Method of Altering the Wettability of a Subterranean Surface to Enhance Protection of Hydrocarbons

Patent metadata

Field	Value
Publication number	US-2025145878-A1
Application number	US-202519015320-A
Country	US
Kind code	A1
Filing date	Jan 9, 2025
Priority date	May 16, 2023
Publication date	May 8, 2025
Grant date	—

Abstract

A method of imparting hydrophobicity and/or oleophobicity to a surface of a subterranean formation penetrated by a well during production of hydrocarbons from the well consists of pumping a surface modifying wettability agent into the well, the surface modifying wettability agent having an anchor, one or more hydrophobic and/or oleophobic functional groups attached to the anchor and one or more alkoxy groups as blocking moieties which increase stability of the agent in the presence of water by slowing down hydrolysis at the formation surface.

First claim

1 . (canceled)

2 . (canceled)

3 . (canceled)

4 . (canceled)

5 . (canceled)

6 . (canceled)

7 . (canceled)

8 . (canceled)

9 . (canceled)

10 . (canceled)

11 . (canceled)

12 . A method of imparting hydrophobicity and/or oleophobicity to a surface of a subterranean formation penetrated by a well during production of hydrocarbons from the subterranean formation comprising:
(a) pumping into the well hydroxy containing nanoparticles surface modified with a surface modifying wettability agent and a difunctional linking agent containing a blocking moiety, —OB, wherein B is independently selected from C 1 -C 20 branched or unbranched alkyl or aryl group and further wherein the surface modifying wettability agent is of the structure:
Z m X(OR) n   (II)

wherein: X is an anchor selected from the group consisting of aluminum, silicon and a transition metal; each Z is a hydrophobic and/or oleophobic moiety attached to the anchor, the moiety comprising a substantially non-branched fluorinated monomer of a member selected from the group consisting of a C 3 -C 40 alkyl, C 3 -C 40 aryl, C 3 -C 40 fluorinated alkyl, C 3 -C 40 fluorinated aryl, C 3 -C 40 fluorinated ethylenically unsaturated monomer and perfluoroalkylene ether; each R is independently selected from a C 1 -C 20 branched or unbranched alkyl or aryl group; and m+n is defined by the valence state of the anchor provided neither m nor n are zero; (b) aligning the hydroxy containing nanoparticles to the surface of the subterranean formation such that the hydrophobic and/or oleophobic moiety is directed away from the surface of the formation; and (c) forming a condensation reaction product directly or indirectly onto the surface of the formation from the one or more blocking moieties and a hydroxy group on the surface of the formation.

13 . The method of claim 12 , wherein the nanoparticles are selected from the group consisting of silica, silicic acid, aluminum oxides, aluminum hydroxides, aluminum hydroxyoxides, aluminosilicates, zirconium oxides, zirconium hydroxides, zirconium hydroxyoxides and mixtures thereof.

14 . The method of claim 12 , wherein the hydrophobic and/or oleophobic group contains at least one terminal trifluoromethyl group.

15 . A method of imparting hydrophobicity and/or oleophobicity to a surface of a subterranean formation penetrated by a well during production of hydrocarbons from the subterranean formation comprising:
(a) pumping into the well a (i) difunctional linking agent having a blocking moiety, —OB, at one terminal end and a —OH, —COOH or amino group at the other terminal end; and (ii) hydroxy containing nanoparticles altered with a surface modifying wettability agent of the structure:
Z m X(OR) n   (II)

wherein: X is an anchor selected from the group consisting of aluminum, silicon and a transition metal; Each Z is independently selected from a hydrophobic and/or oleophobic moiety attached to the anchor, the moiety comprising the hydrophobic and/or oleophobic functional group independently selected from the group consisting of a C 3 -C 40 alkyl, C 3 -C 40 aryl, C 3 -C 40 fluorinated alkyl, C 3 -C 40 fluorinated aryl, C 3 -C 40 fluorinated ethylenically unsaturated monomer and perfluoroalkylene ether; each R and B are independently selected from C 1 -C 20 branched or unbranched alkyl or aryl group; and m+n is defined by the valence state of the anchor provided neither m nor n are zero; (b) forming a condensation product between the —OB of the difunctional linking agent and a free hydroxy group on the surface of the formation; and (c) forming a condensation product with the terminal end of the difunctional linking agent and a hydroxy group attached to the surface of the formation.

