# US 10,480,313 B2 · Multicolor fluorescent silica nanoparticles as tracers for production and well monitoring > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,480,313 B2 - Document ID: US10480313B2 - Status: Granted - Kind: B2 - Application number: 15/626,389 - Filed: 2017-06-19 - Published: 2018-12-20 - Granted: 2019-11-19 - Earliest claimed: 2017-06-19 - Assignees: Baker Hughes, A Ge Company, LLC - Applicants: Sankaran Murugesan; Radhika Suresh; Oleksandr Kuznetsov; Valery Khabashesku; Qusai Darugar - Inventors: Sankaran Murugesan; Radhika Suresh; Oleksandr Kuznetsov; Valery Khabashesku; Qusai Darugar - Web page: https://patentgrep.com/patent/US10480313B2 ## CPC - G01N 21/643: {non-biological material} - B82Y 15/00: Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors - C09K 8/032: {Inorganic additives} - C09K 8/035: Organic additives - C09K 8/56: Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof (compositions for plastering borehole walls C09K8/50; {Soil-conditioning materials or soil-stabilising materials in general C09K17/00}) - C09K 8/58: Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids - C09K 8/665: {containing inorganic compounds (proppants C09K8/80)} - C09K 8/72: Eroding chemicals, e.g. acids - C09K 8/805: {Coated proppants} - E21B 47/11: using tracers; using radioactivity - G01N 33/241: {for hydrocarbon content} - C09K 2208/10: Nanoparticle-containing well treatment fluids - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - 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 A method of determining a property within a subterranean formation comprises introducing silica nanoparticles into a well; obtaining a sample of a fluid produced from the well; and analyzing the sample for presence of the silica nanoparticles, wherein the silica nanoparticles comprise a core, a donor chromophore, an acceptor chromophore, and an outer silica shell; the donor chromophore and the acceptor chromophore being selected such that an emission spectrum of the donor chromophore overlaps with an absorption spectrum of the acceptor chromophore. ## Claims ### Claim 1 A method of determining a property within a subterranean formation, the method comprising: introducing silica nanoparticles into a well; obtaining a sample of a fluid produced from the well; and analyzing the sample for presence of the silica nanoparticles, wherein the silica nanoparticles comprise a silica core, a donor chromophore, an acceptor chromophore, and an outer silica shell; the donor chromophore and the acceptor chromophore being selected such that an emission spectrum of the donor chromophore overlaps with an absorption spectrum of the acceptor chromophore. ### Claim 2 (depends on 1) The method of claim 1, wherein the silica core is doped with the donor chromophore via coating, adsorption, absorption, covalent bonding, or a combination comprising at least one of the foregoing. ### Claim 3 (depends on 2) The method of claim 2, wherein the silica nanoparticles further comprise an intermediate silica shell encapsulating the silica core and the donor chromophore. ### Claim 4 (depends on 3) The method of claim 3, wherein the intermediate silica shell is doped with the acceptor chromophore via coating, adsorption, absorption, covalent bonding, or a combination comprising at least one of the foregoing. ### Claim 5 (depends on 1) The method of claim 1, wherein the donor chromophore is a fluorescent and the acceptor chromophore is a fluorescent or phosphorescent. ### Claim 6 (depends on 1) The method of claim 1, wherein the outer silica shell is functionalized. ### Claim 7 (depends on 1) The method of claim 1, wherein the silica nanoparticles are included in a fluid, and the method comprises injecting the fluid into the well. ### Claim 8 (depends on 1) The method of claim 1, wherein the fluid is injected into the well during a fracturing operation, a sand control operation, a flooding operation, an acidifying operation, or a combination comprising at least one of the foregoing. ### Claim 9 (depends on 1) The method of claim 1, further comprising: introducing silica nanoparticles exhibiting a first optical property into a first zone of the well; introducing silica nanoparticles exhibiting second optical property into a second zone of the well; and analyzing the sample for presence of silica nanoparticles exhibiting the first optical property and the silica nanoparticles exhibiting the second optical property. ### Claim 10 (depends on 1) The method of claim 1, wherein the donor chromophore is present in an amount of about 0.1 micro moles to about 10 milli moles, and