Proppants With Carbide and/or Nitride Phases

• US 20090038797A1
• Filed: 07/18/2008
• Published: 02/12/2009
• Est. Priority Date: 07/18/2007
• Status: Active Grant

• Current Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Original Assignee: Oxane Materials, Inc.
• Inventors: Coker, Christopher E., Skala, Robert D., Loscutova, John R.
• Granted Patent: US 8,047,288 B2
• Time in Patent Office: Days
• US Class Current: 166/280.100
• CPC Class Codes: C01B 21/06 Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boronazides C01B21/08
• CPC Class Codes: C01B 21/0722 Preparation by direct nitridation of aluminium
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2006/11 Powder tap density
• CPC Class Codes: C01P 2006/14 Pore volume
• CPC Class Codes: C01P 2006/21 Attrition-index or crushing strength of granulates
• CPC Class Codes: C04B 2235/3217 Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
• CPC Class Codes: C04B 2235/3222 Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
• CPC Class Codes: C04B 2235/3865 Aluminium nitrides
• CPC Class Codes: C04B 2235/402 Aluminium
• CPC Class Codes: C04B 2235/465 Ammonia
• CPC Class Codes: C04B 2235/528 Spheres
• CPC Class Codes: C04B 2235/5427 millimeter or submillimeter sized, i.e. larger than 0,1 mm
• CPC Class Codes: C04B 2235/5445 submicron sized, i.e. from 0,1 to 1 micron
• CPC Class Codes: C04B 35/581 based on aluminium nitride
• CPC Class Codes: C04B 35/62655 Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
• CPC Class Codes: C04B 35/62695 Granulation or pelletising devices for shaping artificial aggregates from ceramic mixtures B28B1/004
• CPC Class Codes: C04B 35/62807 Silica or silicates
• CPC Class Codes: C04B 35/6281 : Alkaline earth metal oxides
• CPC Class Codes: C04B 35/62813 : Alumina or aluminates
• CPC Class Codes: C04B 35/62823 : Zirconium or hafnium oxide
• CPC Class Codes: C04B 35/62831 : Carbides
• CPC Class Codes: C04B 35/62836 : Nitrides
• CPC Class Codes: C04B 35/62897 : Coatings characterised by their thickness
• 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: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y10S 507/904 : Process of making fluids or additives therefor
• CPC Class Codes: Y10S 507/906 : Solid inorganic additive in defined physical form
• CPC Class Codes: Y10S 507/924 : with specified propping feature
• CPC Class Codes: Y10T 428/294 : including metal or compound thereof [excluding glass, ceramic and asbestos]
• CPC Class Codes: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]

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 method of making a proppant from a proppant material comprising at least one metal oxide, said method comprising reducing in a reactor at least a portion of the at least one metal oxide to respective metal and nitriding and/or carbiding at least a portion of said respective metal to form said proppant.

2. The method of claim 1, wherein said proppant material is at least one metal oxide, glass spheres, or cenospheres.

3. The method of claim 1, wherein said proppant material is in the shape of a solid sphere, hollow sphere, sphere having multiple voids, or any combination thereof.

4. The method of claim 1, wherein said proppant material has an outer surface comprising at least one metal oxide and said nitriding occurs on at least said outer surface.

5. The method of claim 4, wherein said nitriding forms a nitride layer or phase.

6. The method of claim 4, wherein said carbiding forms a carbide layer or phase.

7. The method of claim 4, wherein the entire outer surface is nitrided to form a nitride layer or phase.

8. The method of claim 4, wherein the entire outer surface is carbided to form a carbide layer or phase.

9. The method of claim 1, wherein all of the at least one metal oxide present in the proppant material is reduced to said respective metal.

10. The method of claim 9, wherein said respective metal is nitrided or carbided.

11. The method of claim 1, wherein said reducing occurs in a fluidized bed furnace, static bed furnace, rotary furnace, microwave furnace, drop tower furnace, or muffle furnace.

12. The method of claim 1, wherein said reducing comprises utilizing at least one reducing agent in the presence of said proppant material.

13. The method of claim 12, wherein said reducing agent is carbon monoxide.

14. The method of claim 1, wherein said nitriding comprises nitriding with nitrogen gas, anhydrous ammonia gas, nitrogen oxide, and optionally with hydrogen gas or helium gas or both.

15. The method of claim 11, wherein said method further comprises utilizing air as a fluidizing medium.

16. The method of claim 15, wherein said air is pre-heated.

17. The method of claim 1, wherein said method further comprises introducing a carbonaceous material before, during, and/or after said reducing.

18. The method of claim 17, wherein said carbonaceous material is pulverized.

19. The method of claim 17, wherein said carbonaceous material is petroleum coke, charcoal, graphite, or any combination thereof.

