ROD-SHAPED PROPPANT AND ANTI-FLOWBACK ADDITIVE, METHOD OF MANUFACTURE, AND METHOD OF USE

1 . A high strength sintered rod-shaped proppant for fracturing subterranean formations comprising at least about 90% by weight alumina and between about 0.2% by weight and about 4% by weight aluminum titanate.

2 . The proppant of claim 1 wherein the proppant comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

3 . The proppant of claim 2 wherein the proppant comprises between about 1% by weight and about 2.5% by weight aluminum titanate.

4 . The proppant of claim 1 comprising at least about 95% alumina by weight.

5 . The proppant of claim 1 wherein the proppant comprises less than about 4% SiO 2 by weight.

6 . The proppant of claim 5 wherein the proppant comprises less than about 2% SiO 2 by weight.

7 . The proppant of claim 1 wherein the alumina is contributed by both bauxitic and non-bauxitic sources.

8 . The proppant of claim 7 wherein the bauxitic source contributes at least about 80% of the alumina content by weight of the sintered proppant.

9 . The proppant of claim 8 wherein the bauxitic source contributes at least about 85% of the alumina content by weight of the sintered proppant.

10 . The proppant of claim 7 wherein the non-bauxitic source comprises technical grade alumina.

11 . The proppant of claim 7 wherein the non-bauxitic source contributes at least about 90% of the alumina content by weight of the sintered proppant.

12 . The proppant of claim 11 wherein the non-bauxitic source contributes at least about 95% of the alumina content by weight of the sintered proppant.

13 . The proppant of claim 11 wherein the non-bauxitic source comprises technical grade alumina.

14 . The proppant of claim 13 wherein the bauxitic source contributes between 0.1% and 10% of the alumina content by weight of the sintered proppant.

15 . The proppant of claim 7 wherein the bauxitic source contains a Fe 2 O 3 content of less than 10% by weight by weight of the bauxitic source.

16 . The proppant of claim 15 wherein the bauxitic source contains a Fe 2 O 3 content of less than 8% by weight of the bauxitic source.

17 . The proppant of claim 7 wherein the bauxitic and non-bauxitic sources contain a combined TiO 2 content of between about 0.15% and about 3.5% by weight.

18 . The proppant of claim 17 wherein the bauxitic and non-bauxitic sources contain a combined TiO 2 content of between about 0.3% and about 2.7% by weight.

19 . The proppant of claim 18 wherein the bauxitic and non-bauxitic sources contain a combined TiO 2 content of between about 0.4% and about 2.3% by weight.

20 . The proppant of claim 1 wherein the proppant has an average length to width ratio of between about 1.5:1 to about 20:1.

21 . The proppant of claim 20 wherein the proppant has an average length to width ratio of between about 1.5:1 to about 10:1.

22 . The proppant of claim 21 wherein the proppant has an average length to width ratio of between about 1.5:1 to about 7:1.

23 . The proppant of claim 22 wherein the proppant has an average length to width ratio of between about 2:1 to about 4:1.

24 . The proppant of claim 1 wherein the proppant is substantially cylindrical.

25 . The proppant of claim 1 wherein the proppant has a substantially circular cross-section.

26 . The proppant of claim 25 wherein the substantially circular cross-section has an average diameter of between about 0.5 mm and about 2 mm.

27 . The proppant of claim 26 wherein the substantially circular cross-section has an average diameter of between about 0.5 mm and about 1.5 mm.

28 . The proppant of claim 1 wherein the proppant has an average length between about 0.1 mm and about 20 mm.

29 . The proppant of claim 28 wherein the proppant has an average length between about 0.5 mm and about 10 mm.

30 . The proppant of claim 29 wherein the proppant has an average length between about 1 mm and about 5 mm.

31 . The proppant of claim 30 wherein the proppant has an average length between about 2 mm and about 4 mm.

32 . The proppant of claim 1 wherein the proppant has been extruded.

33 . The proppant of claim 1 wherein the proppant has an apparent specific gravity less than about 3.98.

34 . The proppant of claim 33 wherein the proppant has an apparent specific gravity between about 3.0 and about 3.98.

35 . The proppant of claim 34 wherein the proppant has an apparent specific gravity of between about 3.2 and about 3.95.

36 . The proppant of claim 1 wherein the proppant has a bulk density of between about 1.5 g/cm 3 and about 2.5 g/cm 3 .

37 . The proppant of claim 36 wherein the proppant has a bulk density of between about 1.7 g/cm 3 and about 2.3 g/cm 3 .

