Composition and method for making a proppant

• US 7,459,209 B2
• Filed: 02/03/2006
• Issued: 12/02/2008
• Est. Priority Date: 02/04/2005
• Status: Expired due to Fees

• Current Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Original Assignee: Oxane Materials, Inc.
• Inventors: Whitsitt, Elizabeth A., Coker, Christopher E., Barron, Andrew R., Costantino, Stephen A., Loscutova, John R., Smith, Russell J., Wiesner, Mark, Bordia, Rajendra Kumar
• Primary Examiner(s): KILIMAN, LESZEK B
• Application Number:
  US11/347,664
• Publication Number:
  US 20060177661A1
• Time in Patent Office: 1,033 Days
• Field of Search: 428/402, 428403-406, 427/212, 166/280.2, 507/269
• US Class Current: 428/403
• CPC Class Codes: C04B 18/082 Cenospheres
• CPC Class Codes: C04B 20/1066 Oxides, Hydroxides
• CPC Class Codes: C04B 35/04 based on magnesium oxide
• CPC Class Codes: C04B 35/10 based on aluminium oxide
• CPC Class Codes: C04B 35/14 based on silica
• CPC Class Codes: C04B 35/18 rich in aluminium oxide
• CPC Class Codes: C04B 35/44 based on aluminates
• CPC Class Codes: C04B 35/48 based on zirconium or hafnium oxides, zirconates, zircon or hafnates
• CPC Class Codes: C04B 35/50 based on rare-earth compounds non-oxide rare earth compounds C04B35/5156
• CPC Class Codes: C04B 35/505 based on yttrium oxide
• CPC Class Codes: C04B 38/0045 by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
• CPC Class Codes: C04B 38/009 Porous or hollow ceramic granular materials, e.g. microballoons C04B18/027, C04B20/002 take precedence
• CPC Class Codes: C04B 38/0655 Porous materials C04B38/0625 takes precedence
• CPC Class Codes: C04B 38/08 by adding porous substances
• CPC Class Codes: C09K 8/64 Oil-based compositions
• CPC Class Codes: C09K 8/66 Compositions based on water or polar solvents C09K8/64 takes precedence
• CPC Class Codes: C09K 8/80 Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
• CPC Class Codes: C09K 8/805 Coated proppants
• CPC Class Codes: Y02W 30/91 Use of waste materials as fillers for mortars or concrete
• CPC Class Codes: Y10T 428/2982 Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2991 : Coated
• CPC Class Codes: Y10T 428/2993 : Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• CPC Class Codes: Y10T 428/2995 : Silane, siloxane or silicone coating
• CPC Class Codes: Y10T 428/2996 : Glass particles or spheres

Abstract

The present invention relates to proppants which can be used to prop open subterranean formation fractions. Proppant formulations are further disclosed which use one or more proppants of the present invention. Methods to prop open subterranean formation fractions are further disclosed. In addition, other uses for the proppants of the present invention are further disclosed, as well as methods of making the proppants.

Claims

1. A proppant comprising a template material having an outer surface and a shell fully encapsulating said template material, wherein said shell comprises a ceramic material or oxide thereof or a metal oxide, wherein said proppant has a crush strength and wherein the shell contributes a majority of said crush strength, and said shell is substantially uniform in thickness around the outer surface of said template material.

2. The proppant of claim 1, wherein said template material is porous.

3. The proppant of claim 1, wherein said template material is a hollow sphere.

4. The proppant of claim 1, wherein said template material is a closed foam network.

5. The proppant of claim 1, wherein said template material is a non-composite material.

6. The proppant of claim 1, wherein said template material is a single particle.

7. The proppant of claim 1, wherein said template material is a cenosphere.

8. The proppant of claim 1, wherein said template material has a crush strength of 1,000 psi or less.

9. The proppant of claim 1, wherein said template material has voids.

10. The proppant of claim 1, wherein said shell is a sintered shell.

11. The proppant of claim 1, wherein said shell comprises sintered nanoparticles.

12. The proppant of claim 1, wherein said shell has an average grain size of about 10 microns or less.

13. The proppant of claim 1, wherein said shell further comprises at least one sintering aid, glassy phase formation agent, grain growth inhibitor, ceramic strengthening agent, crystallization control agent, or phase formation control agent, or any combination thereof.

