WO2008026076A2 - Rod-shaped proppants and anti-flowback additives, methods of manufacturing, and methods of use - Google Patents
Rod-shaped proppants and anti-flowback additives, methods of manufacturing, and methods of use Download PDFInfo
- Publication number
- WO2008026076A2 WO2008026076A2 PCT/IB2007/003613 IB2007003613W WO2008026076A2 WO 2008026076 A2 WO2008026076 A2 WO 2008026076A2 IB 2007003613 W IB2007003613 W IB 2007003613W WO 2008026076 A2 WO2008026076 A2 WO 2008026076A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- proppant
- weight
- sintered
- rod
- rods
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 82
- 239000000654 additive Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 61
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000012530 fluid Substances 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims abstract description 19
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 65
- 239000000463 material Substances 0.000 claims description 45
- 238000009826 distribution Methods 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000003921 oil Substances 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000003801 milling Methods 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 15
- 230000005484 gravity Effects 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000005755 formation reaction Methods 0.000 claims description 11
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 8
- 238000010902 jet-milling Methods 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000004922 lacquer Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012184 mineral wax Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920001220 nitrocellulos Polymers 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 239000012169 petroleum derived wax Substances 0.000 claims description 2
- 239000011301 petroleum pitch Substances 0.000 claims description 2
- 235000019381 petroleum wax Nutrition 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000007858 starting material Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 40
- 229910001570 bauxite Inorganic materials 0.000 description 27
- 235000019198 oils Nutrition 0.000 description 22
- 239000003345 natural gas Substances 0.000 description 20
- 230000035699 permeability Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000011800 void material Substances 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- 230000008901 benefit Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 239000008186 active pharmaceutical agent Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002343 natural gas well Substances 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000010187 selection method Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241000758791 Juglandaceae Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- XQCFHQBGMWUEMY-ZPUQHVIOSA-N Nitrovin Chemical compound C=1C=C([N+]([O-])=O)OC=1\C=C\C(=NNC(=N)N)\C=C\C1=CC=C([N+]([O-])=O)O1 XQCFHQBGMWUEMY-ZPUQHVIOSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical class [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004568 cement Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PKIYFBICNICNGJ-UHFFFAOYSA-N monooctyl phthalate Chemical class CCCCCCCCOC(=O)C1=CC=CC=C1C(O)=O PKIYFBICNICNGJ-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/1115—Minute sintered entities, e.g. sintered abrasive grains or shaped particles such as platelets
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
- E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
- C04B2235/5472—Bimodal, multi-modal or multi-fraction
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/94—Products characterised by their shape
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Structural Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Materials For Medical Uses (AREA)
- Powder Metallurgy (AREA)
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.
Description
ROD-SHAPED PROPPANTS AND ANTI-FLOWBACK ADDITIVES, METHODS OF MANUFACTURING, AND METHODS OF USE
Claim of Priority
[001] This International PCT Application claims priority to and the benefit of U.S. non-provisional patent application nos. 11/469,589, filed September 1 , 2006, and 11/624,057, filed January 17, 2007, both of which are incorporated by reference herein in their entireties. Field of the Invention
[002] The present invention relates to methods of making and using proppants for fractured earth having a high compressive strength and simultaneously a good conductivity. It also relates to methods of making and using anti-flowback additives for use in fracturing operations. Background
[003] Naturally occurring deposits containing oil and natural gas have been located throughout the world. Given the porous and permeable nature of the subterranean structure, it is possible to bore into the earth and set up a well where oil and natural gas are pumped out of the deposit. These wells are large, costly structures that are typically fixed at one location. As is often the case, a well may initially be very productive, with the oil and natural gas being pumpable with relative ease. As the oil or natural gas near the well bore is removed from the deposit, other oil and natural gas may flow to the area near the well bore so that it may be pumped as well. However, as a well ages, and sometimes merely as a consequence of the subterranean geology
surrounding the well bore, the more remote oil and natural gas may have difficulty flowing to the well bore, thereby reducing the productivity of the well.
[004] To address this problem and to increase the flow of oil and natural gas to the well bore, companies have employed the well-known technique of fracturing the subterranean area around the well to create more paths for the oil and natural gas to flow toward the well. As described in more detail in the literature, this fracturing is accomplished by hydraulically injecting a fluid at very high pressure into the area surrounding the well bore. This fluid must then be removed from the fracture to the extent possible to ensure that it does not impede the flow of oil or natural gas back to the well bore. Once the fluid is removed, the fractures have a tendency to collapse due to the high compaction pressures experienced at well-depths, which can be more than 20,000 feet. To prevent the fractures from closing, it is well-known to include a propping agent, also known as a proppant, in the fracturing fluid. The goal is to be able to remove as much of the injection fluid as possible while leaving the proppant behind to keep the fractures open. As used in this application, the term "proppant" refers to any non-liquid material that is present in a proppant pack and provides structural support in a propped fracture. "Anti-flowback additive" refers to any material that is present in a proppant pack and reduces the flowback of proppant particles but still allows for production of oil at sufficient rates. The terms "proppant" and "anti-flowback additive" are not necessarily mutually exclusive, so a single particle type may meet both definitions. For example, a particle may provide structural support in a fracture and it may also be shaped to have anti-flowback properties, allowing it to meet both definitions.
[005] Several properties affect the desirability of a proppant. For example, for use in deep wells or wells whose formation forces are high, proppants must be capable of withstanding high compressive forces, often greater than 10,000 pounds per square inch ("psi"). Proppants able to withstand these forces (e.g., up to and greater than 10,000 psi) are referred to as high strength proppants. If forces in a fracture are too high for a given proppant, the proppant will crush and collapse, and then no longer have a sufficient permeability to allow the proper flow of oil or natural gas. Other applications, such as for use in shallower wells, do not demand the same strength proppant, allowing intermediate strength proppants to suffice. These intermediate strength proppants are typically used where the compressive forces are between 5,000 and 10,000 psi. Still other proppants can be used for applications where the compressive forces are low. For example, sand is often used as a proppant at low compressive forces.
