CA2497948C

Method and stimulating oil and gas wells using deformable proppants

Abstract

A method of fracturing using deformable proppants minimizes proppant pack damage, without compromising the fracturing fluid's proppant transport properties during pumping, by use of deformable proppants. Selection of proppant is dependent upon the mechanical properties of the formation rock. The strength of the deformable proppant is dependent upon the modulus of the formation rock being treated such that the proppant is capable of providing, at the very least, a minimum level of conductivity in in- situ stress environments. The maximum elastic modulus of the deformable proppant is less than the minimum modulus of the formation rock which is being treated. The method is particularly applicable in fracturing operations of subterranean reservoirs such as those comprised primarily of coal, chalk, limestone, dolomite, shale, siltstone, diatomite, etc.

CA2497948C, drawing sheet 1
Sheet 1 of 7

Term

Term ended

Expired 22 February 2025, 1.6 years ago.

  1. Priority
  2. Filed
  3. Granted
  4. Expired
  5. Today

251 claims: 69 independent, 182 dependent

  1. 1
    CA 02497948 2010-12-14 1. A method of fracturing a subterranean formation comprising:introducing into the subterranean formation a fracturing fluid at a pressure sufficient to create or enlarge a fracture in the subterranean formation, wherein the fracturing fluid comprises a deformable proppant, the modulus of the deformable proppant being less than the modulus of the rock of the subterranean formation, the proppant being capable of providing at least a minimum level of conductivity;allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock;wherein embedment of the deformable proppant into the subterranean formation is minimized.
  2. 2
    The method of Claim 1, wherein the subterranean formation is susceptible to fines generation.
  3. 3
    The method of Claim 2, wherein the subterranean formation is comprised primarily of coal, chalk, limestone, dolomite, shale, siltstone or diatomite.
  4. 4
    The method of Claim 1, wherein the deformable proppant is a relatively lightweight proppant.
  5. 5
    The method of Claim 1, wherein the deformable proppant is a relatively lightweight proppant selected from the group consisting of furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin or a mixture thereof.
  6. 6
    The method of Claim 1, wherein the deformable proppant is a relatively lightweight proppant selected from the group consisting of polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene, acrylate-based terpolymer or a mixture thereof.
  7. 7
    The method of Claim 1, wherein the deformable proppant has an elastic modulus of between about 500,000 psi and about 4,000,000 psi at in situ formation conditions.
  8. 8
    The method of Claim 4, wherein the deformable proppant is a natural product selected from chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  9. 9
    The method of Claim 8, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells. CA 02497948 2010-12-14
  10. 10
    The method of Claim 8, wherein the natural product is derived from oak, hickory, walnut, poplar or mahogany.
  11. 11
    The method of Claim 1, wherein the deformable proppant is beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape.
  12. 12
    The method of Claim 1, wherein the deformable proppant has an elastic modulus of between about 500 to about 3,000,000 psi and is a natural product selected from (i.) chipped, ground or crushed walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) chipped, ground or crushed peach, plum, olive, cherry, or apricot seed shells;or (iii.) derived from oak, hickory, walnut, poplar or mahogany.
  13. 13
    The method of Claim 4, wherein the relatively lightweight proppant is an ultra lightweight (ULW) proppant.
  14. 14
    The method of Claim 13, wherein the ULW proppant has an apparent specific gravity less than or equal to 1.25.
  15. 15
    The method of Claim 1, wherein the deformable proppant is a substantially spherical or beaded proppant of polystyrene, methyl methacrylate, nylon, polycarbonates, polyethylene, polypropylene, polyvinylchloride, polypropylene, polyvinyl chloride or polyacrylonitrile-butadiene-styrene.
  16. 16
    The method of Claim 15, wherein the deformable proppant is nylon.
  17. 17
    The method of Claim 15, wherein the deformable proppant is relatively lightweight.
  18. 18
    The method of Claim 1, wherein the deformable proppant is a well treating aggregate of an organic lightweight material and a weight modifying agent.
  19. 19
    The method of Claim 18, wherein the organic lightweight material is selected from polystyrene, styrene-divinylbenzene copolymers, polyacrylates, polyalkyl acrylates, polyacrylate esters, polyalkyl acrylate esters, modified starches, polyepoxides, polyurethanes, polyisocyanates, phenol formaldehyde resins, furan resins and melamine formaldehyde resins.
