous-sweep fluid, a fracturing fluid, a frac-packing fluid, a gravel-packing fluid, a spacer fluid, and a fluid for swelling a swellable packer. ### Claim 12 (depends on 1) The method according to claim 1, wherein the well fluid comprises a chemical for modifying the hydrophilic-lipophilic balance of the nanohybrid. ### Claim 13 (depends on 1) The method according to claim 1, wherein the step of modifying the nanohybrid comprises the use of an oxidizer. ### Claim 14 (depends on 1) The method according to claim 1, wherein the step of modifying the nanohybrid comprises the use of a compound that forms a hydrophilic group to be attached to the nanohybrid, which causes the emulsion to break. ### Claim 15 (depends on 1) The method according to claim 1, wherein the step of modifying the nanohybrid comprises wrapping the nanohybrid with a polymer. ### Claim 16 (depends on 1) The method according to claim 1, wherein the hydrophilic inorganic second component of the nanohybrid is silica. ### Claim 17 (depends on 1) The method according to claim 1, wherein the hydrophilic inorganic second component of the nanohybrid is selected from the group consisting of: alumina, magnesium oxide, and titanium oxide. ### Claim 18 (depends on 1) The method according to claim 1, wherein a dispersed phase of the emulsion comprises a chemical to be released from the dispersed phase upon the step of modifying the nanohybrid to break the emulsion. ### Claim 19 (depends on 18) The method according to claim 18, wherein the chemical to be released comprises at least one additive selected from the group consisting of a retarder or accelerator for cement, a corrosion inhibitor, an acid for acidizing, a crosslinker for a polysaccharide, and a breaker for polysaccharide. ### Claim 20 (depends on 1) The method according to claim 1, wherein the hydrophilic inorganic second component of the nanohybrid comprises silica and the step of modifying the nanohybrid comprises the use of a long chain quaternary amine to modify the silica of the nanohybrid. ### Claim 21 (depends on 20) The method according to claim 20, wherein the step of modifying the nanohybrid comprises functionalizing the silica with silane to make it hydrophobic. ### Claim 22 (depends on 1) The method according to claim 1, further comprising the step of mixing the emulsion with a third fluid to form the well fluid prior to or during the step of introducing the well fluid into the well. ### Claim 23 (depends on 22) The method according to claim 22, wherein the well fluid introduced into the well comprises the emulsion as a nested emulsion in the third fluid, wherein the third fluid is the continuous phase of the well fluid as a whole. ### Claim 24 (depends on 23) The method according to claim 23, wherein the third fluid comprises water and a water-soluble polysaccharide. ### Claim 25 (depends on 24) The method according to claim 24, wherein the third fluid comprises at least a sufficient concentration of the water-soluble polysaccharide to be capable of forming a crosslinked gel upon mixing with a crosslinker. ### Claim 26 (depends on 22) The method according to claim 22, wherein the third fluid comprises water and one or more inorganic ionic salts.