[006] In addition to the strength of the proppant, one must consider how the proppant will pack with other proppant particles and the surrounding geological features, as the nature of the packing can impact the flow of the oil and natural gas through the fractures. For example, if the proppant particles become too tightly packed, they may actually inhibit the flow of the oil or natural gas rather than increase it.
[007] The nature of the packing also has an effect on the overall turbulence generated through the fractures. Too much turbulence can increase the flowback of the proppant particles from the fractures toward the well bore. This may undesirably decrease the flow of oil and natural gas, contaminate the well, cause abrasion to the equipment in the well, and increase the production cost as the proppants that flow back toward the well must be removed from the oil and gas.
[008] The useful life of the well may also be shortened if the proppant particles break down. For this reason, proppants have conventionally been designed to minimize breaking. For example, U.S. Patent No. 3,497,008 to Graham et al. discloses a preferred proppant composition of a hard glass that has decreased surface flaws to prevent failure at those flaws. It also discloses that the hard glass should have a good resistance to impact abrasion, which serves to prevent surface flaws from occurring in the first place. These features have conventionally been deemed necessary to avoid breaking, which creates undesirable fines within the fracture.
[009] The shape of the proppant has a significant impact on how it packs with other proppant particles and the surrounding area. Thus, the shape of the proppant can significantly alter the permeability and conductivity of a proppant pack in a fracture. Different shapes of the same material offer different strengths and resistance to closure stress. It is desirable to engineer the shape of the proppant to provide high strength and a packing tendency that will increase the flow of oil or natural gas. The optimum shape may differ for different depths, closure stresses, geologies of the surrounding earth, and materials to be extracted.
[010] The conventional wisdom in the industry is that spherical pellets of uniform size are the most effective proppant body shape to maximize the permeability of the fracture. See, e.g., U.S. Patent No. 6,753,299 to Lunghofer et al. Indeed, the American Petroleum Institute's ("API's") description of the proppant qualification process has a section dedicated to the evaluation of roundness and sphericity as measured on the Krumbein scale. However, other shapes have been suggested in the art. For example, previously-mentioned U.S. Patent No. 3,497,008 to Graham et al. discloses the use of
"particles having linear, parallel, opposite surface elements including cylinders, rods, paralellepipeds, prisms, cubes, plates, and various other solids of both regular and irregular configurations." (CoI. 3, lines 34-37.) According to that patent, the disclosed shape configuration has several advantages when used as a proppant, including increased conductivity over spherical particles (col. 4, lines 29-35), greater load bearing capacity for the same diameter as a spherical particle (col. 4, lines 36-38), a higher resistance to being embedded in the fracture wall (col. 4, lines 45-47), and a lower settling rate (col. 4, lines 58-60).
[011 ] Despite this disclosure of the potential advantages of using rod-like particles for proppants, the industry had not embraced the suggestion. The applicants are not aware of any rod-like particles on the market that are used as proppants or anti- flowback additives. Indeed, more recent patents cast doubt on the effectiveness of using rod-like shapes. For example, U.S. Patent No. 6,059,034 to Rickards et al. discloses the mixing of rod-like fibrous materials with another proppant material to prevent proppant movement and flowback. According to that patent, "in practice this method has proven to have several drawbacks, including reduction in fracture conductivity at effective concentrations of fibrous materials, and an effective life of only about two years due to slight solubility of commonly used fiber materials in brine. In addition, fiber proppant material used in the technique may be incompatible with some common well-treating acids, such as hydrofluoric acid." (CoI. 2, lines 36-43.) Although the rod-like fibrous materials are used in conjunction with another proppant, the patent suggests that rod-like particles in a fracturing fluid are undesirable.
[012] Another property that impacts a proppant's utility is how quickly it settles both in the injection fluid and once it is in the fracture. A proppant that quickly settles may not reach the desired propping location in the fracture, resulting in a low level of proppants in the desired fracture locations, such as high or deep enough in the fracture to maximize the presence of the proppant in the pay zone (i.e., the zone in which oil or natural gas flows back to the well). This can cause reduced efficacy of the fracturing operation. Ideally, a proppant disperses equally throughout all portions of the fracture. Gravity works against this ideal, pulling particles toward the bottom of the fracture. However, proppants with properly engineered densities and shapes may be slow to settle, thereby increasing the functional propped area of the fracture. How quickly a proppant settles is determined in large part by its specific gravity. Engineering the specific gravity of the proppant for various applications is desirable because an optimized specific gravity allows a proppant user to better place the proppant within the fracture.
[013] Yet another attribute to consider in designing a proppant is its acid- tolerance, as acids are often used in oil and natural gas wells and may undesirably alter the properties of the proppant. For example, hydrofluoric acid is commonly used to treat oil wells, making a proppant's resistance to that acid of high importance.
[014] Still another property to consider for a proppant is its surface texture. A surface texture that enhances, or at least does not inhibit, the conductivity of the oil or gas through the fractures is desirable. Smoother surfaces offer certain advantages over rough surfaces, such as reduced tool wear and a better conductivity, but porous
surfaces may still be desirable for some applications where a reduced density may be useful.
[015] All of these properties, some of which can at times conflict with each other, must be weighed in determining the right proppant for a particular situation. Because stimulation of a well through fracturing is by far the most expensive operation over the life of the well, one must also consider the economics. Proppants are typically used in large quantities, making them a large part of the cost.
[016] Attempts have been made to optimize proppants and methods of using them. Suggested materials for proppants include sand, glass beads, ceramic pellets, and portions of walnuts. The preferred material disclosed in previously-mentioned U.S. Patent No. 3,497,008 is a hard glass, but it also mentions that sintered alumina, steatite, and mullite could be used. Conventional belief is that alumina adds strength to a proppant, so many early proppants were made of high-alumina materials, such as bauxite. The strength of these high-alumina materials is believed to be due to the mechanical properties of the dense ceramic materials therein. See, e.g., U.S. Patent Nos. 4,068,718 and 4,427,068, both of which disclose proppants made with bauxite.