  20. 20
    The method of Claim 18, wherein the weight modifying agent is selected from finely ground sand, glass powder, glass spheres, glass beads, glass bubbles, ground glass, borosilicate glass and fiberglass.
  21. 21
    The method of Claim 18, wherein the weight modifying agent is composed of (i.) a cation selected from alkali metal, alkaline earth metals, ammonium, manganese and zinc and CA 02497948 2010-12-14 (ii.) an anion selected from a halide, oxide, a carbonate, nitrate, sulfate, acetate and formate.
  22. 22
    The method of Claim 1, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.75.
  23. 23
    The method of Claim 22, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.5.
  24. 24
    The method of Claim 23, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.25.
  25. 29
    A method of fracturing a subterranean formation susceptible to fines generation comprising:(a) contacting the subterranean formation with a deformable proppant at a pressure sufficient to initiate or enlarge a fracture, wherein the proppant has an apparent specific gravity less than or equal to 2.45;and (b) allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock wherein the fracture contains a partial monolayer of the deformable proppant and embedment of the deformable proppant into the subterranean formation is minimized and further wherein the fracture containing the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  26. 30
    The method of Claim 29, wherein the deformable proppant has an apparent specific gravity less than or equal to 2.0. CA 02497948 2010-12-14
  27. 31
    The method of Claim 30, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.75.
  28. 32
    The method of Claim 31, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.5.
  29. 33
    The method of Claim 32, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.25.
  30. 34
    The method of any one of Claims 29-33, wherein the subterranean formation is selected from the group consisting of coal, chalk, limestone, dolomite, shale, siltstone and diatomite.
  31. 35
    The method of any one of Claims 29-34, wherein the deformable proppant is selected from the group consisting of a furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin, polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene and acrylate-based terpolymer or a mixture thereof.
  32. 36
    The method of any one of Claims 29-34, wherein the deformable proppant is a natural product selected from the group consisting of chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  33. 37
    The method of Claim 36, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells.
  34. 38
    The method of any one of Claim 29-37, wherein the deformable proppant is beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape.
  35. 39
    The method of any one of Claims 29-38, wherein the deformable proppant is at least one member selected from the group consisting of polystyrene, methyl methacrylate, nylon, polycarbonates, polyethylene, polypropylene, polyvinylchloride, polypropylene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene and mixtures thereof.
  36. 40
    The method of Claim 39, wherein the deformable proppant is nylon.
  37. 41
    The method of any one of Claims 29-40, wherein the deformable proppant has an elastic modulus of between about 500 psi and about 4,000,000 psi at in situ formation conditions
  38. 42
    The method of any one of Claims 29-41, wherein the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ CA 02497948 2010-12-14 reservoir stress conditions between from 100 psi to 15,000 psi.
  39. 43
    The method of any one of Claims 29-42, wherein the deformable proppant comprises polystyrene divinylbenzene.
  40. 44
    The method of any one of Claims 29-43, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  41. 45
    The method of any one of Claims 29-40 and 42-44, wherein the deformable proppant has an elastic modulus of between about 500,000 psi and about 4,000,000 psi at in situ formation conditions.
  42. 50
    A method of fracturing a soft subterranean formation comprising:(a) introducing into the soft subterranean formation a deformable proppant having an elastic modulus of between from about 500 to about 3,000,000 psi, wherein the modulus of the deformable proppant is less than the modulus of the subterranean formation and further wherein the soft subterranean formation is selected from the group consisting of coal, chalk, limestone, dolomite, shale, siltstone and diatomite;and (b) allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock;(c) wherein embedment of the deformable proppant into the reservoir is minimized.
  43. 51
    The method of Claim 50, wherein the deformable proppant is selected from the group consisting of a furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine CA 02497948 2010-12-14 formaldehyde resin, urethane resin, polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene and acrylate-based terpolymer or a mixture thereof.
  44. 52
    The method of Claim 50, wherein the deformable proppant is a natural product selected from the group consisting of chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  45. 53
    The method of Claim 52, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells.
  46. 54
    The method of Claim 52, wherein the natural product is derived from oak, hickory, walnut, poplar or mahogany.
  47. 55
    The method of Claim 50, wherein the deformable proppant is beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape.
  48. 56
    The method of Claim 50, wherein the deformable proppant is at least one member selected from the group consisting of polystyrene, methyl methacrylate, nylon, polycarbonates, polyethylene, polypropylene, polyvinylchloride, polypropylene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene and mixtures thereof.
  49. 57
    The method of Claim 56, wherein the deformable proppant is nylon.