38 . The proppant of claim 1 wherein less than about 15% of the proppant is crushed at 10,000 psi.

39 . The proppant of claim 1 wherein less than about 20% of the proppant is crushed at 15,000 psi.

40 . The proppant of claim 1 wherein the proppant is coated with a natural or synthetic coating.

41 . The proppant of claim 40 wherein the natural or synthetic coating is selected from the group consisting of natural rubber; elastomers; butyl rubber; polyurethane rubber; starches; petroleum pitch; tar; asphalt; organic semisolid silicon polymers; dimethyl silicone; methylphenyl silicone; polyhydrocarbons; polyethylene; polyproplylene; polyisobutylene; cellulose lacquer; nitrocellulose lacquer; vinyl resin; polyvinylacetate; phenolformaldehyde resins; urea formaldehyde resins; acrylic ester resins; polymerized ester resins of methyl, ethyl and butyl esters of acrylic; polymerized ester resins of methyl, ethyl and butyl esters of alpha-methylacrylic acids; epoxy resins; melamine resins; drying oils; mineral waxes; petroleum waxes; urethane resins; phenolic resins; epoxide phenolic resins; polyepoxide phenolic resins; novolac epoxy resins; and formaldehyde phenolic resins.

42 . A method of fracturing subterranean formations comprising injecting a fluid comprising a sintered rod-shaped proppant comprising at least about 90% by weight alumina and between about 0.2% by weight and about 4% by weight aluminum titanate.

43 . The method of claim 42 wherein the proppant comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

44 . The proppant of claim 43 wherein the proppant comprises between about 1% by weight and about 2.5% by weight aluminum titanate.

45 . The method of claim 42 wherein the rod-shaped proppant comprises at least about 95% alumina by weight.

46 . The method of claim 42 wherein the rod-shaped proppant comprises less than about 4% SiO 2 by weight.

47 . The method of claim 46 wherein the rod-shaped proppant comprises less than about 2% SiO 2 by weight.

48 . The method of claim 42 wherein the alumina is contributed by both bauxitic and non-bauxitic sources.

49 . The method of claim 48 wherein the bauxitic source contributes at least about 80% of the alumina content by weight of the sintered proppant.

50 . The method of claim 49 wherein the bauxitic source contributes at least about 85% of the alumina content by weight of the sintered proppant.

51 . The method of claim 48 wherein the non-bauxitic source comprises technical grade alumina.

52 . The method of claim 48 wherein the non-bauxitic source contributes at least about 90% of the alumina content by weight of the sintered proppant.

53 . The method of claim 52 wherein the non-bauxitic source contributes at least about 95% of the alumina content by weight of the sintered proppant.

54 . The method of claim 52 wherein the non-bauxitic source comprises technical grade alumina.

55 . The method of claim 52 wherein bauxitic source contributes between 0.1% and 10% of the alumina content by weight of the sintered proppant.

56 . The method of claim 48 wherein the bauxitic source contains a Fe 2 O 3 content of less than 10% by weight of the bauxitic source.

57 . The method of claim 56 wherein the bauxitic source contains a Fe 2 O 3 content of less than 8% by weight of the bauxitic source.

58 . The method of claim 48 wherein the bauxitic and non-bauxitic sources contain a combined TiO 2 content of between about 0.15% and about 3.5% by weight.

59 . The method of claim 58 wherein the bauxitic and non-bauxitic sources contain a combined TiO 2 content of between about 0.3% and about 2.7% by weight.

60 . The method of claim 59 wherein the bauxitic and non-bauxitic sources contain a combined TiO 2 content of between about 0.4% and about 2.3% by weight.

61 . The method of claim 42 wherein the rod-shaped proppant has an average length to width ratio of between about 1.5:1 to about 20:1.

62 . The method of claim 61 wherein the rod-shaped proppant has an average length to width ratio of between about 1.5:1 to about 10:1.

63 . The method of claim 62 wherein the rod-shaped proppant has an average length to width ratio of between about 1.5:1 to about 7:1.

64 . The method of claim 63 wherein the rod-shaped proppant has an average length to width ratio of between about 2:1 to about 4:1.

65 . The method of claim 42 wherein the rod-shaped proppant is substantially cylindrical.

66 . The method of claim 42 wherein the rod-shaped proppant has a substantially circular cross-section.

67 . The method of claim 66 wherein the substantially circular cross-section has an average diameter of between about 0.5 mm and about 2 mm.