20. The method of claim 1, wherein said reducing comprises introducing at least one reactant gas to said reactor.

21. The method of claim 20, wherein said reactant gas at least partially replaces a fluidizing medium that is present in the reactor.

22. The method of claim 1, wherein said nitriding comprises introducing at least one nitrogen-containing gas into said reactor.

23. The method of claim 22, wherein said nitrogen-containing gas replaces said reactant gas.

24. The method of claim 17, wherein said carbonaceous material is at least partially combusted during said method.

25. The method of claim 24, wherein prior to or during said reducing, an oxygen-containing gas is introduced into said reactor to partially combust said carbonaceous material.

26. The method of claim 17, wherein at least a portion of said carbonaceous material reacts with at least a portion of said metal to form a metal-carbide phase.

27. A proppant produced by the method of claim 1.

91. The method of claim 1, wherein said metal oxide is silica, and said metal is silicon.

92. The method of claim 1, wherein said proppant material further comprises at least one metal phase, wherein at least a portion of said metal phase is directly nitrided and/or carbided.

93. The method of claim 1, wherein said proppant material comprises one or more of an oxide of aluminum, antimony, boron, cadmium, cobalt, gold, iron, lead, lithium, magnesium, molybdenum, nickel, platinum, potassium, silver, tin, titanium, tungsten, zinc, or zirconium or any combination thereof.

94. The method of claim 1, wherein said proppant material comprises a metal of aluminum, antimony, boron, cadmium, cobalt, gold, iron, lead, lithium, magnesium, molybdenum, nickel, platinum, potassium, silver, tin, titanium, tungsten, zinc, or zirconium or any combination thereof.

95. The method of claim 1, wherein the metallic carbide phase is formed directly from the metallic oxide phase without having to form the metallic phase first.

96. The method of claim 12, wherein a fluidizing medium is present and comprises a non-oxidizing, oxygen-free fluid, which is optionally pre-heated.

97. The method of claim 17, wherein the carbonaceous material is added to the metal oxide at the commencement of the reaction.

98. The method of claim 17, wherein the carbonaceous material is added to the metal oxide at the commencement of the reaction process in excess of that required for stoichiometry.

99. The method of claim 17, wherein the carbonaceous material is added to the reaction chamber with the metal oxide to cause the reduction of the metal oxide to the metal, and upon completion of the reduction reaction, further carbonaceous material is added to the reaction chamber to form the metal carbide.

100. The method of claim 17, wherein the carbonaceous material is derived from one or more biomass materials.

101. The method of claim 17, wherein the carbonaceous material at least partially reacts with oxygen atoms present in the metal oxide.

104. The method of claim 1, wherein the metal oxide is deposited on a template, wherein the template is pyrolized and forms a carbonaceous material that reacts with the metal oxide to form a metal-carbide phase from internal regions of the proppant towards the outer surface.

105. The method of claim 104, wherein the template is a polymer, petroleum coke, charcoal graphite, or any combination thereof.

106. The method of claim 104, wherein the template material is a biomass material.

114. The method of claim 1, wherein said proppant has an outer surface and said method further comprises treating said proppant to improve the hydrophobic nature of the proppant.

115. The method of claim 1, wherein said proppant has an outer surface and said method further comprises treating said proppant to improve the hydrophilic nature of the proppant.

116. The method of claim 1, wherein said proppant has an outer surface and said method further comprises treating said proppant to produce a hydro neutral surface on the proppant.

28. A proppant comprising at least one metal-nitride phase or respective metal-carbide phase or both.

29. The proppant of claim 28, further comprising at least one metal oxide phase.

30. The proppant of claim 28, further comprising at least one metal phase.

31. The proppant of claim 28, wherein a metal-nitride phase is present, but not a metal-carbide phase.

32. The proppant of claim 28, wherein a metal-carbide phase is present, but not a metal-nitride phase.

33. The proppant of claim 28, wherein said metal-nitride phase is primarily present as the outer surface of the proppant.

34. The proppant of claim 28, wherein said metal-carbide phase is primarily present as the outer surface of the proppant particle.

35. The proppant of claim 30, wherein said metal phase is present in internal regions of the proppant particle.

36. The proppant of claim 28, having at least one void within the interior of the proppant and said proppant having a Krumbein sphericity of at least about 0.5 and a roundness of at least about 0.4.

37. The proppant of claim 36, wherein said metal-nitride phase or metal-carbide phase is a continuous phase that has a thickness of from about 5 microns to 150 microns, and said proppant has a specific gravity of 0.01 g/cc to about 3.2 g/cc, and said proppant has a crush strength of about 1,500 psi or greater, and said proppant has a void volume % of at least 30%.

38. The proppant of claim 36, wherein said proppant has a specific gravity of 0.01 g/cc to about 3.2 g/cc, and said proppant has a crush strength of about 1,500 psi or greater, and said proppant has a void volume % of at least 30%.