[017] Bauxite is a natural mineral comprising various amounts of four primary oxides: alumina (AI2O3, typically from about 80% to about 90% by weight, but as low as 76% by weight), silica (SiO2, typically from about 1 % to about 12% by weight), iron oxide (Fe2O3, typically from about 1 % to about 15% by weight), and titania (TiO2, typically from about 1 % to about 5% by weight). After calcining or sintering, bauxite is known to have a higher toughness but a lower hardness than technical grade alumina- based ceramics. Since toughness is a primary mechanical characteristic to consider in
improving the crush resistance or compressive strength of ceramics, bauxite is of interest for use in proppants. The microstructure of bauxite is characterized primarily by three phases: 1 ) a matrix of fine alumina crystal; 2) a titania phase where titania is complexed with alumina to form aluminum titanate (AI2TiO5); and 3) a mullite phase (3AI2O3, 2SiO2). For the first two phases a partial substitution of aluminum by iron atoms is possible. To achieve good mechanical characteristics as a proppant, bauxite with lower levels of silica and iron oxide are preferred.
[018] For example, previously-mentioned U.S. Patent No. 4,427,068 discloses a spherical proppant comprising a clay containing silica that adds a glassy phase to the proppant, thereby weakening the proppant. Furthermore, the silica of that patent is so- called "free" silica. In general, high amounts of silica reduce the strength of the final proppant. In particular, it is believed that proppants containing more than 2% silica by weight will have reduced strength over those with lower silica contents. Other so-called impurities are also believed to reduce the strength of the proppant.
[019] Early high strength proppants were made using tabular alumina which was a relatively expensive component. For this reason, the industry shifted from using tabular alumina to other alumina sources, such as bauxite. By the late 1970's, the development focus in the industry shifted from high strength proppants to intermediate or lower strength, lower density proppants that were easier to transport and use, and were less expensive. Over the next 20 years, the industry focused on commercialization of lower density proppants and they became commonly used. The primary method of reducing the density of proppants is to replace at least a portion of the higher density alumina with lower density silica. According to U.S. Patent No.
6,753,299, "the original bauxite based proppants of the early 1970's contained >80% alumina (Cooke). Subsequent generations of proppants contained an alumina content of >70% (Fitzgibbons), 40% to 60% (Lunghofer), and later 30% to <40% (Rumpf, Fitzgibbons)." Thus, as to both product development and proppant use, there was a retreat in the industry from proppants manufactured from high-alumina materials such as bauxite.
[020] Today, as resources become more scarce, the search for oil and gas involves penetration into deeper geological formations, and the recovery of the raw materials becomes increasingly difficult. Therefore, there is a need for proppants that have an excellent conductivity and permeability even under extreme conditions. There is also need for improved anti-flowback additives that will reduce the cost of production and increase the useful life of the well. Summary of the Invention
[021] A method is provided for making a proppant or anti-flowback additive. The method comprises providing a composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO2; forming at least one rod from the composition; and sintering the at least one rod.
[022] Another method for making a proppant or anti-flowback additive comprises sintering a rod-shaped article made from a composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO2.
[023] A method is provided for fracturing subterranean formations. The method comprises injecting a fluid containing a sintered rod-shaped article made from a
composition, where the composition comprises at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO2.
[024] Still another method of fracturing subterranean formations is provided 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.
[025] According to another embodiment consistent with the present invention, a high strength sintered rod-shaped proppant is provided for fracturing subterranean formations comprising at least about 80% by weight alumina and between about 0.2% by weight and about 4% by weight aluminum titanate.
[026] The foregoing background and summary are not intended to be comprehensive, but instead serve to help artisans of ordinary skill understand the following implementations consistent with the invention set forth in the appended claims. In addition, the foregoing background and summary are not intended to provide any limitations on the claimed invention. Description of the Invention
[027] Reference will now be made in detail to embodiments of the present invention. A high strength proppant and anti-flowback additive having a rod shape is found to achieve superior conductivity and other benefits when used in hydraulic fracturing of subterranean formations surrounding oil and/or gas wells under relatively high closing pressures.
[028] A high strength proppant in accordance with one embodiment of the present invention is a solid rod-shaped particle prepared by sintering an alumina-
containing material, such as, for example, technical grade alumina, bauxite, or any other suitable combination of oxides thereof. The rod-shaped particle may have a solid trunk bounded by two substantially parallel planes. In one preferred embodiment of the present invention, the two substantially parallel planes may be substantially circular, thereby creating a cylindrical trunk. Other suitable shapes may be also be used as the bounding planes. It is preferable that the bounding plane shapes have a minimum number of angles, such as circles or ovals or other symmetrical or asymmetrical shapes with rounded edges, such as egg curves, because angular particles tend to pack more tightly together and concentrate the pressure on the contact points between the particles because of their sharp edges. This increased pressure can lead to an increased likelihood that the proppants will undesirably break into fine particles. Angular shapes, such as triangles, squares, rectangles, etc., where one or more of the corners is rounded may also be used as the bounding planes without departing from the spirit of the present invention. The rod bounded by these different shapes may take on trunks of different shapes, for example, in the shape of a triangular prism, without departing from the spirit of the present invention.
[029] The sintered rod is found to exhibit superior hardness and toughness. As known in the art, increased alumina (AI2O3) content in the sintered product results in increased hardness and toughness. Sintered rods consistent with one embodiment of the present invention may have a high alumina content, for example, greater than about 80% alumina by weight. In some embodiments, the alumina content may be increased to greater than about 90% by weight. It may further be preferable that the alumina
content be greater than about 92% by weight, with the optimum hardness and toughness being achieved between about 92% and about 96% alumina by weight.
[030] It has also been found that the presence of aluminum titanate (AI2TiO5) in the sintered rod results in improved hardness and toughness. The sintered rod may contain between about 0.2% and about 4% aluminum titanate, preferably between about 0.5% and about 3%, and most preferably between about 1 % and about 2.5%. In one embodiment, the aluminum titanate is formed during sintering when the pre- sintered material includes a small percentage Of TiO2. The TiO2 may be contributed by non-bauxitic sources or, preferably, bauxite. In one embodiment, the pre-sintered mixture may comprise by weight between about 0.15% and about 3.5% TiO2, preferably between about 0.3% and about 2.7% TiO2, and most preferably between about 0.4% and about 2.3% TiO2. During the sintering process, which is preferably conducted at a temperature from 13000C to 15000C, the TiO2 forms a complex with the alumina to form the aluminum titanate phase.