  50. 58
    The method of Claim 50, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.75.
  51. 59
    The method of Claim 58, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.5.
  52. 60
    The method of Claim 59, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.25.
  53. 61
    The method of any one of Claims 50-60, wherein the fracture contains a partial monolayer of the deformable proppant, which is capable of providing at least a minimum level of conductivity at in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  54. 62
    The method of any one of Claims 50, 51 and 56-61, wherein the deformable proppant comprises polystyrene divinylbenzene.
  55. 63
    The method of any one of Claims 50-62, wherein step (a) comprises introducing into the CA 02497948 2010-12-14 subterranean formation particulates consisting essentially of the deformable proppant.
  56. 64
    The method of any one of Claims 50-63, wherein the deformable proppant has an elastic modulus above about 500,000 psi at in situ formation conditions.
  57. 65
    The method of any one of Claims 50-64 wherein the fracture contains a partial monolayer of the deformable proppant and further wherein the fracture containing the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  58. 66
    The method of any one of Claims 50-65, wherein the deformable proppant is introduced into the formation at a pressure sufficient to create or enlarge a fracture.
  59. 71
    A method of fracturing a subterranean formation surrounding an oil or gas well which comprises:(a) contacting the subterranean formation with a deformable proppant at a pressure sufficient to initiate or enlarge a fracture, the proppant comprising an organic lightweight material and a weight modifying agent, the modulus of the deformable proppant being less than the modulus of the rock of the subterranean formation;and (b) allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock wherein embedment of the deformable proppant into the subterranean formation is minimized. CA 02497948 2010-12-14
  60. 72
    The method of Claim 71, wherein the deformable proppant is comprised of a continuous phase composed of the organic lightweight material and a discontinuous phase composed of a weight modifying material.
  61. 73
    The method of Claim 71, wherein the amount of organic lightweight material in the deformable proppant is generally between from about 10 to about 90 percent by volume.
  62. 74
    The method of Claim 72, wherein the organic lightweight material is a polymeric material selected from the group consisting of polystyrene, a styrene-divinylbenzene copolymer, a polyacrylate, a polyalkylacrylate, a polyacrylate ester, a polyalkyl acrylate ester, a modified starch, a polyepoxide, a polyurethane, a polyisocyanate, a phenol formaldehyde resin, a furan resin and a melamine formaldehyde resin.
  63. 75
    The method of Claim 72, wherein the weight modifying agent is selected from the group consisting of sand, glass, hematite, silica, sand, fly ash, aluminosilicate, trimanganese tetraoxide and an alkali metal salt.
  64. 76
    The method of Claim 72, wherein the weight modifying agent is selected from the group consisting of finely ground sand, glass powder, glass spheres, glass beads, glass bubbles, ground glass, borosilicate glass and fiberglass.
  65. 77
    The method of Claim 72, wherein the weight modifying agent contains a cation selected from the group consisting of an alkali metal, alkaline earth metal, ammonium, manganese and zinc and an anion selected from the group consisting of a halide, oxide, a carbonate, nitrate, sulfate, acetate and formate.
  66. 78
    The method of Claim 72, wherein the weight modifying agent is selected from the group consisting of calcium carbonate, potassium chloride, sodium chloride, sodium bromide, calcium chloride, barium sulfate, calcium bromide, zinc bromide, zinc formate, zinc oxide, glass bubbles and fly ash or a mixture thereof.
  67. 79
    The method of Claim 71, wherein the deformable proppant is at least one member selected from the group consisting of polystyrene, methyl methacrylate, nylon, polycarbonates, polyethylene, polypropylene, polyvinylchloride, polypropylene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene and mixtures thereof.
  68. 80
    The method of Claim 79, wherein the deformable proppant is nylon.
  69. 81
    The method of Claim 72, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.75. CA 02497948 2010-12-14
  70. 82
    The method of Claim 81, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.5.
  71. 83
    The method of Claim 82, wherein the deformable proppant has an apparent specific gravity less than or equal to 1.25.
  72. 84
    The method of any one of Claims 71-83, wherein the fracture contains a partial monolayer of the deformable proppant which is capable of providing at least a minimum level of conductivity at in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  73. 85
    The method of any one of Claims 71-84, wherein the deformable proppant comprises polystyrene divinylbenzene.
  74. 86
    The method of any one of Claims 71-85, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  75. 87
    The method of any one of Claims 71-86, wherein the deformable proppant has an elastic modulus between about 500 psi and about 4,000,000 psi at in situ formation conditions.
