Hybrid Fluorescence Magnetic Core-Shell Nanoparticles for Use in Oil and Gas Applications

Patent metadata

Field	Value
Publication number	US-2017361376-A1
Application number	US-201615187603-A
Country	US
Kind code	A1
Filing date	Jun 20, 2016
Priority date	Jun 20, 2016
Publication date	Dec 21, 2017
Grant date	—

Abstract

Nanoparticles for use in the treatment of a well have a magnetic core of iron, nickel or cobalt or an alloy thereof; a carbon shell encapsulating the magnetic core; at least one organic functional group on the surface of the carbon shell through covalent bonding; and a coating of amorphous carbon nitride encapsulating the functionalized carbon shell. The nanoparticles may be used to identify fluids produced from the reservoir, identify the zone within the reservoir from which recovered fluid is produced, in water flooding to determine water breakthrough in the production well and to identify those injection wells from which breakthrough water originates.

First claim

What is claimed is:

1 . A spherical nanoparticle comprising:
(a) a magnetic core comprising iron, nickel or cobalt or alloys thereof; (b) a carbon shell encapsulating the magnetic core; (d) at least one organic functional group on the surface of the carbon shell through covalent bonding (c) a coating of amorphous carbon nitride encapsulating the functionalized carbon shell through chemical reaction

2 . The spherical nanoparticle of claim 1 , wherein the magnetic core comprises iron carbide or metallic iron of zero oxidation state.

3 . The spherical nanoparticle of claim 1 , wherein the carbon shell is a graphitic carbon, carbon onions, graphene or graphene oxide.

4 . The spherical nanoparticle of claim 1 , wherein the at least one organic functional group is a carboxylic, sulfonate, sulfate, sulfosuccinate, thiosulfate, succinate, carboxylate, hydroxyl, glucoside, alkyl, ethoxylate, propoxylate, phosphate, ether, amine, amide, imido or a combination thereof.

5 . The spherical nanoparticle of claim 1 , wherein the at least one organic functional group is —SH, —NH 2 , —NHCO, —OH, —COOH, —F, —Br, —Cl, —I, CN, SCN, O—Si—R, —H, —R—NH, —R—, —R—S, —COP, —COCl and —SCl.

6 . The spherical nanoparticle of claim 1 , wherein the coating of the carbon shell encapsulating the magnetic core is from about 1 nm to about 1 micron.

7 . The spherical nanoparticle of claim 1 , wherein the diameter of the magnetic core is from 5 nm to about 100 nm.

8 . The spherical nanoparticle of claim 1 , wherein the at least one organic functional group is hydrophilic, hydrophobic and/or oleophilic.

9 . The spherical nanoparticle of claim 1 , wherein the nanoparticle has at least two organic functional groups which are qualitatively and/or quantitatively distinguishable from each other.

10 . A plasmonic nanoparticle comprising:
(a) a magnetic core of iron carbide or metallic iron of a zero oxidation state, wherein the diameter of the magnetic core is from about 5 nm to about 100 nm; (b) a protective carbon shell encapsulating the magnetic core, wherein the thickness of the protective carbon shell is from about 1 nm to about 1 micron; (c) a luminescent amorphous carbon nitride coating encapsulating the carbon shell wherein the carbon nitride coating is attached to the carbon shell by an alkyl carboxylic acid and wherein the thickness of the amorphous carbon nitride coating is from about 1 nm to about 1 micron.

11 . The plasmonic nanoparticle of claim 10 , further comprising at least one luminescent organic functional group attached to the carbon shell which is qualitatively and/or quantitatively distinguishable from the alkyl carboxylic acid.

12 . A composite comprising:
(a) the nanoparticle of claim 1 ; (b) a porous adsorbent, wherein the nanoparticle is adsorbed and immobilized into the pores of the porous adsorbent; (c) a polymeric coating encompassing the adsorbent.

13 . The composite of claim 12 , wherein the composite is adsorbed onto a water-insoluble adsorbent.

14 . The composite of claim 13 , wherein the water-insoluble adsorbent is selected from the group consisting of activated carbon, silica particulate, precipitated silica, zeolite, diatomaceous earth, ground walnut shells, fuller's earth and organic synthetic high molecular weight water-insoluble adsorbents.