[031] The sintered rod may also be formulated to restrict its SiO2 content to a specific low level (e.g., less than about 4% by weight, and preferably no more than about 2% by weight). When the level is silica is greater than 4%, silica bridges the alumina crystals during the sintering step and makes the ceramic material more fragile and breakable. By limiting the SiO2 content of the proppant, the sintered rod formulation ensures optimum strength from a high percentage of alumina (e.g., greater than 92%) reinforced by the formation of aluminum titanate while at the same time minimizing the weakening effects of SiO2.
[032] Iron oxide, commonly found in bauxite, can also weaken the proppant. The sintered rod should contain no more than 10% by weight iron oxide. Where a substantial portion of the mixture (e.g., over 80% by weight) to be sintered is compromised of an alumina material that contains iron oxide (e.g., bauxite) that material should comprise iron oxide in amounts not to exceed about 10% by weight, and preferably no more than 8% by weight. This will help ensure that the sintered rod has superior strength throughout while still being able to break into substantially uniform pieces under high closing pressure as will be further discussed below. It may also limit the production of excessive undesirable fines at high closing pressures.
[033] The high percentage of alumina in the sintered rods may come from a number of bauxitic and non-bauxitic sources. For example, a high-quality bauxite containing a high level of alumina (e.g., 85% or more) may be used as the primary source of alumina for the final composition. In addition to containing alumina, bauxite typically also contains additional oxides, such as SiO2, TiO2, Fe2O3, ZrO2, MgO. As mentioned above, excessive amounts of certain of these oxides can weaken the sintered rod. Only bauxite that will not contribute excessive amounts of undesirable impurities to the mixture, based upon the amount of bauxite present in the mixture, should be used. Suitable bauxite may come from, for example, the Weipa mine in Australia, or mines in Brazil, China, or Guinea. Since bauxite may not have a high enough alumina content to achieve the desired high alumina content in the final product, a non-bauxitic source of alumina, such as "technical grade alumina" or "pure alumina" may be used to supplement the alumina in the bauxite. Technical grade alumina contains, for example, 98%-99% alumina with only a small amount of impurities.
[034] In an alternative method of making a suitable sintered rod, a non-bauxitic source such as technical grade alumina may be used as the primary source for the alumina contained in the final sintered rod. A relatively small percentage of bauxite may be used as a supplemental source of alumina, and may contribute a beneficial amount of TiO2 to provide the desired aluminum titanate in the final sintered rod. Because the bauxite is used in smaller amounts in this embodiment, a bauxite containing higher levels of impurities may be used, so long as the overall amount of the impurities is relatively low in the final sintered product.
[035] The alumina-containing material (e.g., bauxite) may optionally be sized using various milling or grinding techniques, including both attrition grinding and autogenous grinding (i.e., grinding without a grinding medium), and may be ground by either a dry or wet grinding process. The grinding may be accomplished in a single step or may involve multiple grinding steps.
[036] Proper sizing prior to forming the sintered rods can increase the compacity of the feed and ultimately result in a stronger proppant or anti-flowback additive. In one embodiment, a jet mill may be used to prepare a first batch of particles having a first particle size distribution. In a jet mill, the particles are introduced into a stream of fluid, generally air, which circulates the particles and induces collisions between the particles. Using known techniques, the forces in the jet mill can alter the particle size distribution of the particles to achieve a desired distribution. For example, one may vary the type of fluid used in the mill, the shape of the milling chamber, the pressure inside the mill, the number and configuration of fluid nozzles on the mill, and whether there is a classifier that removes particles of a desired size while leaving others in the mill for additional
milling. The exact configuration will vary based on the properties of the feed material and the desired output properties. The appropriate configuration for a given application can be readily determined by those skilled in the art.
[037] After the first batch of particles having the first particle size distribution is prepared, a second batch of particles may be jet milled to a second particle size distribution. The first and second batch particle size distributions and milling conditions, and the conditions under which they are combined, are selected to form the desired final particle size distribution of the combined batches prior to sintering. Using this technique, a bi-modal particle size distribution may be obtained. The advantage of preparing a bi-modal feed is that it may contain additional fine particles to pack between the coarser particles, leading to increased compacity and density prior to sintering. Those skilled in the art will appreciate that one need not stop at two batches with different particle size distributions, but could combine three or more batches to achieve multi-modal particle size distributions prior to sintering. The batches of particles can be combined using any mixing technique known in the art for mixing dry powders, such as employing intensive mixers (e.g., Eirich mixers), which can quickly produce a homogeneous powder blend. Using this approach, it has surprisingly been discovered that the resultant sintered rod achieves better compacity and crush resistance.
[038] In another embodiment, the alumina-containing material may optionally be sized in a ball mill. Similar to jet milling multiple batches to different particle sizes and mixing them, ball milling may result in a multi-modal particle size distribution, which can improve the compacity of the powder. However, in contrast to a jet milling process, acceptable results may be achieved in a single ball-milled batch of particles (i.e., there
is no requirement to prepare multiple batches and mix them). Of course, there is no technical reason to avoid combining multiple ball-milled batches, and one embodiment consistent with the present invention involves ball milling multiple batches and mixing them to form a powder with a desired multi-modal particle size distribution. In another embodiment, batches with two different particle size distributions can be simultaneously milled in the ball mill, resulting in a powder with a multi-modal particle size distribution. [039] Regarding the mechanics of the ball milling process, a ball mill contains a chamber in which the alumina-containing material and a collection of balls collide with each other to alter the material's particle size. The chamber and balls are typically made of metal, such as aluminum or steel. The appropriate configuration for the ball mill (e.g., the size and weight of the metal balls, the milling time, the rotation speed, etc.) can be readily determined by those skilled in the art. The ball milling process can be either a batch process or a continuous process. Various additives may also be used to increase the yields or efficiency of the milling. The additives may act as surface tension modifiers, which may increase the dispersion of fine particles and reduce the chance that the particles adhere to the walls and ball media. Suitable additives are known to those skilled in the art, and include aqueous solutions of modified hydroxylated amines and cement admixtures. In one embodiment, the ball mill is configured with an air classifier to reintroduce coarser particles back into the mill for a more accurate and controlled milling process. Like the jet milling embodiment described above, ball milling has surprisingly been discovered to result in a proppant or anti-flowback additive with improved compacity and crush resistance.