68 . The method of claim 67 wherein the substantially circular cross-section has an average diameter of between about 0.5 mm and about 1.5 mm.

69 . The method of claim 42 wherein the rod-shaped proppant has an average length between about 0.1 mm and about 20 mm.

70 . The method of claim 69 wherein the rod-shaped proppant has an average length between about 0.5 mm and about 10 mm.

71 . The method of claim 70 wherein the rod-shaped proppant has an average length between about 1 mm and about 5 mm.

72 . The method of claim 71 wherein the rod-shaped proppant has an average length between about 2 mm and about 4 mm.

73 . The method of claim 42 wherein the rod-shaped proppant has been extruded.

74 . The method of claim 42 wherein the rod-shaped proppant has an apparent specific gravity less than about 3.98.

75 . The method of claim 74 wherein the rod-shaped proppant has an apparent specific gravity between about 3.0 and about 3.98.

76 . The method of claim 75 wherein the rod-shaped proppant has an apparent specific gravity of between about 3.2 and about 3.95.

77 . The method of claim 42 wherein the rod-shaped proppant has a bulk density of between about 1.5 g/cm 3 and about 2.5 g/cm 3 .

78 . The method of claim 77 wherein the rod-shaped proppant has a bulk density of between about 1.7 g/cm 3 and about 2.3 g/cm 3 .

79 . The method of claim 42 wherein less than about 15% of the rod-shaped proppant is crushed at 10,000 psi.

80 . The method of claim 42 wherein less than about 20% of the rod-shaped proppant is crushed at 15,000 psi.

81 . The method of claim 42 wherein the rod-shaped proppant is coated with a natural or synthetic coating.

82 . The method of claim 81 wherein the natural or synthetic coating is selected from the group consisting of natural rubber; elastomers; butyl rubber; polyurethane rubber; starches; petroleum pitch; tar; asphalt; organic semisolid silicon polymers; dimethyl silicone; methylphenyl silicone; polyhydrocarbons; polyethylene; polyproplylene; polyisobutylene; cellulose lacquer; nitrocellulose lacquer; vinyl resin; polyvinylacetate; phenolformaldehyde resins; urea formaldehyde resins; acrylic ester resins; polymerized ester resins of methyl, ethyl and butyl esters of acrylic; polymerized ester resins of methyl, ethyl and butyl esters of alpha-methylacrylic acids; epoxy resins; melamine resins; drying oils; mineral waxes; petroleum waxes; urethane resins; phenolic resins; epoxide phenolic resins; polyepoxide phenolic resins; novolac epoxy resins; and formaldehyde phenolic resins.

83 . A method of making a proppant comprising extruding a mixture of at least about 90% bauxite by weight and between about 0.1% by weight and about 10% by weight of technical grade alumina to form a rod, and sintering the rod to form a rod-shaped proppant.

84 . The method of claim 83 wherein the rod-shaped proppant comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

85 . The method of claim 84 wherein the rod-shaped proppant comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

86 . The method of claim 85 wherein the rod-shaped proppant comprises between about 1% by weight and about 2.5% by weight aluminum titanate.

87 . The method of claim 83 wherein the bauxite contains a SiO 2 content of less than about 4% by weight of the bauxite.

88 . The method of claim 87 wherein the bauxite contains a SiO 2 content of less than about 2% by weight of the bauxite.

89 . The method of claim 83 wherein the bauxite contains a Fe 2 O 3 content of less than 10% by weight of the bauxite.

90 . The method of claim 89 wherein the bauxite contains a Fe 2 O 3 content of less than 8% by weight of the bauxite.

91 . A method of fracturing subterranean formations comprising injecting a fluid containing sintered rod-shaped proppants, wherein the closing pressure breaks a majority of the sintered rod-shaped proppants into at least two smaller rod-shaped proppants.

92 . The method of claim 91 wherein the rod-shaped proppants comprise between about 0.2% by weight and about 4% by weight aluminum titanate.

93 . The method of claim 92 wherein the rod-shaped proppants comprise between about 0.5% by weight and about 3% by weight aluminum titanate.

94 . The method of claim 93 wherein the rod-shaped proppants comprise between about 1% by weight and about 2.5% by weight aluminum titanate.

95 . The method of claim 91 wherein the broken rods are substantially uniform in size.

96 . The method of claim 91 wherein the closing pressure breaks at least 65% of the sintered rods into at least two smaller proppants.

97 . The method of claim 93 wherein the closing pressure breaks at least 80% of the sintered rods into at least two smaller proppants.