15 . The composite of claim 12 , wherein the polymeric coating is a thermosetting resin.

16 . A process of preparing the nanoparticle of claim 1 comprising:
(a) attaching the least one organic functional group onto the carbon shell encapsulating the magnetic core to render a functionalized carbon encapsulated core;
(b) reacting cyanuric chloride and lithium nitride in the presence of the functionalized carbon encapsulated core to form carbon nitride; and
(c) encompassing the carbon shell with the carbon nitride.

17 . The process of claim 16 , wherein the cyanuric chloride and lithium nitride are reacted in the presence of the functionalized carbon encapsulated core at a temperature from 50° C. to 175° C. in an organic solvent.

18 . The process of claim 16 , wherein the at least one functional group on the functionalized carbon encapsulated core is an alkyl carboxylic acid.

19 . A process of preparing a fluorescent, plasmonic and magnetic nanoparticle comprising the steps of:
(a) coating a carbon shell onto a magnetic material and encompassing the magnetic material with the carbon shell, wherein the thickness of the carbon shell is between from about 1 nm to about 1 micron and further wherein the magnetic material is iron carbide or iron having a zero oxidation state; (b) attaching an alkyl carboxylic acid onto the carbon shell; and (b) reacting cyanuric chloride and lithium nitride in the presence of the product of step (b) and attaching amorphous carbon nitride onto the alkyl carboxylic acid.

20 . A method of treating a well or a subterranean formation penetrated by a well, the method comprising:
(a) introducing into the well the composite of claim 12 ; (b) degrading or solubilizing the polymeric coating into a fluid within the well; (c) releasing the nanoparticle from the adsorbent into the fluid; (d) recovering the fluid containing the nanoparticle from the well; (e) concentrating the nanoparticle at the surface of the well by subjecting the fluid to a magnetic field; and (f) subjecting a sample containing the concentrated nanoparticle to luminescence.

21 . The method of claim 20 , further comprising:
(g) qualitatively and/or quantitatively identifying the at least one functional group in fluid produced from the well by luminescence.

22 . A method of fracturing multiple zones of a subterranean formation penetrated by a well which comprises:
(a) pumping into each zone of the formation to be fractured a fracturing fluid, wherein the fracturing fluid pumped into each zone comprises nanoparticles of claim 1 and further wherein the at least one organic functional group on the nanoparticles introduced into each zone is qualitatively and quantitatively distinguishable; (b) enlarging or creating a fracture in the formation; (c) recovering fluid from at least one of the multiple zones; and (d) identifying the zone within the subterranean formation from which the recovered fluid was produced by identifying the at least one functional group of the nanoparticles in the recovered fluid.

23 . A method of increasing hydrocarbon production from a production well penetrating a hydrocarbon-bearing reservoir, wherein more than one injection well is associated with the production well, the method comprising:
(a) injecting an aqueous fluid having a water soluble nanoparticle comprising the nanoparticles of claim 1 into the more than one injection well and maintaining pressure in the hydrocarbon-bearing reservoir above the bubble point of the hydrocarbons in the reservoir, wherein the aqueous fluid pumped into each of the injection wells contains qualitatively distinguishable functional groups on the surface of the carbon shell; (b) identifying from hydrocarbons recovered from the production well, upon water breakthrough in the production well, the injection well into which the breakthrough water was injected by qualitatively determining the presence of the functional groups in the recovered hydrocarbons; and (c) shutting off the injector well identified in step (b).

Assignees

• Baker Hughes Inc

Inventors

• Murugesan Sankaran
• Kuznetsov Oleksandr
• Khabashesku Valery N

Classifications

• C09B67/0097

  Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes · CPC title

• B22F7/06

  of composite workpieces or articles from parts, e.g. to form tipped tools {(B22F7/002 takes precedence)} · CPC title

• B22F2999/00

  Aspects linked to processes or compositions used in powder metallurgy · CPC title

• B01J13/22

  Coating · CPC title

• B22F1/056

  Submicron particles having a size above 100 nm up to 300 nm · CPC title