  76. 88
    The method of Claim 87, wherein the deformable proppant has an elastic modulus above about 500,000 psi at in situ formation conditions.
  77. 89
    The method of any one of Claims 71-88, wherein the fracture contains a partial monolayer of the deformable proppant and further wherein the fracture containing the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  78. 94
    A method of fracturing a subterranean formation susceptible to fines generation comprising:CA 02497948 2010-12-14 (a) introducing into the subterranean formation particulates consisting essentially of deformable proppants, wherein the particulates have an apparent specific gravity less than or equal to 2.45;and (b) allowing the subterranean formation to close on the created partial monolayer such that the energy of the closure stress is absorbed by the deformable proppants and not by the face of the rock wherein said formation contains a partial monolayer of said particulates and embedment of the deformable proppants into the subterranean formation is minimized and further wherein the fracture containing the partial monolayer of deformable proppants is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  79. 95
    The method of Claim 94, wherein the deformable proppants have an apparent specific gravity less than or equal to 2.0.
  80. 96
    The method of Claim 95, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.75.
  81. 97
    The method of Claim 96, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.5.
  82. 98
    The method of Claim 97, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.25.
  83. 99
    The method of Claim 94, wherein the subterranean formation is selected from the group consisting of coal, chalk, limestone, dolomite, shale, siltstone and diatomite.
  84. 100
    The method of Claim 94, wherein the deformable proppants are at least one member selected from the group consisting of a furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin, polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene and acrylate-based terpolymer or a mixture thereof.
  85. 101
    The method of Claim 100, wherein the deformable proppants are at least one member of a natural product selected from the group consisting of chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent. CA 02497948 2010-12-14
  86. 102
    The method of Claim 101, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells.
  87. 103
    The method of Claim 94, wherein the deformable proppants are beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape.
  88. 104
    The method of any one of Claims 94-103, wherein the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  89. 105
    The method of any one of Claims 94-99, 103 and 104, wherein the deformable proppant comprises polystyrene divinylbenzene.
  90. 106
    The method of any one of Claims 94-105, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  91. 107
    The method of any one of Claims 94-106, wherein the deformable proppant has an elastic modulus between about 500 psi and about 4,000,000 psi at in situ formation conditions.
  92. 108
    The method of Claim 107, wherein the deformable proppant has an elastic modulus above about 500,000 psi at in situ formation conditions.
  93. 109
    The method of any one of Claims 94-108 wherein the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  94. 110
    The method of any one of Claims 94-109, wherein the deformable proppant is introduced into the formation at a pressure sufficient to create or enlarge a fracture.
  95. 115
    A method of fracturing a soft subterranean formation comprising:A. introducing into the soft subterranean formation a deformable proppant, wherein the deformable proppant consists essentially of either: (a) particulates having an apparent specific gravity less than or equal to 2.45;or (b) particulates having an apparent specific gravity less than or equal to 2.45 having a coating or modifying agent which increases the resistance of the particulates to deformation and further wherein the deformable proppant has an elastic modulus of between from about 500 to about 3,000,000 psi, wherein the modulus of the deformable proppant is less than the modulus of the subterranean formation and further wherein the soft subterranean formation is selected from the group consisting of coal, chalk, limestone, dolomite, shale, siltstone and diatomite;and allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock;wherein embedment of the deformable proppant into the reservoir is minimized.
  96. 116
    The method of Claim 115, wherein the soft subterranean formation is selected from the group consisting of coal, chalk, siltstone and diatomite.
  97. 117
    The method of Claim 115, wherein the deformable proppant is selected from the group consisting of a furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin, polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene and acrylate-based terpolymer or a mixture thereof.
  98. 118
    The method of Claim 115, wherein the deformable proppant is a natural product selected from the group consisting of chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  99. 119
    The method of Claim 118, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells.
  100. 120
    The method of Claim 118, wherein the natural product is derived from oak, hickory, walnut, poplar or mahogany. CA 02497948 2010-12-14
  101. 121
    The method of Claim 115, wherein the deformable proppant is beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape.
  102. 122
    The method of any one of Claims 115-121, wherein the fracture contains a partial monolayer of the deformable proppant which is capable of providing at least a minimum level of conductivity at in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  103. 123
    The method of any one of Claims 115, 116 and 121-122, wherein the deformable proppant comprises polystyrene divinylbenzene.