[040] While various particle sizes and size distributions may be useful in preparing proppants and anti-flowback additives, the pre-milled alumina-containing material may have at least 95% of its particles smaller than 500 microns as measured by sieving or a Microtrac particle size analyzer, and may have all of its particles smaller than 500 microns. After milling, in certain embodiments the material has a d50 of less than 10 microns, and may have a d50 of less than 5 microns, less than 3 microns, or even less than 1.5 microns. In one embodiment, the powder has a d50 from 1.5 microns to 2 microns, and ratio of the d90 to the di O from 4 to 8. The d10, d50, and d90 may be measured using a laser microsizer, such as the Malvern Mastersizer 2000. The milled material may also have substantially all of its particles smaller than 30 microns. A broad particle size distribution is preferred to a narrow one, as it is believed that the broader distribution results in an increase of the compacity of the material and the strength of the final sintered rod.
[041] The sintered rod in accordance with one embodiment of the present invention may be prepared by first mixing the desired alumina-containing materials with at least one binding agent and/or solvent. The binding agent and/or solvent is one of those well known in the industry. Some possible binding agents include, for example, methyl cellulose, polyvinyl butyrals, emulsified acrylates, polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylics, starch, silicon binders, polyacrylates, silicates, polyethylene imine, lignosulfonates, alginates, etc. Some possible solvents may include, for example, water, alcohols, ketones, aromatic compounds, hydrocarbons, etc. Other additives well known in the industry may be added as well. For example, lubricants may be added, such as ammonium stearates, wax emulsions, elieic acid, Manhattan fish oil,
stearic acid, wax, palmitic acid, linoleic acid, myristic acid, and lauric acid. Plasticizers may also be used, including polyethylene glycol, octyl phthalates, and ethylene glycol. The mixture may then be extruded, for example, through a die, to form a rod having a cross-section of a desired shape, such as a substantially circular shape or any other suitable shape. The process of extrusion may be performed using extrusion methods known in the industry. For example, the extrusion process may be a batch process, such as by forming the rods using a piston press, or may be a continuous process using an extruder containing one or more screws. Loomis manufactures a piston press that may be used to batch produce the rods, while Dorst and ECT both make extruders that contain one or more screws that may be used in the continuous extrusion production method. Other suitable equipment and manufacturers will be readily ascertainable to those of skill in the art.
[042] The extruded rod is then dried, for example, at about 50 degrees Celsius or any other effective temperature, and reduced to the desired rod length, as needed. Any suitable drying process known to the industry may be used. For example, the rods may be dried using electric or gas driers. In some embodiments, the drying process may be performed by microwave, with a continuous drying process being preferred. The reduction to the desired length may be achieved through cutting using, for example, a rotating blade, a cross cutter, a strand cutter, a longitudinal cutter, a cutting mill, a beating mill, a roller, or any other suitable reducing mechanism. In one embodiment of the invention the reduction to the desired length occurs as a result of the drying process, forming a mixture of rods having a broad length distribution, and no cutting step is required. The length reduction occurs during the drying as a result of the
mechanical properties of the extruded rod. In this embodiment, the manufacturing process is simplified and lower in cost as waste levels are reduced, cutting equipment need not be purchased nor maintained, and less energy will be consumed in the process. In another embodiment, where a narrow length distribution is desired, the rods having the desired length are obtained by any one of various selection methods known to those skilled in the art, including visual or mechanical inspection, or sieving. However, classical sieving methods tend to break the weaker rods. This is not necessarily a disadvantage, as only the stronger rods are selected by sieving. The appropriate selection method will need to be determined on a case-by-case basis, and will depend on the goal of the selection process.
[043] The formed rod is then sintered at about 1 ,300 degrees Celsius to about 1 ,700 degrees Celsius to form the sintered rod suitable for use as a proppant or anti- flowback additive. In some embodiments, the sintering temperature is preferably between about 1 ,400 degrees Celsius to about 1 ,600 degrees Celsius. The sintering equipment may be any suitable equipment known in the industry, including, for example, rotary or vertical furnaces, or tunnel or pendular sintering equipment.
[044] The sintered rods may optionally be coated with one or more coatings. Applying such a coating can provide various advantages, including the ability to control the dispersion of fines that may be generated when the rods break under injection or closure pressures. Many coatings have been suggested in the art, with U. S Patent No. 5,420,174 to Dewprashad providing the following non-exhaustive list of natural and synthetic coatings: "natural rubber, elastomers such as butyl rubber, and polyurethane rubber, various starches, petroleum pitch, tar, and asphalt, organic semisolid silicon
polymers such as dimethyl and methylphenyl silicones, polyhydrocarbons such as polyethylene, polyproplylene, polyisobutylene, cellulose and nitrocellulose lacquers, vinyl resins such as polyvinylacetate, phenolformaldehyde resins, urea formaldehyde resins, acrylic ester resins such as polymerized esters resins of methyl, ethyl and butyl esters of acrylic and alpha-methylacrylic acids, epoxy resins, melamine resins, drying oils, mineral and petroleum waxes." Additional coatings include urethane resins, phenolic resins, epoxide phenolic resins, polyepoxide phenolic resins, novolac epoxy resins, and formaldehyde phenolic resins. One or more of these coatings can be applied to the sintered rods using any known method, including both batch and on-the- fly mixing.
[045] In one embodiment of the present invention, the sintered rod has parallel bounding planes that are substantially circular, where the substantially circular planes have an average diameter of between about 0.5 mm and about 2 mm. In some embodiments, the preferred diameters may be between about 0.5 mm and about 1.5 mm. Sintered rods having a length of up to about 20 mm, preferably up to 10 mm, may be suitable for use as proppants or anti-flowback additives in accordance with embodiments of the present invention. In some embodiments, the preferred rod length may be between about 1 mm and about 5 mm, or more preferably between about 2 mm and about 4 mm.
