METHOD OF MANUFACTURING AND USING ROD-SHAPED PROPPANTS AND ANTI-FLOWBACK ADDITIVES

• US 20080053657A1
• Filed: 01/17/2007
• Published: 03/06/2008
• Est. Priority Date: 09/01/2006
• Status: Active Grant

• Current Assignee: US Ceramics, LLC (First Bauxite LLC)
• Original Assignee: Imerys SA (Parjointco N.V.)
• Inventors: Parias, Thomas, Alary, Jean Andre
• Granted Patent: US 8,562,900 B2
• Time in Patent Office: Days
• US Class Current: 166/280.2
• CPC Class Codes: C04B 2235/3232 Titanium oxides or titanates, e.g. rutile or anatase
• CPC Class Codes: C04B 2235/3234 Titanates, not containing zirconia
• CPC Class Codes: C04B 2235/3418 Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint glass constituents C04B2235/36
• CPC Class Codes: C04B 2235/349 Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/5472 Bimodal, multi-modal or multi-fraction
• CPC Class Codes: C04B 2235/80 Phases present in the sintered or melt-cast ceramic products other than the main phase
• CPC Class Codes: C04B 2235/94 Products characterised by their shape
• CPC Class Codes: C04B 35/111 Fine ceramics
• CPC Class Codes: C04B 35/1115 Minute sintered entities, e.g. sintered abrasive grains or shaped particles such as platelets abrasives C09K3/14
• CPC Class Codes: C04B 35/6261 Milling
• CPC Class Codes: C09K 8/62 Compositions for forming crevices or fractures
• 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: E21B 43/26 by forming crevices or fractures
• CPC Class Codes: E21B 43/267 reinforcing fractures by propping

Abstract

A sintered rod-shaped proppant and anti-flowback agent possesses high strength and high conductivity. The sintered rods comprise between about 0.2% by weight and about 4% by weight aluminum titanate. In some embodiments, the sintered rods are made by mixing bauxitic and non-bauxitic sources of alumina that may also contain several so-called impurities (such as TiO₂), extruding the mixture, and sintering it. The starting material may optionally be milled to achieve better compacity and crush resistance in the final sintered rod. A fracturing fluid may comprise the sintered rods alone or in combination with a proppant, preferably a proppant of a different shape.

Claims

1-54. -54. (canceled)

55. A method of making a proppant or anti-flowback additive comprising sintering a rod-shaped article made from a milled composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO₂.

56. The method of claim 55 wherein the milled composition comprises between about 0.3% by weight and about 2.7% by weight TiO₂.

57. The method of claim 56 wherein the milled composition comprises between about 0.4% by weight and about 2.3% by weight TiO₂.

58. The method of claim 55 wherein the sintered article comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

59. The method of claim 58 wherein the sintered article comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

60. The method of claim 59 wherein the sintered article comprises between about 1% by weight and about 2.5% by weight aluminum titanate.

61. The method of claim 55 wherein the milled composition has been jet milled.

62. The method of claim 55 wherein the milled composition has a multi-modal particle size distribution.

63. The method of claim 55 wherein the milled composition has been ball milled.

64. The method of claim 55 wherein the milled composition has a d50 less than 10 microns.

65. The method of claim 64 wherein the milled composition has a d50 less than 5 microns.

66. The method of claim 65 wherein the milled composition has a d50 less than 3 microns.

67. The method of claim 66 wherein the milled composition has a d50 less than 1 .5 microns.

68. The method of claim 55 wherein the milled composition has 95 weight percent of its particles smaller than 30 microns.

69. The method of claim 68 wherein the milled composition has 100% of its particles smaller than 30 microns.

70. The method of claim 55 wherein the sintered article has an average length of less than 15 mm.

71. The method of claim 55 wherein the sintered article has an average length of less than 10 mm.

72. The method of claim 55 wherein the sintered article has an average length of less than 5 mm.

73. The method of claim 55 wherein the sintered article has an average length of about 4 mm.

74. The method of claim 55 wherein the forming of the article comprises extruding the milled composition.

76. The method of claim 55 wherein more than one sintered article is produced.

77. The method of claim 76 wherein from about 7% by weight and about 13% by weight of the sintered articles are crushed at 15,000 psi.