  104. 124
    The method of any one of Claims 115-123, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  105. 125
    The method of any one of Claims 115-124, wherein the deformable proppant has an elastic modulus above about 500,000 psi at in situ formation conditions.
  106. 126
    The method of any one of Claims 115-125 wherein the fracture contains a partial monolayer of the deformable proppant and further wherein the fracture containing the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  107. 127
    The method of any one of Claims 115-126 wherein the deformable particulates have an elastic modulus of between about 500,000 psi and about 2,000,000 psi at in situ formation conditions.
  108. 128
    The method of any one of Claims 115-127, wherein the deformable proppant is introduced into the formation at a pressure sufficient to create or enlarge a fracture.
  109. 129
    The method of any one of Claims 95-128, wherein the deformable proppants have an apparent specific gravity less than or equal to 2.0.
  110. 130
    The method of Claim 129, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.75.
  111. 131
    The method of Claim 130, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.5.
  112. 132
    The method of Claim 131, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.25. CA 02497948 2010-12-14
  113. 137
    A method of fracturing a subterranean formation surrounding an oil or gas well which comprises:(a) introducing into the subterranean formation a deformable proppant, wherein the deformable proppant consists essentially of: (i) an aggregate of an organic lightweight material and a weight modifying, agent;or (ii) an aggregate of an organic lightweight material and weight modifying agent, the aggregate having a coating or modifying agent which increases the resistance of the aggregate to deformation the modulus of the deformable proppant being less than the modulus of the rock of the subterranean formation;and (b) allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock wherein embedment of the deformable proppant into the subterranean formation is minimized.
  114. 138
    The method of Claim 137, wherein the deformable proppant is comprised of a continuous phase composed of the organic lightweight material and a discontinuous phase composed of a weight modifying material.
  115. 139
    The method of Claim 137, wherein the amount of organic lightweight material in the aggregate is generally between from about 10 to about 90 percent by volume.
  116. 140
    The method of Claim 137, wherein the organic lightweight material is a polymeric material selected from the group consisting of polystyrene, a styrene29 CA 02497948 2010-12-14 divinylbenzene copolymer, a polyacrylate, a polyalkylacrylate, a polyacrylate ester, a polyalkyl acrylate ester, a modified starch, a polyepoxide, a polyurethane, a polyisocyanate, a phenol formaldehyde resin, a furan resin and a melamine formaldehyde resin.
  117. 141
    The method of Claim 137, wherein the weight modifying agent is selected from the group consisting of sand, glass, hematite, silica, sand, fly ash, aluminosilicate, trimanganese tetraoxide and an alkali metal salt.
  118. 142
    The method of Claim 137, wherein the weight modifying agent is selected from the group consisting of finely ground sand, glass powder, glass spheres, glass beads, glass bubbles, ground glass, borosilicate glass and fiberglass.
  119. 143
    The method of Claim 137, wherein the weight modifying agent contains a cation selected from the group consisting of an alkali metal, alkaline earth metal, ammonium, manganese and zinc and an anion selected from the group consisting of a halide, oxide, a carbonate, nitrate, sulfate, acetate and formate.
  120. 144
    The method of Claim 137, wherein the weight modifying agent is selected from the group consisting of calcium carbonate, potassium chloride, sodium chloride, sodium bromide, calcium chloride, barium sulfate, calcium bromide, zinc bromide, zinc formate, zinc oxide, glass bubbles and fly ash or a mixture thereof.
  121. 145
    The method of any one of Claims 137-144, wherein the fracture contains a partial monolayer of the deformable proppant which is capable of providing at least a minimum level of conductivity at in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  122. 146
    The method of Claim 137, wherein the deformable proppant comprises polystyrene divinylbenzene.
  123. 147
    The method of any one of Claims 137-146, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  124. 148
    The method of any one of Claims 137-147, wherein the deformable proppant has an elastic modulus between about 500 psi and about 4,000,000 psi at in situ formation conditions. CA 02497948 2010-12-14
  125. 150
    The method of any one of Claims 137-149, wherein the fracture contains a partial monolayer of the deformable proppant and further wherein the fracture containing the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  126. 151
    The method of any one of Claims 137-150 wherein the deformable particulates have an elastic modulus of between about 500,000 psi and about 2,000,000 psi at in situ formation conditions.
  127. 152
    The method of any one of Claims 137-151, wherein the deformable proppant is introduced into the formation at a pressure sufficient to create or enlarge a fracture.
  128. 153
    The method of any one of Claims 137-152, wherein the deformable proppants have an apparent specific gravity less than or equal to 2.0.