[046] In some embodiments, the diameter of the substantially circular planes may correspond with diameters specified in the API standard for spherical proppants. In one embodiment, the preferred rod length may be the naturally sustainable length limited by the drying process, for example, the length at which the rod will not break
during the drying process. As discussed above, this approach can provide a useful proppant or anti-flowback additive without the step of cutting it to a particular length, thereby simplifying and lowering the cost of the manufacturing process, reducing waste produced during the cutting step, simplifying logistics due to the reduced need to produce, store, package, and ship proppants and anti-flowback additives of different sizes, and simplifying the planning of the fracturing job as there is no need to determine the needed length of the proppant or anti-flowback additive for a particular job.
[047] Depending on the requirements for a particular fracture or proppant pack, the fracturing fluid may include either a narrow or broad length distribution of the rods before closure. To create a narrow length distribution, rods may be cut as described above to ensure a more uniform length distribution. More varied lengths may exist in a fracturing fluid with a broader length distribution before closure. While prior to closure a collection of sintered rods with a broad length distribution may have different physical properties from a collection having a narrow length distribution, after closure both collections of sintered rods may behave similarly in the fracture. This is primarily because the sintered rods in accordance with an embodiment of the present invention have the unique ability to break into substantially uniform rods of smaller sizes under a closing pressure. This unique breaking property is discussed in more detail below. However, as a brief example, in a pack formed from a fracturing fluid of sintered rods having varied lengths, the longer rods will break first under lower closing pressure (e.g., 2,000 psi) into intermediate and smaller rods, which may break again into smaller pieces at higher closing pressure (e.g., 5,000 psi). In this way, the pack made from fracturing fluid of varied length sintered rods may ultimately achieve substantially
uniform lengths at certain higher closing pressures. As used herein, rods having "substantially uniform length" are rods that have the same length, plus or minus 20%. Preferably, these rods will have the same length, plus or minus 10%.
[048] Although the sintered rods will break to the appropriate size in the fracture, it has been discovered that shorter sintered rods with a narrow length distribution may perform better than longer rods that break to the same size. Thus, for some fracturing applications it may be desirable to determine an optimum length and prepare the sintered rod accordingly. Achieving the desired length distribution may be accomplished by a) cutting the material after extrusion, such as by using a rotating knife next to the extrusion die; b) cutting the material before or after drying, such as by using a combination of mesh and knives, with the mesh being placed after the knives to sieve the rods using known sieving techniques, including the use of bouncing rubber balls on top of the mesh to aid in sieving; c) cutting the material after sintering, such as by using an Eirich mixer or a ball mill; or d) any of the other various methods for sizing known to those skilled in the art.
[049] A sintered rod having the above dimensions may have a length to width ratio (this term is also intended to encompass the length to diameter ratio, if the rod has a circular cross-section) of about 1.5:1 to about 20:1. In some embodiments, it may be desirable that the length to width ratio be between about 1.5:1 to about 10:1 , more preferably between about 1.5:1 and about 7:1. It may be further preferable to restrict the length to width ratio from about 2:1 to about 4:1 in some embodiments. It is desirable that the sintered rod have a length to width ratio of greater than 1 :1 because the elongated shape introduces more disorder into the proppant pack, which increases
void spaces between the proppants and in turn increases the conductivity of the proppant pack. As an example, an experiment was conducted in which equal volumes of a spherical proppant of the prior art and a rod-shaped proppant of the present invention, each with a bulk density of about 2.01 g/cm3 were placed in separate Erlenmeyer flasks. Distilled water was introduced into each flask until the proppants were submerged in water. The water volume needed to penetrate the voids was then measured. The volume of water poured into the flask represents the void volume. For the spherical proppant, 5.8 mis of water was necessary to fill the void volume. For the rod-shaped proppant, 10.7 mis of water was necessary — almost double that of the spherical proppant. This comparison demonstrates that for the same volume of proppant, the rod-shaped proppant may have significantly more void volume than the same volume of a spherical proppant.
[050] In another experiment, approximately 32.9 g each of two spherical proppants and one rod-shaped proppant consistent with the present invention were placed in separate Erlenmeyer flasks each filled with 50 mis of distilled water. The rod- shaped proppant had a broad length distribution and an average width or diameter of between about 1.1 mm and about 1.3 mm. All three of the proppants had a bulk density between about 2.00 g/cm3 and about 2.01 g/cm3. The flasks were shaken slightly, but only to the extent necessary to provide a level surface on the top of the proppant. The volume level of the proppants was then measured, as was the level of the water. From this information, the void volume within the proppant was calculated using the following equations:
Vvoid = Vproppants " ΔV|ιqUιd Where
ΔV|ιqUιd — V|ιqUιd fmal " V hqUιd initial
[051] The void volumes of the two spherical proppants were measured to be about 33% and about 38%, while the void volume of the rod-shaped proppant was found to be about 50%. This further demonstrates that for the same mass of proppant, a rod-shaped proppant consistent with the present invention may exhibit more void volume in the proppant pack, leading to a larger space for oil or natural gas to flow to the well bore. The flasks were then shaken and tapped for approximately 2 minutes with the goal of packing the proppant particles more tightly. The same levels were measured, and the void volume in the spherical proppants did not change in any significant manner. As expected, the void volume in the rod-shaped proppant decreased somewhat, but it still contained a void volume of about 44%. This packed void volume was still higher than that of either of the spherical proppants. Table 1 below provides the data from these experiments.