98 . The method of claim 91 , wherein the total alumina content of the rods is at least about 90% by weight.

99 . The method of claim 98 , wherein the total alumina content of the rods is at least about 92% by weight.

100 . The method of claim 99 , wherein the total alumina content of the rods is at least about 95% by weight.

101 . The method of claim 100 , wherein the total alumina content of the rods is at least about 96% by weight.

102 . A fracturing fluid comprising a mixture of sintered rods and at least one proppant.

103 . The fracturing fluid of claim 102 wherein the at least one proppant comprises a substantially spherical proppant.

104 . The fracturing fluid of claim 102 wherein the sintered rods comprise between about 0.2% by weight and about 4% by weight aluminum titanate.

105 . The fracturing fluid of claim 104 wherein the sintered rods comprise between about 0.5% by weight and about 3% by weight aluminum titanate.

106 . The fracturing fluid of claim 105 wherein the sintered rods comprise between about 1% by weight and about 2.5% by weight aluminum titanate.

107 . A high strength proppant for fracturing subterranean formations comprising a total alumina content of at least about 90% by weight, where between about 0.1% by weight and about 10% by weight of the alumina is contributed by a mixture containing at least one other oxide, and wherein the proppant is rod-shaped and sintered.

108 . The proppant of claim 107 wherein the at least one other oxide comprises TiO 2 .

109 . The proppant of claim 107 wherein the sintered, rod-shaped proppant comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

110 . The proppant of claim 109 wherein the sintered, rod-shaped proppant comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

111 . The proppant of claim 110 wherein the sintered, rod-shaped proppant comprises between about 1% by weight and about 2.5% by weight aluminum titanate.

112 . A method of making a proppant comprising extruding a mixture of at least about 80% technical grade alumina by weight and between about 0.1% by weight and about 20% by weight of material containing at least one other oxide to form a rod-shaped proppant.

113 . The method of claim 112 wherein the rod-shaped proppant comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

114 . The method of claim 113 wherein the rod-shaped proppant comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

115 . The method of claim 114 wherein the rod-shaped proppant comprises between about 1% by weight and about 2.5% by weight aluminum titanate.

116 . The method of claim 112 further comprising drying the extruded mixture.

117 . The method of claim 116 further comprising sintering the extruded mixture.

118 . The method of claim 112 wherein the at least one other oxide is selected from the group consisting of MgO, Fe 2 O 3 , SiO 2 , ZrO 2 , and TiO 2

119 . The method of claim 112 wherein the material containing at least one other oxide comprises bauxite.

120 . The method of claim 112 wherein the mixture comprises at least 90% technical grade alumina by weight and between about 0.1% by weight and about 10% by weight bauxite.

121 . The method of claim 120 wherein the mixture comprises at least 95% technical grade alumina by weight and between about 0.1% by weight and about 5% by weight bauxite.

122 . A method of fracturing subterranean formations comprising injecting a fluid containing a sintered rod-shaped proppant wherein the sintered proppant comprises a total alumina content of at least about 90% by weight, where between about 0.1% by weight and about 10% by weight of the alumina is contributed by a mixture containing at least one other oxide.

123 . The method of claim 122 wherein the rod-shaped proppant comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

124 . The method of claim 123 wherein the rod-shaped proppant comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

125 . The method of claim 124 wherein the rod-shaped proppant comprises between about 1% by weight and about 2.5% by weight aluminum titanate.

126 . The method of claim 122 wherein the fluid further comprises a second proppant.

127 . The method of claim 126 wherein the second proppant comprises a substantially spherical proppant.

128 . A method of making a proppant comprising a) providing a mixture comprising at least about 90% by weight alumina and between about 0.15% and about 3.5% by weight TiO 2 ; b) extruding the mixture to form rods; and c) sintering the rods.

129 . The method of claim 128 wherein the mixture comprises between about 0.3% by weight and about 2.7% by weight TiO 2 .

130 . The method of claim 129 wherein the mixture comprises between about 0.4% by weight and about 2.3% by weight TiO 2 .

131 . The method of claim 128 further comprising drying the extruded rods.

132 . The method of claim 128 wherein the sintered rods comprise between about 0.2% by weight and about 4% by weight aluminum titanate.

133 . The method of claim 132 wherein the sintered rods comprise between about 0.5% by weight and about 3% by weight aluminum titanate.

134 . The method of claim 133 wherein the sintered rods comprise between about 1% by weight and about 2.5% by weight aluminum titanate.