  129. 154
    The method of Claim 153, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.75.
  130. 155
    The method of Claim 154, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.5.
  131. 156
    The method of Claim 155, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.25.
  132. 161
    A method of fracturing a subterranean formation susceptible to fines generation comprising:(A) introducing into the subterranean formation a fracturing fluid at a pressure sufficient to create or enlarge a fracture in the subterranean formation, wherein the CA 02497948 2010-12-14 fracturing fluid comprises a deformable proppant, wherein the deformable proppant consists essentially of either: (a) particulates having an apparent specific gravity less than or equal to 2.45;or (b) particulates having an apparent specific gravity less than or equal to 2.45 having a coating or modifying agent which increases the resistance of the particulates to deformation, the modulus of the deformable proppant being less than the modulus of the rock of the subterranean formation, the proppant being capable of providing at least a minimum level of conductivity;(B) allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock;wherein embedment of the deformable proppant into the subterranean formation is minimized.
  133. 162
    The method of Claim 161, wherein the subterranean formation is comprised primarily of coal, chalk, limestone, dolomite, shale, siltstone or diatomite.
  134. 163
    The method of Claim 161, wherein the apparent specific gravity of the deformable proppant is less than or equal to 2.25.
  135. 164
    The method of Claim 161, wherein the deformable proppant is selected from the group consisting of furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin or a mixture thereof.
  136. 165
    The method of Claim 161, wherein the deformable proppant is selected from the group consisting of polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene, acrylate-based terpolymer or a mixture thereof.
  137. 166
    The method of Claim 161, wherein the deformable proppant has an elastic modulus of between about 500,000 psi and about 4,000,000 psi at in situ formation conditions.
  138. 167
    The method of Claim 161, wherein the deformable proppant is a natural product selected from chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent. CA 02497948 2010-12-14
  139. 168
    The method of Claim 167, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells.
  140. 169
    The method of Claim 167, wherein the natural product is derived from oak, hickory, walnut, poplar or mahogany.
  141. 170
    The method of Claim 161, wherein the deformable proppant is beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape.
  142. 171
    The method of Claim 163, wherein the deformable proppant has an apparent specific gravity less than or equal to 2.0.
  143. 172
    The method of Claim 163, wherein the deformable proppant is selected from the group consisting of furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin, polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene, acrylate-based terpolymer, polystyrene, methyl methacrylate, polycarbonates, polyethylene, polypropylene, polyvinylchloride, polypropylene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene and mixtures thereof.
  144. 173
    The method of Claim 161, wherein the deformable proppant is a natural product selected from chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  145. 174
    The method of any one of Claims 161-173, wherein the fracture contains a partial monolayer of the deformable proppant which is capable of providing at least a minimum level of conductivity at in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  146. 175
    The method of any one of Claims 161, 163, 170, 171 and 174, wherein the deformable proppant comprises polystyrene divinylbenzene.
  147. 176
    The method of any one of Claims 161-75, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  148. 177
    The method of any one of Claims 161-176, wherein the deformable particulates have an elastic modulus of between about 500,000 psi and about 2,000,000 psi at in situ formation conditions. CA 02497948 2010-12-14
  149. 178
    The method of any one of Claims 161-177, wherein the fracture contains a partial monolayer of the deformable proppant and further wherein the fracture containing the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  150. 179
    The method of Claim 161, wherein the deformable proppants have an apparent specific gravity less than or equal to 2.0.
  151. 180
    The method of Claim 179, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.75.
  152. 181
    The method of Claim 180, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.5.
  153. 182
    The method of Claim 181, wherein the deformable proppants have an apparent specific gravity less than or equal to 1.25.
  154. 187
    A method of fracturing a subterranean formation comprising:(a) introducing into the subterranean formation a fracturing fluid at a pressure sufficient to create or enlarge a fracture in the subterranean formation, wherein the fracturing fluid comprises a deformable proppant, the modulus of the deformable proppant being less than the modulus of the rock of the subterranean formation, wherein the proppant has an apparent specific gravity between from about 1.0 and about 1.2;and (b) allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant and not by the face of the rock CA 02497948 2010-12-14 wherein a fracture contains a partial monolayer of the deformable proppant and embedment of the deformable proppant into the subterranean formation is minimized and further wherein the fracture containing the partial monolayer of deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  155. 188
    The method of Claim 187, wherein the deformable proppants are at least one member selected from the group consisting of polystyrene, methyl methacrylate, nylon, polycarbonates, polyethylene, polypropylene, polyvinylchloride, polypropylene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene and mixtures thereof.
