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EP-4419618-B1 - FLUORESCENT BARCODED QUANTUM DOTS FOR DRILLING DEPTH CORRELATION

EP4419618B1EP 4419618 B1EP4419618 B1EP 4419618B1EP-4419618-B1

Inventors

  • ALJABRI, Nouf, M.
  • SOLOVYEVA, VERA
  • MARSALA, Alberto, F.

Dates

Publication Date
20260513
Application Date
20221024

Claims (15)

  1. A composition of matter comprising: a core-shell quantum dot particle having an inorganic core and an organic shell, wherein the organic shell comprises an organic ligand or is a polymer; and drilling fluid; and formation cuttings, wherein the core-shell quantum dot particle is attached to the formation cuttings.
  2. The composition of claim 1, wherein the inorganic core is a cadmium-containing chalcogenide.
  3. The composition of claim 1 or 2, wherein the inorganic core is selected from the group consisting of InP, CuInS 2 , InP/ZnSeS/ZnS, PbS, PbO, ZnO, ZnS, HgS, GaAs, GaP, AlGaAs HgTe, InAs, and graphene.
  4. The composition of any one of claims 1-3, wherein the inorganic core is a perovskite.
  5. The composition of claim 4, wherein the perovskite is selected from the group consisting of CsPbBr 3 , and CH 3 NH 3 PbBr 3 .
  6. The composition of any one of claims 1-5, wherein the inorganic core includes a dopant selected from the group consisting of Mn 2+ , Tm 3+ , Er 3+ , Tb 3+ , Eu 3+ , Ag + , and combinations thereof.
  7. The composition of any one of claims 1-6, wherein the organic shell comprises an organic ligand selected from the group consisting of thiols, phosphines and peptides.
  8. The composition of any one of claims 1-7 wherein the organic shell is a polymer; optionally wherein the polymer is of a polymer type selected from the group consisting of polythiols, poly(ethylene glycol), thiolated poly(ethylene glycol), peptides, multidentate phosphine polymers, poly(acrylamide)s, poly(amidoamine)s, poly(ethyleneimine)s, poly(N,N-dimethylaminoethyl methacrylate)s, amphiphilic di- and triblock-co-polymers, poly(maleic acid) derivatives, poly(maleic anhydride-alt-1-tetradecene), and combinations thereof.
  9. The composition of claim 8, wherein the polymer is selected from the group consisting of poly ethyleneimine, polyacrylamide, poly chlorostyrene, poly bromostyrene, and poly methylstyrene.
  10. The composition of claim 8, wherein the polymer is derived from units of at least one monomer, wherein the monomer is selected from the group consisting of styrene, aminostyrene, bromostyrene, chlorostyrene, butylmetacrylate, t-butyoxystyrene, trifluoromethyl styrene, pentafluorostyrene, ethylene glycol dimetacrylate, triethyl orthosilicate, ethylene oxide, acrylic acid, methacrylic acid, ethylene, propylene, and combinations thereof.
  11. A method comprising: introducing a core-shell quantum dot particle having an inorganic core and a polymer shell into a drilling fluid; circulating the drilling fluid through a well during a drilling operation that creates formation cuttings such that the core-shell quantum dot particle interacts with the formation cuttings, creating tagged cuttings; collecting returned cuttings from the circulating drilling fluid at a surface of the well; detecting the presence of the core-shell quantum dot particle on the returned cuttings to identify the tagged cuttings; and correlating the tagged cuttings with a drill depth in the well at a time during the drilling operation.
  12. The method of claim 11, wherein detecting the core-shell quantum dot particle comprises illuminating the tagged cuttings with UV light and obtaining images of the cuttings with a camera.
  13. The method of claim 11 or 12, wherein the detecting the core-shell quantum dot particle comprises using a detection method selected from the group consisting of UV-visible spectroscopy, fluorimetry, and mass spectroscopy.
  14. The method of any one of claims 11-13, further comprising: pumping a second core-shell quantum dot particle with the drilling fluid down the well after circulating the core-shell quantum dot particle, wherein the second core-shell quantum dot particle is configured to attach to and tag formation cuttings as the well is drilled; returning the drilling fluid and tagged formation cuttings from the well; and detecting the presence of the second core-shell quantum dot particle on the tagged cuttings.
  15. The method of claim 14, wherein the core-shell quantum dot particle comprises a first emission wavelength, wherein the second core-shell quantum dot particle comprises a second emission wavelength, and wherein the first emission wavelength is different from the second emission wavelength such that the core-shell quantum dot particle may be differentiated from the second core-shell quantum dot particle by illuminating the core-shell quantum dot particles with UV light and obtaining images of the tagged cuttings with a camera.

