Organophosphorus containing composites for use in well treatment operations

Patent metadata

Field	Value
Publication number	US-10047280-B2
Application number	US-201414491919-A
Country	US
Kind code	B2
Filing date	Sep 19, 2014
Priority date	Sep 20, 2013
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

A composite having a solid particulate and a surface modifying treatment agent on the solid particulate wherein the surface modifying treatment agent has a hydrophobic tail and an anchor for adhering the hydrophobic tail onto the solid particulate. The anchor is an organophosphorus acid derivative. The composite may be used as a proppant in a hydraulic fracturing operation as well as a sand control particulate in a gravel packing operation. The presence of the surface modifying treatment agent on the surface of the solid particulate reduces the generation of fines and dust as well as the migration of sand during a hydraulic fracturing operation or a sand control operation. The presence of the surface modifying treatment agent on the surface of the solid particulate further enhances the crush resistance of the solid particulate.

First claim

What is claimed is:

1. A method for treating a well penetrating a subterranean formation, comprising introducing into the well a composite or forming a composite in-situ in the well, the composite comprising a surface modifying treatment agent at least partially coated onto a solid particulate and wherein the surface modifying treatment agent comprises a hydrophobic tail and an anchor for adhering the hydrophobic tail to the solid particulate and further wherein the anchor is an organophosphorus acid derivative.

2. The method of claim 1 , wherein the hydrophobic tail is a fluorine containing moiety.

3. The method of claim 2 , wherein the fluorine containing moiety is R f —(CH 2 ) p — where R f is a perfluorinated alkyl group, a perfluorinated alkylene group or a perfluorinated alkylene ether group and p is 2 to 4, preferably 2.

4. The method of claim 2 , wherein the fluorine containing moiety has a number average molecular weight of less than 2000.

5. The method of claim 2 , wherein the hydrophobic tail contains a perfluoro group of the structure:

where Y is F or C n F 2n+1 ; m is 4 to 20 and n is 1 to 6.

6. The method of claim 2 , wherein the hydrophobic tail is a fluorine containing moiety of the formula:

where A is an oxygen radical or a chemical bond; n is 1 to 20; Y is H, F, C n H 2n+1 or C n F 2n+1 ;
b is at least 1, m is 0 to 50, and p is 1 to 20.

7. The method of claim 1 , wherein the anchor is an organophosphorus acid derivative of an organophosphoric acid, organophosphonic acid or an organophosphinic acid.

8. The method of claim 7 , wherein the organophosphorus acid derivative is at least one member selected from the group consisting of:
(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; 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.

9. The method of claim 8 , wherein R″ is an aliphatic or aromatic substituent substituted with a fluoro or perfluoro group.

10. The method of claim 8 , wherein the surface modifying treatment agent is of the formula:
R f —(CH 2 ) p —Z

wherein:
R f is a perfluorinated alkyl group or contains a perfluorinated alkylene ether group;
p is 2 to 4; and
Z is selected from the group consisting of:

11. The method of claim 8 , wherein R″ is aliphatic or aromatic substituent substituted with a perfluorinated alkyl group or a perfluorinated alkylene ether group.

12. The method of claim 1 , wherein the surface modifying treatment agent is selected from the group consisting of CF 3 (C n F 2n )CH 2 CH 2 PO 3 H 2 where n is between 3 and 5, and CF 3 (CF 2 ) x O(CF 2 CF 2 ) y —CH 2 CH 2 —PO 3 H 2 where x is from 0 to 7, y is from 1 to 20 and x+y is less than or equal to 27.

13. The method of claim 8 , wherein R, R′ or R″ contains a terminal or omega functional groups.

14. The method of claim 13 , wherein the terminal or omega functional group is selected from the group consisting of carboxyl, hydroxyl, amino, imino, amido, thio, cyano, sulfonate, carbonate, phosphonic acid or a mixture thereof.