  156. 189
    The method of Claim 188, wherein the deformable proppant is nylon.
  157. 190
    The method of Claim 187, wherein the deformable proppant comprises polystyrene divinylbenzene.
  158. 191
    The method of any one of Claims 187-190, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  159. 192
    The method of any one of Claims 187-191, wherein the deformable proppant has an elastic modulus of between about 500 psi and about 4,000,000 psi at in situ formation conditions.
  160. 193
    The method of Claim 192, wherein the deformable proppant has an elastic modulus of above about 500,000 psi at in situ formation conditions.
  161. 198
    A method of fracturing a subterranean formation susceptible to fines generation comprising:CA 02497948 2010-12-14 (a) introducing deformable proppants into the subterranean formation at a pressure sufficient to hydraulically create or enlarge fractures in the formation, wherein the deformable proppants consist essentially of deformable particulates which have an elastic modulus of between about 500 psi and about 4,000,000 psi at in situ formation conditions and which have an apparent specific gravity less than or equal to 2.45 wherein fractures are created or enlarged and the created or enlarged fractures have a partial monolayer of said deformable proppants;and (b) allowing the subterranean formation to close on the created partial monolayer such that the energy of the closure stress is absorbed by the deformable proppants and not by the face of the rock wherein embedment of the deformable proppants into the subterranean formation is minimized and further wherein the fracture containing the partial monolayer of deformable proppants is capable of providing at least a minimum level of conductivity at in-situ reservoir conditions.
  162. 199
    The method of Claim 198, wherein the deformable particulates have an apparent specific gravity less than or equal to 2.0.
  163. 200
    The method of Claim 199, wherein the deformable particulates have an apparent specific gravity less than or equal to 1.75.
  164. 201
    The method of Claim 200, wherein the deformable particulates have an apparent specific gravity less than or equal to 1.5.
  165. 202
    The method of Claim 201, wherein the deformable particulates have an apparent specific gravity less than or equal to 1.25.
  166. 203
    The method of Claim 198, wherein the subterranean formation is selected from the group consisting of coal, chalk, limestone, dolomite, shale, siltstone and diatomite.
  167. 204
    The method of Claim 198, wherein the deformable particulates are at least one member selected from the group consisting of a furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin, polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene and acrylate-based terpolymer or a mixture thereof. CA 02497948 2010-12-14
  168. 205
    The method of Claim 204, wherein the deformable particulates are at least one member of a natural product selected from the group consisting of chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  169. 206
    The method of Claim 205, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells.
  170. 207
    The method of Claim 198, wherein the deformable particulates are beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape.
  171. 208
    The method of any one of Claims 198-203 and 207, wherein the deformable proppant comprises polystyrene divinylbenzene.
  172. 213
    A method of fracturing a subterranean formation susceptible to fines generation comprising; introducing into the subterranean formation at a pressure sufficient to create or enlarge a fracture in the subterranean formation a fracturing fluid containing deformable particulates; hydraulically creating or enlarging a fracture in the formation, wherein a proppant pack of the deformable particulates is deposited in the fracture, wherein the deformable particulates of the proppant pack consist essentially of either:(a) deformable particulates having an apparent specific gravity less than or equal to 2.45;or (b) deformable particulates having an apparent specific gravity less CA 02497948 2010-12-14 than or equal to 2.45 having a coating or modifying agent which increases the resistance of the deformable particulates to deformation, the modulus of the deformable-particulates being less than the modulus of the rock of the subterranean formation, the particulates being capable of providing at least a minimum level of conductivity;allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable proppant pack and not by the face of the rock;wherein embedment of the deformable particulates into the subterranean formation is minimized.
  173. 214
    The method of Claim 213, wherein the apparent specific gravity of the deformable particulates is less than or equal to 2.25.
  174. 215
    The method of Claim 213, wherein the deformable particulates are selected from the group consisting of furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin and mixtures thereof.
  175. 216
    The method of Claim 213, wherein the deformable particulates are selected from the group consisting of polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene, acrylate-based terpolymer and mixtures thereof.
  176. 217
    The method of Claim 213, wherein the deformable particulates have an elastic modulus of between about 500,000 psi and about 2,000,000 psi at in situ formation conditions.