TABLE 1
[052] The desirable properties of sintered rods made in accordance with the present invention are believed to be associated, at least in part, with their relatively high apparent specific gravity. While "specific gravity" is known in the art to refer to the weight per unit volume of a material as compared to the weight per unit volume of water at a given temperature, "apparent specific gravity" as used in this application refers to the weight per unit volume of a material including only the material itself and its internal porosity as compared to the weight per unit volume of water. Thus, in the apparent specific gravity computation first the weight of the material being measured is determined. Then the volume of the material, including only the volume of the material and its internal pores, is determined. For some materials, this step is easily accomplished by placing the material in water and measuring the volume of the displaced water. Indeed, under certain circumstances water may appropriately be used for applications that compare one proppant to another, such as in the void volume experiments described above. For proppants of this type, however, water may permeate and fill in the interior pores, giving inaccurate absolute results such as those desired when computing apparent specific gravity. Consequently, it is necessary to measure the displacement in mercury or some similar fluid that will not permeate the material and fill its internal pores. The weight per unit volume measured in this manner is then compared to the weight per unit volume of water at a given temperature. The specific temperature used in accordance with this application is room temperature, or about 25 degrees Celsius.
[053] A sintered rod prepared as described above may have an apparent specific gravity of up to about 3.98. In some embodiments, it may be desirable that the
apparent specific gravity of the sintered rods be between about 3.0 and about 3.98. It may be further preferable that the apparent specific gravity be between about 3.2 and about 3.95 in some embodiments. The specific range chosen may be based on a variety of factors including, for example, the intended use, which may involve considerations such as fracture depth, the type of carrier fluid, etc. The sintered rod may also have a bulk density of about 1.5 g/cm3 to about 2.5 g/cm3. In some embodiments, the bulk density may preferably be between about 1.7 g/cm3 to about 2.3 g/cm3. Bulk density as used in this application and understood within the art refers to the mass of a particular volume of sintered rods divided by the volume occupied by the sintered rods where the mass has been compacted. This is sometimes referred to as "packed" or "tapped" bulk density. The measurement method of the "packed" or "tapped" bulk density is that set forth by the Federation of European Producers of Abrasives (FEPA) as standard number 44-D. The volume used for the calculation of bulk density includes both the space between the sintered rods and the pore spaces (both interior and exterior) of the sintered rods.
[054] It is known within the art that proppants having a high apparent specific gravity and high alumina content exhibit superior crush resistance. Crush resistance as used in this application is measured according to procedures promulgated by the API for measuring proppant crush. Specifically, a certain volume of the sintered rods of a particular dimension range (i.e., 1.1 mm - 1.3 mm in diameter and 2 mm - 14 mm in length) is loaded into a crush cell with a floating piston. For a desired stress level, the piston presses onto the sintered rods at the required stress level (e.g., 20,000 psi) for a set period of time (e.g., two minutes). The weight percentage of crushed materials, for
example, gathered by sieving the fines through a sieve of a desired size (e.g., less than about 1 mm), is measured.
[055] Results of tests using API crush resistance procedures indicate the sintered rods consistent with the present invention exhibit high crush resistance up to 20,000 psi. At 10,000 psi only between about 5% by weight and about 9% by weight were crushed. At 15,000 psi between about 9% by weight and about 19% by weight were crushed. When the optional milling step is used, it is believed that in some embodiments only about 7% to about 15% of the particles may be crushed at 15,000 psi, in other embodiments only about 7% to about 13% may be crushed, still others may have only about 8% to about 12% crushed, and in other embodiments only about 9% to about 11 % of the particles may be crushed, with all percentages being given by weight. For example, in a sample of sintered rods consistent with one embodiment of the invention, only about 12% by weight were crushed at 15,000 psi. The variation in the crush resistance at a given pressure is due, at least in part, to variations in the lengths of the rods, the diameters of the rods, the feed material, any impurities in the feed, the sintering temperature, and the sintering time.
[056] Because crush resistance alone is generally insufficient to illustrate the potential conductivity that is essential to a proppant, a conductivity test according to the API Recommended Practice 61 for measuring conductivity was also conducted. In a particular test, a quantity of sintered rods in accordance with one embodiment of the present invention was placed and leveled in a test cell between Ohio sandstone rocks. Ohio sandstone has a static elastic modulus of approximately 4 million psi and a permeability of 0.1 mD. Heated steel plates provided the desired temperature simulation
for the test. A thermocouple was inserted into the middle portion of the rod pack to record the temperature. A servo-controlled loading ram provided a closing pressure on the proppant between the Ohio sandstone rocks. The test cell was initially set at 8O0F and 1 ,000 psi. The cell was then heated to 25O0F and held for 4 hours before the stress was increased to 2,000 psi over 10 minutes. After 50 hours at 2,000 psi, measurements were made, and then the stress level was raised to 3,000 psi. The same procedures were applied and subsequent measurements were made at 5,000 psi, 7,500 psi, and 10,000 psi over a total of 254 hours.
[057] Measurements were taken of the pressure drop in the middle of the sintered rod pack to enable calculation of the permeability at a particular stress condition according to Darcy's Law. Specifically, permeability is part of the proportionality constant in Darcy's Law, which relates flow rate and fluid physical properties (e.g., viscosity) to the stress level applied to a pack of sintered rods. Permeability is a property specifically relating to a pack of sintered rods, not the fluid. Conductivity, on the other hand, describes the ease with which fluid moves through pore spaces in a pack of sintered rods. Conductivity depends on the intrinsic permeability of a sintered rod pack as well as the degree of saturation. In particular, conductivity expresses the amount of water that will flow through a cross-sectional area of a sintered rod pack under the desired stress level.
[058] Specifically, to measure conductivity, a 70 mbar full range differential pressure transducer was started. When the differential pressure appeared to be stable, a tared volumetric cylinder was placed at the outlet and a stopwatch was started. The output from the differential pressure transducer was fed to a data collector, which
recorded the output every second. Fluid was collected for 5 to 10 minutes and then the flow rate was determined by weighing the collected effluent. The mean value of the differential pressure was retrieved from a multi-meter, as were the peak high and low values. If the difference between the high and low values was greater than 5% of the mean, the data was disregarded. Temperature was recorded at the start and end of the flow test period. Viscosity of the fluid was obtained using the measured temperature and viscosity tables. At least three permeability determinations were made at each stage using Darcy's Law. The standard deviation of the determined permeabilities had to be less than 1 % of the mean value before the test was accepted.
[059] The following table summarizes the results of the above conductivity test conducted on sintered rods consistent with the present invention, as well as high strength and intermediate strength spherical particles. The rods were between about 0.9 mm and 1.1 mm in diameter, and had a narrow length distribution centered at 10 mm.
