Composites for use in stimulation and sand control operations

• US 9,562,188 B2
• Filed: 09/19/2014
• Issued: 02/07/2017
• Est. Priority Date: 09/20/2013
• Status: Active Grant

• Current Assignee: Baker Hughes Holdings LLC (Baker Hughes Company)
• Original Assignee: Baker Hughes Incorporated (Baker Hughes Company)
• Inventors: Monroe, Terry D., Beall, Brian B., Bestaoui-Spurr, Naima, Bhaduri, Sumit, Lant, Kimberly, Le, Hoang, Qu, Qi
• Primary Examiner(s): Bates, Zakiya W
• Application Number:
  US14/491,944
• Publication Number:
  US 20150083415A1
• Time in Patent Office: 872 Days
• US Class Current: 1/1
• CPC Class Codes: C09K 8/524 organic depositions, e.g. paraffins or asphaltenes
• CPC Class Codes: C09K 8/528 inorganic depositions, e.g. sulfates or carbonates
• CPC Class Codes: C09K 8/56 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 Class Codes: C09K 8/805 Coated proppants
• CPC Class Codes: E21B 43/025 Consolidation of loose sand or the like round the wells without excessively decreasing the permeability thereof
• CPC Class Codes: E21B 43/14 Obtaining from a multiple-zone well
• CPC Class Codes: E21B 43/16 Enhanced recovery methods for obtaining hydrocarbons
• CPC Class Codes: E21B 43/267 reinforcing fractures by propping

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 may be metal and the hydrophobic tail may be an organo-silicon material, a fluorinated hydrocarbon or both an organo-silicon material and a fluorinated hydrocarbon. 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.

Claims

1. A composite for treating a well wherein the composite comprises a surface modifying treatment agent at least partially coated onto a solid particulate and wherein the surface modifying treatment agent comprises a metallic anchor and a hydrophobic tail wherein the hydrophobic tail is an organo-silicon material, a fluorinated hydrocarbon or both a hydrophobic organo-silicon material and a fluorinated hydrocarbon and further wherein the metallic anchor of the surface modifying treatment agent is attached to the solid particulate.

2. The composite of claim 1, wherein the hydrophobic tail is a derivative of a silane, polysiloxane or a polysilazane.

5. The composite of claim 1, wherein the hydrophobic tail is a derivative of an organo-silicon of the formula:

R¹_4-xSiA_x or (R¹₃Si)_yB

or an organo(poly)siloxane or organo(poly)silazane of the formula;

6. The composite of claim 5, wherein the organo(poly)siloxane or organo(poly)silazane has units of the formula:

7. The composite of claim 1, wherein the fluorinated hydrocarbon contains the structure:

8. The composite of claim 1, wherein the fluorinated hydrocarbon is of the structure:

9. The composite of claim 1, wherein the hydrophobic tail contains units of R⁵₂SiO₂ where R⁵ is halogen.

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

11. The composite of claim 10, wherein the adherent is an organometallic compound.

12. The composite of claim 11, wherein the organometallic compound comprises a transition metal selected from the group consisting of titanium, zirconium, lanthanum, hafnium, tantalum and tungsten and mixtures thereof.

13. The composite 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.

14. The composite of claim 13, wherein the polymeric particles are beads or pellets of polystyrene, nylon, polystyrene divinylbenzene, polyethylene terephthalate or a combination thereof.

15. The composite of claim 13, wherein the solid particulate further has a resinous coating.

16. A proppant or sand control particulate comprising the composite of claim 1.

17. The composite of claim 1, wherein the solid particulate comprises an elastomer.

18. The composite of claim 17, 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.

19. The composite of claim 18, 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).

20. A method for treating a well penetrating a subterranean formation, comprising introducing into the well the composite of claim 1 or forming the composite in-situ in the well.

21. The method of claim 20 wherein at least one of the following conditions prevail:

(a) the surface modifying treatment agent functions as a passive anti-microbial agent;

(b) the surface modifying treatment agent functions to passively inhibit or control scale deposition onto or within the subterranean formation;

(c) the surface modifying treatment agent of the composite passively prevents or controls deposition of organic particulates onto or within the surface of the subterranean formation;

or

(d) the surface modifying treatment agent of the composite controls proppant flowback.

22. The method of claim 20, wherein the composite is pumped into the well during a hydraulic fracturing operation and further wherein the solid particulate is capable of withstanding stresses greater than about 1500 psi at a temperature greater than 150°

F.

23. The method of claim 20, wherein the composite is formed in-situ in the well by first pumping the solid particulate into the well and then at least partially coating the solid particulate by subsequently pumping the surface modifying treatment agent into the well.

3. The composite of 1, wherein the metal of the metallic anchor is a Group 3, 4, 5, or 6 metal.

4. The composite of claim 3, wherein the metal of the metallic anchor is selected from the group consisting of Ti, Zr, La, Hf, Ta, W and Nb.

24. A composite for treating a wellbore, wherein the composite comprises a solid particulate and a surface modifying treatment agent at least partially coated onto a solid particulate, the surface modifying treatment agent comprising an anchor and at least one hydrophobic tail attached to the anchor wherein the anchor is attached to the solid particulate.

25. The composite of claim 24, wherein the surface modifying treatment agent is a reaction product of an organometallic compound having an oxygen ligand and an organo-silicon containing material.

26. The composite of claim 24, wherein the surface modifying treatment agent is of the formula X-M where M is a metal containing organic ligand and X is a hydrophobic tail.

27. A method for treating a well penetrating a subterranean formation, comprising introducing into the well the composite of claim 24 or forming the composite in-situ within the well.

28. The method of claim 27, wherein the composite is pumped into the well or is formed in-situ within the well during a hydraulic fracturing operation or a sand control operation.

29. The method of claim 27, wherein the formation penetrated by the well has multiple productive zones and wherein the composite isolates a pre-determined productive zone from other zones of the well.

30. The method of claim 27, wherein the composite minimizes tubular friction pressures within the well.

31. The method of claim 27, wherein the amount of fines and/or sand migrated during treatment of the well is decreased by the presence of the surface modifying treatment agent coated onto the solid particulate.

32. The method of claim 27, wherein the hydrophobic tail of the composite is aligned away from the surface of the solid particulate.

33. The method of claim 27, wherein a fluid containing the composite is pumped into the well during a hydraulic fracturing operation and wherein the solid particulate is a proppant and further wherein the crush resistance of the proppant at a closure stress of 1,500 psi, AAPI 56 or API RP 60, is greater than the crush resistance of a pristine proppant not having the surface modifying treatment agent at least partially coated onto the proppant.

34. The method of claim 27, further comprising producing hydrocarbons from the well and reducing frictional drag during hydrocarbon production.

35. The method of claim 27, wherein the fluid in the well has a sliding angle on the surface of the composite which is less than the sliding angle of the same fluid on the surface of a pristine solid particulate not having the surface modifying treatment agent attached thereto.