  177. 218
    The method of Claim 213, wherein the deformable particulates are a natural product selected from chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  178. 219
    The method of Claim 218, wherein the natural product is selected from chipped, ground or crushed (i.) walnut, pecan, coconut, almond, ivory or brazil nuts;(ii.) peach, plum, olive, cherry, or apricot seed shells.
  179. 220
    The method of Claim 213, wherein the natural product is derived from oak, hickory, walnut, poplar or mahogany.
  180. 221
    The method of Claim 213, wherein the deformable particulates are beaded, cubic, cylindrical, bar-shaped, multi-faceted, irregular or tapered in shape. CA 02497948 2010-12-14
  181. 222
    The method of Claim 221, wherein the deformable particulates have an apparent specific gravity less than or equal to 2.0.
  182. 223
    The method of Claim 222, wherein the deformable particulates have an apparent specific gravity less than or equal to 1.25.
  183. 224
    The method of Claim 213, wherein the deformable particulates are selected from the group consisting of furan, furfuryl, phenol formaldehyde, phenolic epoxy, melamine formaldehyde resin, urethane resin, polystyrene divinylbenzene, polystyrene/vinyl/divinyl benzene, acrylate-based terpolymer, polystyrene, methyl methacrylate, polycarbonates, polyethylene, polypropylene, polyvinylchloride, polypropylene, polyvinyl chloride, polyacrylonitrile-butadiene-styrene and mixtures thereof.
  184. 225
    The method of Claim 213, wherein the deformable particulates are a natural product selected from chipped, ground or crushed nut shells, seed shells, fruit pits and processed wood at least partially coated or hardened with a protective coating or modifying agent.
  185. 226
    The method of any one of Claims 213-225, wherein the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  186. 227
    The method of any one of Claims 213, 214, 216, 217, 221-223 and 226 wherein the deformable proppant comprises polystyrene divinylbenzene.
  187. 228
    The method of any one of Claims 213-227, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  188. 233
    A method of fracturing a subterranean formation comprising:(a) introducing into the subterranean formation a fracturing fluid at a pressure sufficient to hydraulically create or enlarge a fracture in the formation, wherein the fracturing fluid comprises deformable proppants having an apparent specific gravity less than or equal to 1.25, wherein the deformable proppants are composed only of particulates which are deformable;(b) allowing the subterranean formation to close such that the energy of the closure stress is absorbed by the deformable particulates and not by the face of the rock, wherein the permeability and porosity of the fracture is maintained by the deformable particulates while embedment of the deformable particulates into the subterranean formation is minimized while the fracture is held open by the deformable proppants.
  189. 234
    The method of Claim 233, wherein the deformable particulates are nylon.
  190. 235
    The method of Claim 233, wherein the deformable proppants in the created or enlarged fracture are in the form of a partial monolayer.
  191. 236
    The method of Claim 233, wherein the deformable particulates have an elastic modulus of between about 500,000 psi and about 2,000,000 psi at in situ formation conditions.
  192. 237
    The method of Claim 233, wherein the subterranean formation is comprised primarily of coal, chalk, limestone, dolomite, shale, siltstone or diatomite.
  193. 238
    The method of Claim 233, wherein the deformable particulates are substantially spherical or beaded.
  194. 239
    The method of Claim 238, wherein the deformable particulates are beaded.
  195. 240
    The method of Claim 233, wherein the deformable proppant further comprises a weight modifying agent.
  196. 241
    The method of Claim 240, wherein the weight modifying agent is selected from the group consisting of sand, glass, hematite, silica, fly ash, aluminosilicate, alkali metal salts and trimanganese tetraoxide.
  197. 242
    The method of Claim 241, wherein the weight modifying agent is fly ash.
  198. 243
    The method of any one of Claims 233-242, wherein the partial monolayer of the deformable proppant is capable of providing at least a minimum level of conductivity at CA 02497948 2010-12-14 in-situ reservoir stress conditions between from 100 psi to 15,000 psi.
  199. 244
    The method of any one of Claims 233 and 235-239, wherein the deformable proppant comprises polystyrene divinylbenzene.
  200. 245
    The method of any one of Claims 233-244, wherein step (a) comprises introducing into the subterranean formation particulates consisting essentially of the deformable proppant.
  201. 246
    The method of any one of Claims 233-245, wherein the deformable proppant has an elastic modulus of between about 500,000 psi and about 4,000,000 psi at in situ formation conditions.
  202. 247
    The method of any one of Claims 233-245, wherein the deformable proppant has an elastic modulus of between about 500,000 psi and about 2,000,000 psi at in situ formation conditions.
Independent claims202