39. The proppant of claim 37, wherein said crush strength is at least 2,500 psi.

40. The proppant of claim 37, wherein said crush strength is 2,500 psi to 20,000 psi.

41. The proppant of claim 38, wherein said crush strength is at least 2,500 psi.

42. The proppant of claim 38, wherein said crash strength is 2,500 psi to 20,000 psi.

43. The proppant of claim 37, wherein said void volume % is from 30% to 95%.

44. The proppant of claim 37, wherein said void volume % is from 50% to 95%.

45. The proppant of claim 37, wherein said void volume % is from 60% to 90%.

46. The proppant of claim 37, wherein said proppant has one central void.

47. The proppant of claim 37, wherein said proppant has one central void and multiple voids throughout said proppant.

48. The proppant of claim 36, wherein said proppant comprises a mixture of aluminum oxide and at least one other metal oxide.

49. The proppant of claim 36, further comprising a shell that comprises aluminum oxide, respective metal oxide, zirconium oxide, magnesium oxide, or any combination thereof.

50. The proppant of claim 36, wherein said proppant comprises aerogel, xerogel, pumice, envirospheres, perlite, vermiculite, or fired template spheres.

51. The proppant of claim 28, wherein further comprising a shell of one or more layers.

52. The proppant of claim 51, wherein at least one layer of said shell comprises a resin layer or polymer layer.

53. The proppant of claim 52, wherein said resin layer or polymer layer is the outermost layer comprising said shell.

54. The proppant of claim 51, wherein said shell comprises at least one reinforcement material.

55. The proppant of claim 54, wherein said reinforcement material is a fiber, whisker, filler, or any combination thereof.

56. The proppant of claim 51, wherein said reinforcement material is carbon black, fiberglass, carbon fibers, ceramic whiskers, ceramic particulates, hollow spheres, solid spheres, resin material, metallic particles, or any combination thereof.

57. The proppant of claim 51, wherein said shell comprises a metal carbide, metal nitride, or any combination thereof.

58. The proppant of claim 51, wherein said shell comprises a zirconium oxide, a zirconium carbide, a zirconium nitride, or any combination thereof.

59. The proppant of claim 58, wherein said shell further comprises magnesium oxide, calcium oxide, cerium oxide, yttrium oxide, scandium oxide, titanium dioxide, or any combination thereof.

60. The proppant of claim 51, wherein said shell comprises a metal oxide, a metal carbide, a metal nitride, or any combination thereof, derived from a silicon source, titanium source, tungsten source, zirconium source, aluminum source, boron source, or any combination thereof.

61. The proppant of claim 51, wherein said shell is surface modified with the addition of silicon oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, aluminum oxide, lithium oxide, iron oxide, cordierite, spinel, spodumene, steatite, a silicate, a substituted alumino silicate clay or any combination thereof.

62. The proppant of claim 51, wherein said shell is surface modified by applying at least one organic material to said shell.

63. The proppant of claim 51, wherein said shell comprises multiple layers, wherein one of the layers comprises a metal nitride or metal carbide or both.

64. The proppant of claim 28, wherein a glazing layer is present on said proppant and in immediate contact with said proppant.

65. The proppant of claim 64, wherein said glazing layer comprises silica, mullite, spodumene, silicon oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, aluminum oxide, lithium oxide, iron oxide, cordierite, spinet steatite, a silicate, a substituted alumino silicate clay or any combination thereof.

66. The proppant of claim 64, wherein at least a portion of said glazing layer penetrates or infiltrates below the surface of said proppant.

67. The proppant of claim 28, 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) an optional shell that has voids or is porous or non-porous;

(d) said proppant has a crush strength of about 1,000 psi or greater;

(e) said optional shell, when present has a wall thickness of from about 15 to about 200 microns; and

(f) said proppant has a specific gravity of from about 0.6 to about 4 g/cc.

68. A proppant formulation comprising the proppant of claim 28 and a carrier.

69. A method to prop open subterranean formation fractures comprising introducing the proppant formulation of claim 68 into said subterranean formation.

70. 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 fluid, energized fluid, foam, or a gas carrier having the proppant of claim 28 suspended therein, and (b) pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.

71. The method of claim 70, wherein said treating fluid is a fracturing fluid and said particles are deposited in fractures formed in said subterranean producing zone.

72. The method of claim 70, wherein said treating fluid is a gravel packing fluid and said particles are deposited in said well bore adjacent to said subterranean producing zone.

73. A concrete product comprising a plurality of the proppant of claim 28 and cement.

74. A matrix comprising a plurality of the proppant of claim 28 and at least one matrix material.

75. 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 fluid, energized fluid, foam or gas carrier having the proppant of claim 28 suspended therein, and (b) pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.