14. The proppant of claim 1, wherein said sintering aid, grain growth inhibitor, ceramic strengthening agent, crystallization control agent, or phase formation control agent comprises yttrium, zirconium, iron, magnesium, alumina, bismuth, lanthanum, silicon, calcium, cerium, silicates, borates, or oxides thereof or any combination thereof.

15. The proppant of claim 13, wherein said sintering aid, grain growth inhibitor, ceramic strengthening agent, glassy phase formation agent, crystallization control agent, or phase formation control agent is present in said shell in an amount of from about 0.1% to about 5% by weight of said shell.

16. The proppant of claim 1, wherein said template material is a hollow cenosphere.

17. The proppant of claim 1, wherein said template material comprises fly ash particles or particles derived from fly ash.

18. The proppant of claim 1, wherein said template material is a hollow spheroidal particle.

19. The proppant of claim 1, wherein said template material is precipitator fly ash.

20. The proppant of claim 1, wherein said shell is substantially non-porous.

21. The proppant of claim 1, wherein said shell is a non-reactive coating on said template material.

22. The proppant of claim 1, wherein said shell chemically bonds to said template material or a portion thereof.

23. The proppant of claim 1, wherein at least a portion of said shell diffuses, infiltrates, or impregnates a portion of said template material.

24. The proppant of claim 1, wherein at least a portion of said shell adsorbs or absorbs onto at least a portion of said template material.

25. The proppant of claim 1, wherein said shell is in direct contact with the outer surface of said template material.

26. The proppant of claim 1, wherein said proppant has a crush strength of 3,000 psi or greater.

27. The proppant of claim 1, wherein said proppant has a specific gravity of from 0.6 g/cc to about 2.5 g/cc.

28. The proppant of claim 1, wherein said shell has a wall thickness of from about 15 to about 120 microns.

29. The proppant of claim 1, wherein said proppant is spherical and has a sphericity of at least about 0.9.

30. The proppant of claim 1, wherein said shell is a spray-coated shell.

31. The proppant of claim 1, wherein said shell comprises at least one alumina, aluminosilicate, aluminate, or silicate.

32. The proppant of claim 31, wherein said aluminate or silicate or aluminosilicate is an aluminate or silicate or aluminosilicate of calcium, yttrium, magnesium, titanium, lanthanum, barium, silicon, or any combination thereof.

33. The proppant of claim 1, wherein said template material is a naturally occurring material.

34. The proppant of claim 1, wherein one or more intermediate coatings are present between said template material and said shell.

35. A method of making the proppant of claim 1, comprising coating said template material with a formulation comprising said ceramic material or oxide thereof or metal oxide to form said shell around said template and then sintering said shell.

36. The method of claim 35, wherein said sintering occurs at a sintering temperature of from about 800°

C. to about 1700°

C.

37. The method of claim 35, wherein said coating of said template material is achieved by spray coating.

38. The method of claim 35, wherein said shell is a non-alpha aluminum oxide that upon said sintering forms an α

-aluminum oxide coating.

39. The method of claim 35, wherein said formulation is a slurry comprising said ceramic material or oxide thereof or metal oxide, along with a liquid carrier.

40. The method of claim 35, wherein said formulation is introduced into a spray coating chamber as an atomized spray and said template material is suspended in air during said coating of said template material.

41. The method of claim 35, wherein said sintering is sufficient to densify said ceramic material or oxide thereof or metal oxide and form a continuous coating.

42. The method of claim 35, wherein said formulation comprises at least one acid, surfactant, suspension aid, glassy phase formation agent, sintering aid, grain growth inhibitor, ceramic strengthening agent, crystallization control agent, or phase formation control agent, or any combination thereof.

43. The method of claim 35, wherein said ceramic material or oxide thereof or metal oxide is in the form of nanoparticles.

