Compositions of and methods for using hydraulic fracturing fluid for petroleum production

1. A hydraulic fracturing fluid formulation for use in oilfield applications, the hydraulic fracturing fluid formulation comprising:

a micellar forming surfactant;

a curing agent;

a bead-forming compound;

a non-solids bearing liquid solvent; and

a pH control agent, where components of the hydraulic fracturing fluid formulation form solid, individual, spherical beads in situ in a hydrocarbon-bearing reservoir upon mixing, and where the solid, individual, spherical beads are of sufficient mechanical strength to act as a proppant in situ and hold fractures open against an overburden pressure.

2. The formulation of claim 1 , where the formulation comprises a primary liquid precursor and a secondary liquid precursor.

3. The formulation of claim 2 , where the primary liquid precursor comprises a component selected from the group consisting of: the micellar forming surfactant; the curing agent; the bead-forming compound; the non-solids bearing liquid solvent; the pH control agent, and combinations of the same.

4. The formulation of claim 3 , where the primary liquid precursor comprises the curing agent.

5. The formulation of claim 3 , where the primary liquid precursor comprises the micellar forming surfactant.

6. The formulation of claim 3 , where the primary liquid precursor comprises the non-solids bearing liquid solvent.

7. The formulation of claim 2 , where the secondary liquid precursor comprises a component selected from the group consisting of: the micellar forming surfactant; the curing agent; the non-solids bearing liquid solvent; the pH control agent, and combinations of the same.

8. The formulation of claim 7 , where the secondary liquid precursor comprises the curing agent.

9. The formulation of claim 7 , where the secondary liquid precursor comprises the micellar forming surfactant.

10. The formulation of claim 7 , where the secondary liquid precursor comprises the non-solids bearing liquid solvent.

11. The formulation of claim 2 , where the primary liquid precursor comprises a co-curing agent.

12. The formulation of claim 11 , where the co-curing agent is selected from the group consisting of water, fatty acids, tall oil fatty acid, ricinoleic acid, benzoic acid, salicylic acid, stearic acid, alkoxylated alcohols, dicarboxylic acids, carboxylic acids, imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphatic polyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acid anhydrides, imidazoline salts, dicyandamides, phenols, alkylphenols, and combinations thereof.

13. The formulation of claim 2 , where the secondary liquid precursor comprises a co-curing agent.

14. The formulation of claim 13 , where the co-curing agent is selected from the group consisting of water, fatty acids, tall oil fatty acid, ricinoleic acid, benzoic acid, salicylic acid, stearic acid, alkoxylated alcohols, dicarboxylic acids, carboxylic acids, imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphatic polyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acid anhydrides, imidazoline salts, dicyandamides, phenols, alkylphenols, and combinations thereof.

15. The formulation of claim 2 , where the primary liquid precursor comprises an anti-foaming agent.

16. The formulation of claim 2 , where the secondary liquid precursor comprises an anti-foaming agent.

17. The formulation of claim 2 , where the primary liquid precursor comprises a retarder.

18. The formulation of claim 2 , where the secondary liquid precursor comprises a retarder.

19. The formulation of claim 2 , where a first non-solids bearing liquid solvent of the primary liquid precursor and a second non-solids bearing liquid solvent of the secondary liquid precursor are substantially immiscible upon combining the primary liquid precursor and secondary liquid precursor, and where the primary liquid precursor and secondary liquid precursor are operable to form an emulsion when mixed.

20. The formulation of claim 1 , where the micellar forming surfactant is selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, betaines, amphoteric surfactants, and combinations thereof.

21. The formulation of claim 1 , where the bead-forming compound is selected from the group consisting of bis-phenol A diglycidyl ether, bis-phenol F diglycidyl ether, cycloaliphatic epoxides, glycidyl ethers, poly glycidyl ethers, novalac resins, polyurethane resins, acrylic resin, phenol-formaldehyde resin, epoxy functional resins, and combinations thereof.

22. The formulation of claim 1 , where the non-solids bearing liquid solvent is selected from the group consisting of water, brine containing mono and polyvalent salt, sea water, mineral oil, kerosene, diesel, crude oil, petroleum condensate, low molecular weight alcohols, fatty alcohols, low molecular weight alcohol ethers, benzyl alcohol, and benzyl alcohol ethers, ethyl carbitol ether, γ-butyrolactone, phenol alkoxylates, alkylphenol alkoxylates, and combinations thereof.

23. The formulation of claim 1 , where the pH control agent is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium aluminate, potassium carbonate, potassium phosphate, sodium silicate, potassium silicate, organic acids, and combinations thereof.

24. The formulation of claim 1 , where the curing agent is selected from the group consisting of lewis acids, tertiary amines, mono ethanol amine, benzyl dimethylamine, 1,4-diaza-bicylo[2,2,2]octane, 1,8-diazabicylo[5,4,0]undec-7ene, cycloaliphatic amines, alkyl heterocyclic amines, polyalkyl heterocyclic polyamine, alkyl heterocyclic polyamines, amidoamines, aliphatic amines, aromatic amines, isophorone, isophorone diamine, polyamides, boron tri-fluoride derivatives, functional resins, imidazoles, imidazolines, mercaptans, sulfide, hydrazides, amides and combinations thereof.

25. The formulation of claim 1 , where upon initial mixing components of the formulation form a non-solids bearing homogenous liquid.