Description

BACKGROUND Drilling fluid, also referred to as "drilling mud" or simply "mud," is used to facilitate drilling boreholes into the earth, such as drilling oil and natural gas wells. The main functions of drilling fluids include providing hydrostatic pressure to prevent formation fluids from entering into the borehole, keeping the drill bit cool and clean during drilling, carrying out drill cuttings, and suspending the drill cuttings while drilling is paused and when the drilling assembly is brought in and out of the borehole. Drill cuttings, also referred to as "rock cuttings" or "formation cuttings" are rock fragments generated by the drill bit as the drill bit advances along the borehole. Mud logging is the creation of a well log of a borehole by examining the rock cuttings brought to the surface by the circulating drilling mud. A taggant or "tag" is a chemical or physical marker added to materials to allow various forms of testing of the marked materials. The taggant can be detected using a taggant detector. A physical taggant can take many different forms but is typically microscopic in size, added to the materials at low levels, and simple to detect. The taggant may be encoded based on a specific characteristic (e.g., optical, chemical, electrical, or mechanical characteristic) to act as a virtual "fingerprint." Examples of encoded taggant include microscopic, metallic tags, e.g., between 0.3 and 1.0 millimeters, that have unique multi-digit alphanumeric identification codes. For example, the identification code may be etched into an optically variable (holographic) substrate of the tag. The tags may be suspended in a UV sensitive clear adhesive which is either brushed or sprayed onto any item for authentication or other security purposes. WO2012154332 discloses surface-modified nanomaterials and methods of making surface-modified nanomaterials comprising synthesizing an amphiphilic copolymer, providing a nanomaterial, and modifying the surface of the nanomaterial with the amphiphilic copolymer. US2018283173 discloses a process for developing a subterranean formation, in which at least one fluid is injected. In accordance with the invention, the fluid comprises at least one additive, the additive being labelled with at least one luminescent semiconductor nanocrystal (fluorescent or phosphorescent). In this manner, and by optical analysis of the presence of luminescent semiconductor nanocrystal in the fluid recovered from the subterranean formation, the presence and/or quantity of additive in the recovered fluid can be determined. Given that the semiconductor nanocrystal is either phosphorescent or fluorescent, the additive is rendered readily detectable and quantitatively determinable in the fluids recovered from the subterranean formation. SUMMARY This summary is provided to introduce a selection of concepts that are further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter. In one aspect, embodiments disclosed herein relate to a composition of matter comprising a core-shell quantum dot particle having an inorganic core and an organic shell, wherein the organic shell comprises an organic ligand or is a polymer; and drilling fluid; and formation cuttings, wherein the core-shell quantum dot particle is attached to the formation cuttings. In another aspect, embodiments disclosed herein relate to a method that includes introducing a core-shell quantum dot particle having an inorganic core and a polymer shell into a drilling fluid, circulating the drilling fluid through a well during a drilling operation that creates formation cuttings such that the core-shell quantum dot particle interacts with the formation cuttings, creating tagged cuttings, collecting returned cuttings from the circulating drilling fluid at a surface of the well, detecting the presence of the core-shell quantum dot particle on the returned cuttings to identify the tagged cuttings, and correlating the tagged cuttings with a drill depth in the well at a time during the drilling operation. Other aspects and advantages of the claimed subject matter will be apparent from the following description and the appended claims. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 shows a system according to embodiments of the present disclosure.FIG. 2 shows a schematic depiction of a core/shell quantum dot in accordance with one or more embodiments.FIG. 3 shows a block flow diagram of a method in accordance with one or more embodiments of the present disclosure. DETAILED DESCRIPTION Specific embodiments of the disclosure will now be described in detail with reference to the accompanying figures. Like elements in the various figures are denoted by like reference numerals for consistency. In the following detailed description of embodiments of the disclosure, numerous specific details