78. The method of claim 77 wherein from about 8% by weight to about 12% by weight of the sintered articles are crushed at 15,000 psi.

79. The method of claim 78 wherein from about 9% by weight to about 11% by weight of the sintered articles are crushed at 15,000 psi.

75. (canceled)

80. A method of making a proppant or anti-flowback additive comprising sintering a rod-shaped article formed from a milled composition, the milled composition comprising 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.

81-106. -106. (canceled)

107. A method of fracturing subterranean formations comprising injecting a fluid containing a sintered rod-shaped article made from a milled composition comprising at least about 90% by weight alumina and between about 0.15% and about 3.5% by weight TiO₂.

108. The method of claim 107 wherein the milled composition comprises between about 0.3% by weight and about 2.7% by weight TiO2.

109. The method of claim 108 wherein the milled composition comprises between about 0.4% by weight and about 2.3% by weight TiO2.

110. The method of claim 107 wherein the sintered article comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

111. The method of claim 110 wherein the sintered article comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

112. The method of claim 111 wherein the sintered article comprises between about 1 % by weight and about 2.5% by weight aluminum titanate.

113. The method of claim 107 wherein the milled composition has been jet milled.

114. The method of claim 107 wherein the milled composition has a multi-modal particle size distribution.

115. The method of claim 107 wherein the milled composition has been ball milled.

116. The method of claim 107 wherein the milled composition has a d50 less than 10 microns.

117. The method of claim 116 wherein the milled composition has a d50 less than 5 microns.

118. The method of claim 117 wherein the milled composition has a d50 less than 3 microns.

119. The method of claim 118 wherein the milled composition has a d50 less than 1.5 microns.

120. The method of claim 107 wherein the milled composition has 95 weight percent of its particles smaller than 30 microns.

121. The method of claim 120 wherein the milled composition has 100% of its particles smaller than 30 microns.

122. The method of claim 107 wherein the sintered article has an average length of less than 15 mm.

123. The method of claim 107 wherein the sintered article has an average length of less than 10 mm.

124. The method of claim 107 wherein the sintered article has an average length of less than 5 mm.

125. The method of claim 107 wherein the sintered article has an average length of about 4 mm.

126. The method of claim 107 wherein more than one sintered article is injected.

127. The method of claim 126 wherein from about 7% by weight and about 13% by weight of the sintered articles are crushed at 15,000 psi.

128. The method of claim 127 wherein from about 8% by weight to about 12% by weight of the sintered articles are crushed at 15,000 psi.

129. The method of claim 128 wherein from about 9% by weight to about 11 % by weight of the sintered articles are crushed at 15,000 psi.

130. A method of fracturing subterranean formations comprising injecting a fluid containing a sintered rod-shaped article formed from a milled composition, the milled composition comprising 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.

131. The method of claim 130 wherein the sintered article comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

132-154. -154. (canceled)

155. A fracturing fluid comprising at least one proppant or anti-flowback additive comprising a sintered rod-shaped article made from a milled composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO₂.

156. The fracturing fluid of claim 155 wherein the milled composition comprises between about 0.3% by weight and about 2.7% by weight TiO₂.

157. The fracturing fluid of claim 156 wherein the milled composition comprises between about 0.4% by weight and about 2.3% by weight TiO₂.

158. The fracturing fluid of claim 155 wherein the sintered article comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

159. The fracturing fluid of claim 158 wherein the sintered article comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

160. The fracturing fluid of claim 159 wherein the sintered article comprises between about 1 % by weight and about 2.5% by weight aluminum titanate.

161. The fracturing fluid of claim 155 wherein the milled composition has been jet milled.

162. The fracturing fluid of claim 155 wherein the milled composition has a multi-modal particle size distribution.

163. The fracturing fluid of claim 155 wherein the milled composition has been ball milled.

164. The fracturing fluid of claim 155 wherein the milled composition has a dSO less than 10 microns.

165. The fracturing fluid of claim 164 wherein the milled composition has a d50 less than 5 microns.

166. The fracturing fluid of claim 165 wherein the milled composition has a d50 less than 3 microns.

167. The fracturing fluid of claim 166 wherein the milled composition has a d50 less than 1.5 microns.

168. The fracturing fluid of claim 155 wherein the milled composition has 95 weight percent of its particles smaller than 30 microns.

