Methods of altering the wettability of surfaces to enhance hydrocarbon production

Patent metadata

Field	Value
Publication number	US-11359130-B2
Application number	US-201817047285-A
Country	US
Kind code	B2
Filing date	Apr 10, 2018
Priority date	Apr 10, 2018
Publication date	Jun 14, 2022
Grant date	Jun 14, 2022

Abstract

A method of reducing water saturation onto surfaces exposed to hydrocarbons during the production of hydrocarbons from subterranean formations by altering the wettability of the surface of the formation with surface modified nanoparticles.

First claim

What is claimed is:

1. A method of imparting hydrophobicity and/or oleophobicity to a surface of a subterranean formation during production of hydrocarbons from the subterranean formation comprising exposing the surface of the subterranean formation to surface modified nanoparticles which comprise a substrate of nanoparticles and a hydrophobic and/or oleophobic surface modifying agent attached onto surfaces of the nanoparticles wherein at least a portion of the nanoparticles are attached to the surface of the subterranean formation and further wherein (a) the diameter of the substrate of the nanoparticles is less than or equal to 100 nm and 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; and (b) the hydrophobic and/or oleophobic surface modifying agent is selected from the group consisting of (i) organosilicon materials; (ii) fluorinated organic acids or reactive derivatives thereof; (iii) linear or branched alkyl organic acids or reactive derivatives thereof; (iv) substituted alkyl organic acids or reactive derivatives thereof; (v) aryl or substituted aryl organic acids or reactive derivatives thereof; and (vi) mixtures of (i), (ii), (iii), (iv) and/or (v).

2. The method of claim 1 , wherein the hydrophobic and/or oleophobic surface modifying agent is covalently bonded onto at least a portion of the nanoparticles.

3. The method of claim 1 , wherein the hydrophobic and/or oleophobic surface modifying agent is (ii), (iii), (iv) or (v) and wherein the organic acid is selected from the group consisting of carboxylic acids, phosphonic acids, phosphoric acids, phosphinic acids, sulfonic acids and mixtures thereof.

4. The method of claim 3 , wherein the hydrophobic and/or oleophobic surface treating agent contains:
(a) a derivative of a phosphoric acid having the structure (RO) x —P(O)—(OR′) y ;
(b) a derivative of a phosphonic acid of the structure:

and
(c) a derivative of a phosphinic acid of the structure:

wherein:
R and R″ are each independently a radical having a total of 1 to 30 carbon atoms, optionally substituted with a perfluorinated alkyl group or a perfluorinated alkylene ether group;
R′ is H, a metal or a lower alkyl having from 1 to 4 carbon atoms;
x is 1 to 2; y is 1 to 2; x+y=3;
a is 0-1;
b is 1;
c is 1-2;
a+b+c is 3;
d is 0-2;
e is 0-2;
f is 1; and
d+e+f is 3.

5. The method of claim 1 , wherein the organic acid:
(i) contains a fluorine containing moiety;
(ii) is a carboxylic acid of the formula R—COOH where R is a linear or branched C 9 -C 24 hydrocarbon group or a hydroxylated derivative thereof or a C 6 -C 20 aryl, alkylaryl or arylalkyl group; or
(iii) has two or more carboxylic acid moieties.

6. The method of claim 5 , wherein the organic acid contains a fluorine containing moiety of:
(a) R f —(CH 2 ) p — where R f is a perfluorinated alkyl group or contains a perfluorinated alkylene ether group and p is 2 to 4;
(b)

where Y is F or C n F 2n+1 ; m is 4 to 20 and n is 1 to 6; or
(c) an oligomeric or perfluoroalkylene ether group of the structure:

where A is an oxygen atom or CF 2 ; n is 1 to 20; Y is H, F, C n H 2n+1 or C n F 2n+1 ; X is H or F; b is at least 1, m is 0 to 50, and p is 1 to 20.

7. The method of claim 1 , wherein the hydrophobic and/or oleophobic surface modifying agent is of the formula R f —(CH 2 ) p —Z, wherein Z is:

where R and R″ are a hydrocarbon or substituted hydrocarbon radical having up to 200 carbons or R and R″ is a perfluoroalkyl group, and R′ is H or an aliphatic radical having from about 1 to about 50 carbon atoms or a substituted or unsubstituted aryl group having 6 to about 50 carbons.

8. The method of claim 1 , wherein the organo-silicon material is a silane, polysiloxane or a polysilazane.

9. The method of claim 1 , wherein the organo-silicon material has a formula selected from:
R 1 4-x SiA x and (R 1 3 Si) y B
or an organo(poly)siloxane or organo(poly)silazane of the formula:

where:
R 1 are identical or different and are a hydrocarbon or substituted hydrocarbon radical containing from 1 to 100 carbon atoms;
A is hydrogen, halogen, OH, OR 2 or

B is NR 3 3-y ;
R 2 is a hydrocarbon or substituted hydrocarbon radical containing from 1 to 12 carbon atoms;
R 3 is hydrogen or R 1 ;
x is 1, 2 or 3; and
y is 1 or 2.

10. The method of claim 1 , wherein the surface modified nanoparticles are prepared by (i) adding the hydrophobic and/or oleophobic surface modifying agent to a dispersion containing the nanoparticles as dispersants in a solvent, the nanoparticles having a charge resulting in a Zeta potential in the dispersion; (ii) removing the solvent from the dispersion; and then (iii) drying the product of step (ii).

11. The method of claim 10 , wherein at least one of the following conditions is true:
(a) the nanoparticle dispersants have a particle size between from about 90 nm to about 225 nm;
(b) the nanoparticles are pre-treated with an acid prior to dispersing the nanoparticles in the dispersion; or
(c) the nanoparticles have a diameter of crystallized size, prior to being dispersed in the dispersion, of 100 nm or less.

12. The method of claim 1 , wherein the nanoparticles are first attached to the surface of the subterranean formation by pumping into a well penetrating the subterranean formation a first fluid containing the nanoparticles; and (b) the hydrophobic and/or oleophobic surface treating agent is attached to surfaces of the nanoparticles by pumping into the well a second fluid containing the hydrophobic and/or oleophobic surface treating agent, thereby forming the surface modified nanoparticles.

13. The method of claim 1 , wherein the contact angle between the surface modified nanoparticles attached to the formation and aqueous formation fluid is greater than or equal to 105° and further wherein the contact angle between the surface modified nanoparticles attached to the formation and hydrocarbon formation fluid is greater than or equal to 60°.

14. The method of claim 1 , wherein at least one of the following conditions prevail:
(i) the surface of the subterranean formation is more rough after the surface modified nanoparticles are attached to the surface than before the surface modified nanoparticles are attached to the surface; or
(ii) the surface tension of the surface of the subterranean formation is less after the surface modified nanoparticles are attached to the surface than before the surface modified nanoparticles are attached to the surface.

15. The method of claim 1 , wherein at least one of the following conditions prevail:
(a) the surface modified nanoparti

Assignees

• Baker Hughes Holdings Llc

Inventors

• Suresh Radhika
• Gupta D V Satyanarayana
• Khabashesku Valery
• Darugar Qusai
• Murugesan Sankaran

Classifications

• C09K8/58

  Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids · CPC title

• E21B43/26

  by forming crevices or fractures · CPC title

• C09K2208/10

  Nanoparticle-containing well treatment fluids · CPC title

• E21B37/06

  using chemical means for preventing or limiting {, e.g. eliminating,} the deposition of paraffins or like substances · CPC title

• C09K8/506

  containing organic compounds · CPC title