76. The proppant of claim 51, wherein said shell comprises one or more layers and said one or more layers comprises a fugitive phase or hollow material or both.

77. The proppant of claim 76, wherein said fugitive phase or hollow material or both is present uniformly throughout said layer.

78. The proppant of claim 51, wherein said shell comprises Steatite.

79. The proppant of claim 51, wherein said shell comprises two or more layers and wherein at least two layers contain a fugitive phase material or a hollow material or both, wherein the fugitive phase material or hollow material or both are the same or different in each layer.

80. The proppant of claim 79, wherein said two or more layers comprise at least an outer layer and an inner layer, wherein said outer layer has a higher amount of said fugitive phase material and/or hollow material compared to said inner layer.

81. The proppant of claim 79, wherein said two or more layers comprise at least an outer layer and an inner layer, wherein said outer layer has a higher amount of said fugitive phase material and/or hollow material compared to said inner layer and said outer layer has a higher amount of said fugitive phase material and/or hollow material compared to said proppant without said layers.

82. The proppant of claim 76, wherein said layer comprises from about 0.5% to about 15% by volume of said fugitive phase material and/or hollow material.

83. The proppant of claim 76, wherein said layer comprises from about 15% to about 25% by volume of said hollow material when the diameter size of the hollow material is from 0.1 to 0.2 microns.

84. The proppant of claim 76, wherein said layer comprises from about 15 volume % to about 80 volume % of said fugitive phase material and/or hollow material.

85. The proppant of claim 28, wherein said proppant comprises fugitive phase material and/or hollow material in an amount of from about 0.1 volume % to about 15 volume %.

86. The proppant of claim 28, wherein said proppant comprises fugitive phase material and/or hollow material in an amount of from about 15 volume % to about 80 volume %.

87. The proppant of claim 51, wherein said shell comprises a coating layer to fill in at least a portion of the pores or voids that are present on a layer comprising a shell or surface of said template sphere.

88. The proppant of claim 54, wherein said reinforcement material is surface treated by a thermal treatment, densification, surface modification, coating, glazing, mechanical treatment, chemical treatment, a direct particle deposition from a slurry containing precursor particles, preferential dissolution of one or more species on the particulates or components, or spark discharge treatment, or any combination thereof.

102. The proppant of claim 28, wherein the proppant comprises silicon carbide, titanium carbide, boron carbide, zirconium carbide, aluminum carbide, tungsten carbide, molybdenum carbide, silicon nitride, titanium nitride, boron nitride, zirconium nitride, aluminum nitride, tungsten nitride, molybdenum nitride, or any combination thereof.

103. The proppant of claim 28, wherein the metallic-carbide phase is primarily present as an internal surface or region of the proppant particle.

107. The proppant of claim 36, wherein said Krumbein sphericity is at least 0.7 and said roundness is at least about 0.6.

108. The proppant of claim 36, wherein said Krumbein sphericity is at least 0.8 and said roundness is at least 0.7.

109. The proppant of claim 36, wherein said Krumbein sphericity is at least 0.9 and said roundness is at least 0.8.

110. The proppant of claim 36, wherein said Krumbein sphericity is greater than 0.9 and said roundness is greater than 0.9.

111. The proppant of claim 67, wherein the specific gravity of the proppant is between 1.0 and 3.5 g/cc.

112. The proppant of claim 67, wherein the specific gravity of the proppant is between 2.0 and 3.0 g/cc.

113. The proppant of claim 67, wherein the specific gravity of the proppant is between 2.5 and 3.5 g/cc.

89. A method of making a proppant from a proppant material comprising at least one metal oxide or metal or both, said method comprising nitriding or carbiding at least a portion of said at least one metal oxide or metal or both to form said proppant.

90. The method of claim 89, wherein said carbiding occurs at a temperature of less than about 1800°

C.

117. A method of making a proppant comprising forming a mixture of a micron or sub-micron metal carbide powder and/or metal nitride powder, with at least one metal powder that has a corresponding metal to the metal carbide or metal nitride and having a micron or sub-micron particle size and optionally a binder, suspending said mixture in a liquid carrier system to form a slurry and forming the slurry into one or more proppants.

118. The method of claim 117, further comprising spray coating the slurry onto a shape forming template to form a hollow sphere with controlled diameter and shell thickness.

119. The method of claim 117, further comprising forming the slurry into a hollow sphere using a coaxial nozzle without the requirement for a shape forming template.

120. The method of claim 117, further comprising forming the slurry into a solid sphere using a spray drier or a granulator.

121. The method of claim 117, wherein the metal carbide or metal nitride powder has a particle size of from 0.2 μ

m to 10 μ

m, and said metal powder has a particle size of from 0.2 μ

m to 10 μ

m, wherein the particle size of the metal powder is the same or different from the particle size of the metal carbide or metal nitride powder.