169. The fracturing fluid of claim 168 wherein the milled composition has 100% of its particles smaller than 30 microns.

170. The fracturing fluid of claim 155 wherein the sintered article has an average length of less than 15 mm.

171. The fracturing fluid of claim 155 wherein the sintered article has an average length of less than 10 mm.

172. The fracturing fluid of claim 155 wherein the sintered article has an average length of less than 5 mm.

173. The fracturing fluid of claim 155 wherein the sintered article has an average length of about 4 mm.

174. The fracturing fluid of claim 155 wherein the forming of the article comprises extruding the milled composition.

175. The fracturing fluid of claim 155 wherein more than one sintered article is produced.

176. The fracturing fluid of claim 175 wherein from about 7% by weight and about 13% by weight of the sintered articles are crushed at 15,000 psi.

177. The fracturing fluid of claim 176 wherein from about 8% by weight to about 12% by weight of the sintered articles are crushed at 15,000 psi.

178. The fracturing fluid of claim 177 wherein from about 9% by weight to about 11 % by weight of the sintered articles are crushed at 15,000 psi.

179. A fracturing fluid comprising at least one proppant or anti-flowback additive comprising a sintered rod-shaped article formed from a milled composition, the milled composition comprising 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.

180. A proppant or anti-flowback additive comprising a sintered rod-shaped article made from a milled composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO₂.

181. The proppant or anti-flowback additive of claim 180 wherein the milled composition comprises between about 0.3% by weight and about 2.7% by weight TiO₂.

182. The proppant or anti-flowback additive of claim 181 wherein the milled composition comprises between about 0.4% by weight and about 2.3% by weight TiO₂.

183. The proppant or anti-flowback additive of claim 180 wherein the sintered article comprises between about 0.2% by weight and about 4% by weight aluminum titanate.

184. The proppant or anti-flowback additive of claim 183 wherein the sintered article comprises between about 0.5% by weight and about 3% by weight aluminum titanate.

185. The proppant or anti-flowback additive of claim 184 wherein the sintered article comprises between about 1 % by weight and about 2.5% by weight aluminum titanate.

186. The proppant or anti-flowback additive of claim 180 wherein the milled composition has been jet milled.

187. The proppant or anti-flowback additive of claim 180 wherein the milled composition has a multi-modal particle size distribution.

188. The proppant or anti-flowback additive of claim 180 wherein the milled composition has been ball milled.

189. The proppant or anti-flowback additive of claim 180 wherein the milled composition has a d50 less than 10 microns.

190. The proppant or anti-flowback additive of claim 189 wherein the milled composition has a d50 less than 5 microns.

191. The proppant or anti-flowback additive of claim 190 wherein the milled composition has a d50 less than 3 microns.

192. The proppant or anti-flowback additive of claim 191 wherein the milled composition has a d50 less than 1.5 microns.

193. The proppant or anti-flowback additive of claim 180 wherein the milled composition has 95 weight percent of its particles smaller than 30 microns.

194. The proppant or anti-flowback additive of claim 193 wherein the milled composition has 100% of its particles smaller than 30 microns.

195. The proppant or anti-flowback additive of claim 180 wherein the sintered article has an average length of less than 15mm.

196. The proppant or anti-flowback additive of claim 180 wherein the sintered article has an average length of less than 10mm.

197. The proppant or anti-flowback additive of claim 180 wherein the sintered article has an average length of less than 5 mm.

198. The proppant or anti-flowback additive of claim 180 wherein the sintered article has an average length of about 4 mm.

199. The proppant or anti-flowback additive of claim 180 wherein the forming of the article comprises extruding the milled composition.

200. The proppant or anti-flowback additive of claim 180 wherein more than one sintered article is produced.

201. The proppant or anti-flowback additive of claim 200 wherein from about 7% by weight and about 13% by weight of the sintered articles are crushed at 15,000 psi.

202. The proppant or anti-flowback additive of claim 201 wherein from about 8% by weight to about 12% by weight of the sintered articles are crushed at 15,000 psi.

203. The proppant or anti-flowback additive of claim 202 wherein from about 9% by weight to about 11 % by weight of the sintered articles are crushed at 15,000 psi.

204. A proppant or anti-flowback additive comprising a sintered rod-shaped article formed from a milled composition, the milled composition comprising 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.