26. A method of fracturing a reservoir with a hydraulic fracturing fluid formulation that generates fractures in the reservoir, the method comprising the steps of:

mixing a primary liquid precursor and a secondary liquid precursor to form a spherical bead-forming liquid composition, where the spherical bead-forming liquid composition comprises:

a micellar forming surfactant;

a curing agent;

a bead-forming compound;

a non-solids bearing liquid solvent; and

a pH control agent, where components of the spherical bead-forming liquid composition form spherical beads in situ in the reservoir upon mixing;

pumping the spherical bead-forming liquid composition into an injection well in the reservoir at an external pressure greater than a pressure required to generate fractures in the reservoir;

allowing the spherical bead-forming liquid composition to migrate into the fractures of the reservoir; and

allowing the primary liquid precursor and secondary liquid precursor to react to form in-situ solid, individual, spherical beads, where the solid, individual, spherical beads are operable to keep the fractures open against an overburden pressure after the external pressure is released.

27. The method of claim 26 , where the primary liquid precursor comprises a component selected from the group consisting of: the micellar forming surfactant; the curing agent; the bead-forming compound; the non-solids bearing liquid solvent; the pH control agent, and combinations of the same.

28. The method of claim 27 , where the primary liquid precursor comprises the curing agent.

29. The method of claim 27 , where the primary liquid precursor comprises the micellar forming surfactant.

30. The method of claim 27 , where the primary liquid precursor comprises the non-solids bearing liquid solvent.

31. The method of claim 26 , where the secondary liquid precursor comprises a component selected from the group consisting of: the micellar forming surfactant; the curing agent; the non-solids bearing liquid solvent; the pH control agent, and combinations of the same.

32. The method of claim 31 , where the secondary liquid precursor comprises the curing agent.

33. The method of claim 31 , where the secondary liquid precursor comprises the micellar forming surfactant.

34. The method of claim 31 , where the secondary liquid precursor comprises the non-solids bearing liquid solvent.

35. The method of claim 26 , where the primary liquid precursor comprises a co-curing agent.

36. The method of claim 35 , where the co-curing agent is selected from the group consisting of water, fatty acids, tall oil fatty acid, ricinoleic acid, benzoic acid, salicylic acid, stearic acid, alkoxylated alcohols, dicarboxylic acids, carboxylic acids, imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphatic polyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acid anhydrides, imidazoline salts, dicyandamides, phenols, alkylphenols, and combinations thereof.

37. The method of claim 26 , where the secondary liquid precursor comprises a co-curing agent.

38. The method of claim 37 , where the co-curing agent is selected from the group consisting of water, fatty acids, tall oil fatty acid, ricinoleic acid, benzoic acid, salicylic acid, stearic acid as well as alkoxylated alcohols, dicarboxylic acids, carboxylic acids, imidazolines, dicyandiamides, ureas, imidazoles, thiols, aliphatic polyamines, cycloaliphatic polyamides, cycloaliphatic dicarboxylic acid anhydrides, imidazoline salts, dicyandamides, phenols, alkylphenols, and combinations thereof.

39. The method of claim 26 , where the primary liquid precursor comprises an anti-foaming agent.

40. The method of claim 26 , where the secondary liquid precursor comprises an anti-foaming agent.

41. The method of claim 26 , where the primary liquid precursor comprises a retarder.

42. The method of claim 26 , where the secondary liquid precursor comprises a retarder.

43. The method of claim 26 , where a first non-solids bearing liquid solvent of the primary liquid precursor and a second non-solids bearing liquid solvent of the secondary liquid precursor are substantially immiscible upon combining the primary liquid precursor and secondary liquid precursor, and where the primary liquid precursor and secondary liquid precursor are operable to form an emulsion when mixed.

44. The method of claim 26 , where the micellar forming surfactant is selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, betaines, amphoteric surfactants, and combinations thereof.

45. The method of claim 26 , where the bead-forming compound is selected from the group consisting of bis-phenol A diglycidyl ether, bis-phenol F diglycidyl ether, cycloaliphatic epoxides, glycidyl ethers, poly glycidyl ethers, novalac resins, polyurethane resins, acrylic resin, phenol-formaldehyde resin, epoxy functional resins, and combinations thereof.

46. The method of claim 26 , where the non-solids bearing liquid solvent is selected from the group consisting of water, brine containing mono and polyvalent salt, sea water, mineral oil, kerosene, diesel, crude oil, petroleum condensate, low molecular weight alcohols, fatty alcohols, low molecular weight alcohol ethers, benzyl alcohol, and benzyl alcohol ethers, ethyl carbitol ether, γ-butyrolactone, phenol alkoxylates, alkylphenol alkoxylates, and combinations thereof.

47. The method of claim 26 , where the pH control agent is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium aluminate, potassium carbonate, potassium phosphate, sodium silicate, potassium silicate, organic acids, and combinations thereof.

48. The method of claim 26 , where the curing agent is selected from the group consisting of lewis acids, tertiary amines, mono ethanol amine, benzyl dimethylamine, 1,4-diaza-bicylo[2,2,2]octane, 1,8-diazabicylo[5,4,0]undec-7ene, cycloaliphatic amines, alkyl heterocyclic amines, polyalkyl heterocyclic polyamine, alkyl heterocyclic polyamines, amidoamines, aliphatic amines, aromatic amines, isophorone, isophorone diamine, polyamides, boron tri-fluoride derivatives, functional resins, imidazoles, imidazolines, mercaptans, sulfide, hydrazides, amides, and combinations thereof.

49. The method of claim 26 , where upon initial mixing components of the formulation form a non-solids bearing homogenous liquid.

50. The method of claim 26 , where the step of allowing the primary liquid precursor and secondary liquid precursor to react to form solid, individual, spherical beads comprises the step of allowing solid, individual, spherical beads of increasingly smaller size to form at increasing distances from the injection well.