16 . The method of claim 15 , wherein the hydrophobic and/or oleophobic group contains at least one terminal trifluoromethyl group.

17 . The method of claim 15 , wherein the hydrophobic and/or oleophobic group is a C 3 -C 40 fluorinated alkyl, fluorinated aryl group or a fluorinated ethylenically unsaturated monomer.

18 . The method of claim 15 , wherein the nanoparticles are selected from the group consisting of silica, silicic acid, aluminum oxides, aluminum hydroxides, aluminum hydroxyoxides, aluminosilicates, zirconium oxides, zirconium hydroxides, zirconium hydroxyoxides and mixtures thereof.

19 . The method of claim 15 , further comprising aligning the surface modifying wettability agent to the subterranean formation such that the hydrophobic and/or oleophobic moiety is directed away from the surface of the formation.

20 . The method of claim 15 , wherein at least one of the following conditions prevail:
(a) the contact angle between the surface modifying wettability agent attached to the formation and aqueous formation fluid is greater than or equal to 80°; (b) the surface of the subterranean formation is more rough after the surface modifying wettability agent is attached to the surface than before the surface modifying wettability agent is attached to the surface; (c) surface tension of the surface of the subterranean formation is less after the surface modifying wettability agents are attached to the surface than before the surface modifying wettability agents are attached to the surface; (d) the surface modifying wettability agents alter the surface energy of the formation; (e) the surface modifying wettability agents alter the wettability of the surface of the formation to be neutrally wet; (f) the surface modifying wettability agents stabilize fines in the subterranean formation; (g) the well is a producing well and the surface modifying wettability agents decrease the amount of formation solids flowed back from the surface of the subterranean formation into the producing well; (h) the surface modifying wettability agents are passive anti-microbial agents and minimize or prevent the retention of water on the surface of the subterranean formation; (i) the surface modifying wettability agents passively inhibit or control scale deposition onto or within the subterranean formation; (j) the surface modifying wettability agents passively prevent or control deposition of organic particulates onto or within the surface of the subterranean formation; (k) the surface modifying wettability agents decrease the swelling of clay within the subterranean formation; (l) the surface modifying wettability agents increase the relative permeability of the formation to oil/gas with respect to water, thus preventing water banking behind the formation surface; (m) the well is a retrograde condensate gas reservoir and the surface modifying wettability agents minimize condensation within the reservoir while maintaining the permeability of the reservoir; (n) the well is a gas or oil well and the surface modifying wettability agents enhance the amount of flowback water and produced water from the well following completion of a well treatment operation; (o) the fluid containing the surface modifying wettability agents is pumped into the well at a pressure sufficient to create or enlarge a fracture in the subterranean formation; (p) the surface modifying wettability agents control water condensation in the pores of the near wellbore region of the subterranean formation; (q) the formation is a tar sand formation and the surface modifying wettability agents enhance the recovery of hydrocarbons from deposits within the tar sand; (r) the subterranean formation is subjected to acidizing and the surface modifying

Assignees

• Baker Hughes Oilfield Operations Llc

Inventors

• Suresh Radhika
• Bestaoui-Spurr Naima
• Spurlock-Lant Kimberly

Classifications

• E21B43/16

  Enhanced recovery methods for obtaining hydrocarbons · CPC title

• C09K2208/10

  Nanoparticle-containing well treatment fluids · CPC title

• C09K8/584

  characterised by the use of specific surfactants · CPC title

• C09K8/506 Primary

  containing organic compounds · CPC title

• C09K8/60 Primary

  Compositions for stimulating production by acting on the underground formation · CPC title