the acceptor chromophore is present in an amount of about 0.001 micromoles to about 10 milli moles, each based on 1 gram of the silica core. ### Claim 11 (depends on 1) The method of claim 1, wherein the donor chromophore is present in an amount of about 1 micro moles to about 10 milli moles, and the acceptor chromophore is present in an amount of about 0.01 micro moles to about 10 milli moles, each based on 1 gram of the silica core. ### Claim 12 (depends on 1) The method of claim 1, wherein the donor chromophore comprises fluorescein isothiocyanate and the acceptor chromophore comprises tris(1,10-phenanathroline) ruthenium. ### Claim 13 A method of fracturing multiple productive zones of a subterranean formation penetrated by a well, the method comprising: injecting a fracturing fluid into the multiple production zones at a pressure sufficient to enlarge or create fractures in the multiple productive zones, wherein the fracturing fluid comprises silica nanoparticles; recovering a fluid containing hydrocarbons from one or more of the multiple productive zones; detecting the silica nanoparticles in the recovered fluid; and identifying the zone from which the recovered fluid was produced or monitoring an amount of fluids produced from at least one of the multiple productive zones by identifying the silica nanoparticles in the recovered fluid, wherein the silica nanoparticles comprise a silica core, a donor chromophore, an acceptor chromophore, and an outer silica shell; the donor chromophore and the acceptor chromophore being selected such that an emission spectrum of the donor chromophore overlaps with an absorption spectrum of the acceptor chromophore. ### Claim 14 (depends on 13) The method of claim 13, further comprising determining the presence of dispersed oil in produced water from the silica nanoparticles. ### Claim 15 (depends on 13) The method of claim 13, wherein the silica nanoparticles injected into each of the multiple productive zones is qualitatively distinguishable, quantitatively distinguishable, or a combination thereof. ### Claim 16 A method of enhancing the production of hydrocarbon from a production well penetration a hydrocarbon bearing formation, wherein one or more of the injection well are associated with the production well, the method comprising: introducing into one or more of the injection wells a fluid comprising silica nanoparticles; flowing at least a portion of the fluid comprising the silica nanoparticles from the injection well to the production well; and recovering a production fluid from the production well, wherein the silica nanoparticles comprise a silica core, a donor chromophore, an acceptor chromophore, and an outer silica shell; the donor chromophore and the acceptor chromophore being selected such that an emission spectrum of the donor chromophore overlaps with an absorption spectrum of the acceptor chromophore. ### Claim 17 (depends on 16) The method of claim 16, wherein the donor chromophore is a fluorescent and the acceptor chromophore is a fluorescent or phosphorescent. ### Claim 18 (depends on 16) The method of claim 16, wherein the silica nanoparticles are functionalized. ### Claim 19 A method of determining water breakthrough in a production well associated with one or more injection wells, the method comprising: introducing a fluid comprising silica nanoparticles into an injection well; flowing the fluid from the injection well into the production well; producing a production fluid from the production well; determining water breakthrough in the production well by qualitatively determining the presence or quantitatively measuring the amount of the silica nanoparticles in the production fluid, wherein the silica nanoparticles comprise a silica core, a donor chromophore, an acceptor chromophore, and an outer silica shell; the donor chromophore and the acceptor chromophore being selected such that an emission spectrum of the donor chromophore overlaps with an absorption spectrum of the acceptor chromophore. ### Claim 20 (depends on 19) The method of claim 19, further comprising identifying, upon water breakthrough in the production well, the injection well into which the breakthrough water was injected by qualitatively determining the presence of silica nanoparticles in a fluid recovered from the production well. ### Claim 21 (depends on 20) The method of claim 20, further comprising shutting off the identified injection well. ### Claim 22 (depends on 19) The method of claim 19, wherein the donor chromophore is a fluorescent and the acceptor chromophore is a fluorescent or phosphorescent.