44. A proppant formulation comprising the proppant of claim 1, and a carrier.

45. The proppant formulation of claim 44, wherein said carrier is water or brine.

46. A method to prop open subterranean formation fractions comprising introducing the proppant formulation of claim 44 into said subterranean formation.

47. The proppant of claim 1, wherein said proppant has each of the following characteristics:

(a) an overall diameter of from about 90 microns to about 1,600 microns;

(b) spherical;

(c) said shell is substantially non-porous;

(d) said proppant has said crush strength of about 3,000 psi or greater;

(e) said coating has a wall thickness of from about 15 to about 120 microns;

(f) said proppant has a specific gravity of from about 0.9 to about 1.5 g/cc; and

(g) said template material is a hollow sphere.

48. The proppant of claim 47, wherein said template material is a cenosphere.

49. The proppant of claim 47, wherein said template material is an aluminate.

50. The proppant of claim 47, wherein said template material is a sintered aluminum oxide.

51. The proppant of claim 47, wherein said template material alone has a crush strength of less than 1,000 psi.

52. The proppant of claim 47, wherein said template material is a non-composite material.

53. The proppant of claim 1, wherein said shell is an α

-aluminum oxide coating.

54. The proppant of claim 1, wherein said proppant has said crush strength of from 5,000 psi to 10,000 psi.

55. The proppant of claim 1, wherein said shell comprises Mullite, Cordierite, or both.

56. The method of claim 35, wherein said shell, prior to said sintering, comprises nanoparticles as a mixture of primary particles and agglomerates.

57. The method of claim 56, wherein said primary particles have an average particle size of from about 1 nm to about 150 nm, and said agglomerates have an average particle size of from about 10 nm to about 350 nm.

58. The method of claim 35, wherein said formulation is prepared by peptizing Boehmite with at least one acid to form a sol-gel formulation comprising alumoxane.

59. The method of claim 35, wherein said formulation is a slurry comprising an alumoxane, along with a liquid carrier.

60. The proppant of claim 55, wherein said sintering aid, grain growth inhibitor, ceramic strengthening agent, glassy phase formation agent, crystallization control agent, or phase formation control agent comprises yttrium, zirconium, iron, magnesium, alumina, bismuth, silicon, lanthanum, calcium, cerium, silicates, borates, or oxides thereof or any combination thereof.

61. The proppant of claim 1, wherein said template material is a blown sphere.

62. The proppant formulation of claim 44, wherein said carrier comprises a gel, a foam, a gas, a hydrocarbon, oil, or any combination thereof.

63. The proppant of claim 1, wherein said shell has an average grain size of 1 micron or less.

64. The proppant of claim 1, wherein said shell has an average grain size of 0.1 micron to 0.5 micron.

65. The proppant of claim 64, wherein said shell has a maximum grain size of 1 micron.

66. The proppant of claim 63, wherein at least 90% of all grain sizes are within the range of from 0.1 to 0.6 micron.

67. The proppant of claim 1, wherein said proppant has a specific gravity of from 0.9 g/cc to about 1.5 g/cc.

68. The proppant of claim 1, wherein said proppant has a specific gravity of from 1.0 g/cc to about 1.3 g/cc.

69. The proppant in claim 1, wherein said shell comprises one or more crystalline phases or one or more glassy phases, or combinations thereof.

70. The proppant of claim 1, wherein said template material is a synthetic ceramic microsphere.

71. The proppant of claim 70, wherein said template is formed from a blowing process.

72. The proppant of claim 70, wherein said template is formed from a drop tower process.

73. A method of treating a subterranean producing zone penetrated by a well bore comprising the steps of:

(a) preparing or providing a treating fluid that comprises a hydrocarbon or water carrier fluid having the proppant of claim 1 suspended therein, and (b) pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.

74. The method of claim 73, wherein said treating fluid is a fracturing fluid and said particles are deposited in fractures formed in said subterranean producing zone.

75. The method of claim 73, wherein said treating fluid is a gravel packing fluid and said particles are deposited in said well bore adjacent to said subterranean producing zone.