15. The method of claim 1 , wherein the anchor of the surface modifying treatment agent is a derivative of an organophosphorus acid selected from the group consisting of amino trismethylene phosphonic acid, aminobenzylphosphonic acid, 3-amino propyl phosphonic acid, O-aminophenyl phosphonic acid, 4-methoxyphenyl phosphonic acid, aminophenylphosphonic acid, aminophosphonobutyric acid, aminopropylphosphonic acid, benzhydrylphosphonic acid, benzylphosphonic acid, butylphosphonic acid, carboxyethylphosphonic acid, diphenylphosphinic acid, dodecylphosphonic acid, ethylidenediphosphonic acid, heptadecylphosphonic acid, methylbenzylphosphonic acid, naphthylmethylphosphonic acid, octadecylphosphonic acid, octylphosphonic acid, pentylphosphonic acid, phenylphosphinic acid, phenylphosphonic acid, bis-(perfluoroheptyl) phosphinic acid, perfluorohexyl phosphonic acid, styrene phosphonic acid, and dodecyl bis-1,12-phosphonic acid.

16. The method of claim 1 , further comprising an adherent between the solid particulate and the anchor of the surface modifying agent for bonding the anchor to the solid particulate.

17. The method of claim 16 , wherein the adherent is an organometallic compound.

18. The method of claim 17 , wherein the organometallic compound comprises a transition metal selected from the group consisting of titanium, zirconium, lanthanum, hafnium, tantalum and tungsten and mixtures thereof.

19. The method of claim 1 , wherein the solid particulate is selected from the group consisting of ceramics, sand, minerals, nut shells, gravel, polymeric particles, and mixtures thereof.

20. The method of claim 1 , wherein the solid particulate has an apparent specific gravity less than 2.45 and/or the polymeric particles are beads or pellets of polystyrene, nylon, polystyrene divinylbenzene, polyethylene terephthalate or a combination thereof.

21. The method of claim 1 , wherein the solid particulate further has a resinous coating.

22. The method of claim 1 , wherein the composite is a proppant or sand control particulate.

23. The method of claim 1 , wherein the solid particulate comprises an elastomer.

24. The method of claim 23 , wherein the elastomer is selected from the group consisting of natural rubber, ethylene-propylene-diene polymers (EPDM), nitrile rubbers, carboxylated acrylonitrile butadiene copolymers, polyvinylchloride-nitrile butadiene blends, chlorinated polyethylene, chlorinated sulfonate polyethylene, aliphatic polyesters having chlorinated side chains, polyacrylate rubbers, ethylene-acrylate terpolymers, copolymers of ethylene and propylene, and optionally with one or more other ethylenically unsaturated monomers, ethylene vinyl acetate copolymers, fluorocarbon polymers and copolymers, polyvinyl methyl ether, butadiene rubber, polychloroprene rubber, polyisoprene rubber, polynorbornenes, polysulfide rubbers, polyurethanes, silicone rubbers, vinyl silicone rubbers, fluoromethyl silicone rubber, fluorovinyl silicone rubbers, phenylmethyl silicone rubbers, styrene-butadiene rubbers, copolymers of isobutylene and isoprene or butyl rubbers, brominated copolymers of isobutylene and isoprene and chlorinated copolymers of isobutylene and isoprene and mixtures thereof.

25. The method of claim 23 , wherein the elastomer is natural rubber or a polymer of at least one of the monomers selected from the group consisting of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, perfluoro(alkyl vinyl ether).

Assignees

• Baker Hughes Inc
• Baker Hughes A Ge Co Llc

Inventors

• Monroe Terry D
• Beall Brian B
• Bestaoui-Spurr Naima
• Bhaduri Sumit
• Lant Kimberly
• Le Hoang
• Qu Qi

Classifications

• E21B43/16

  Enhanced recovery methods for obtaining hydrocarbons · CPC title

• C09K8/805 Primary

  Coated proppants · CPC title

• E21B43/267

  reinforcing fractures by propping · CPC title

• E21B43/14

  Obtaining from a multiple-zone well · CPC title

• C09K8/56

  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}) · CPC title