TABLE 2 - Conductivity
All measures except pressure are in mD-ft.
[060] When the optional milling step is employed, the conductivity of the rods increases to about 5200 mD-ft at 10,000 psi and about 3600 mD-ft at 12,500 psi. The surprisingly superior conductivity and permeability of the rod-shaped proppants at high closure pressure as compared to spherical proppants that are currently being used in the industry was found to be largely attributable to the proppant's unique rod shape and its unexpected breaking behavior under closing pressure. Particularly, unlike a sphere, which has a single load bearing point at which the closing pressure converges, often leading to crushing, a rod has a much broader area of contact in a multi-layered pack under pressure, allowing it to distribute the pressure more evenly and thereby reducing crushing and embedment at comparable closing pressures.
[061] It is known that crushing of the current spherical proppants leads to the creation of fines. Essentially the spheres break under pressure into very minute, dust- like pieces that have a tendency to create densely packed fine layers that significantly reduce both permeability and conductivity. Additionally, the fines tend to have sharp edges, which when in contact with surrounding intact spheres, concentrate the compression forces onto other spheres at the sharp contact points and contribute to the destruction of the surrounding spheres in the proppant pack.
[062] The sintered rods, besides being more resistant to crushing under comparable closing pressures due to their unique shape, also exhibit the surprising property of being able to break into generally uniform sized smaller rods when breakage does occur. This behavior is in contrast to the failure of spherical particles, described above, which typically disintegrate when they fail and create a large amount of fines. Instead of creating dust-like fines, the rod-shaped proppants break into smaller rod-
shaped proppants. The breaking behavior of the sintered rods is attributable, at least in part, to the specific composition of a large amount of alumina with a small amount of other synergistic oxides in the sintered rod formulation. For example, a small percentage of Tiθ2 in the sintered rod composition, preferably contributed by bauxite, allows for the formation of aluminum titanate (AI2TiO5) during the sintering process, which provides extra strength to the sintered rod proppant or anti-flowback additive. In one embodiment, the sintered rod may contain between about 0.2% and about 4% aluminum titanate by weight, preferably between about 0.5% and about 3% by weight, and more preferably between about 1 % and about 2.5% by weight. In some embodiments the bauxite before sintering may comprise by weight between about 0.5% and about 4% TiO2, preferably between about 1 % and about 3% TiO2, and more preferably between about 2% and about 3% TiO2.
[063] The rods also maintain their unique rod shape as they break into smaller rods, thereby maintaining their efficacy as a proppant. In one experiment, two collections of 100 g of sintered rods, one having a broad length distribution and the other having a narrow one, were tested according to API Procedure 60 at 22,000 psi. As used in this application, a narrow length distribution is one where at least about 60% of the rods have lengths within about 1 mm of the mean. All other distributions are considered broad. After the experiment, the sintered rods of both sizes were examined and found to have reached a very narrow length distribution centered around 4 mm. Even at this high pressure numerous rods were still intact.
[064] The manner in which the sintered rods break has a number of advantages. The smaller rods do not behave like fines that settle into dense packs
between still-intact spherical proppants. Thus, there is little to no reduction in conductivity or destruction of neighboring proppants as occurs with fines in spherical proppant packs. It is also believed that the smaller rod pieces that result from breaking of a larger sintered rod exhibit the same or similar beneficial properties as the larger sintered rod. The smaller rods remain superior in their load carrying capability and resistance to embedment. Moreover, to the extent fines are generated, they are believed to be less destructive to the proppant pack than the fines generated when other proppants, such as spherical proppants, break down. This further maintains permeability and conductivity. In view of these advantages, a pack of sintered rods may therefore exhibit superior longevity, conductivity, and permeability over a pack of sintered spheres under similarly high closure pressure, even when the closing pressure causes breakage of the sintered rods. As discussed above, in some applications better performance may be achieved by using shorter rods with a narrow length distribution.
[065] It is also observed that the sintered rod reduces the non-Darcy flow effect (a characterization of fluid flow that accounts for the turbulence generated as the oil or natural gas flows through the proppant pack). Non-Darcy flow reduces well production significantly and strips the deposited proppants from the fracture, causing them to flow back to the well bore with the natural gas or oil. In particular, the non-Darcy flow effect is mainly experienced in high flow-rate gas and volatile oil wells. The effect arises from the fact that fluid flow near the well bore has a turbulence component due to a significant pressure drop along the fracture and the convergence of flow at the well bore, which results in high flow velocities. This effect is particularly significant in natural
gas wells due to the highly expandable and less viscous nature of natural gas. The non-Darcy flow effect is expressed as: dp/dl = μv/k + βpv2 where p is the pressure drop in the fracture, I is the length of the fracture, μ is the viscosity of the gas, v is the velocity of the gas, k is the permeability of the fracture, β is the turbulence coefficient in the fracture, and p is the density of the natural gas/oil.
[066] A comparison was performed with regard to three different possible proppant shapes to determine the effect of shape on the turbulence coefficient β. It was found that an elongated shape, such as the sintered rod of the present invention, is associated with a much reduced β as compared to a spherical or irregular shape. Therefore, rod-shaped proppants would be subject to less stripping due to the non- Darcy flow effect and result in less proppant flowing back to the well bore.
[067] Reducing flow back to the well has a number of advantages. For example, less flowback reduces the abrasive wear on expensive well equipment, reduces the cost of clean up, and ensures that more of the proppant stays in the pack, providing a longer useful life for the well and a better return on investment.
[068] Although rod-shaped proppants may be used by themselves in a fracture, they may have additional utility when used in conjunction with another type of proppant, such as a spherical proppant. A mixture containing 10% of a rod-shaped proppant consistent with the present invention (having a diameter of between about 1.1 mm and 1.3 mm and length of about 10 mm to about 20 mm) and 90% of a spherical proppant (having a diameter of 0.7 mm) was tested according to API test 60 to determine the
effect of the combination under pressure. At 15,000 psi, the rods were smaller but were still present in rod-shaped form (i.e., they cracked into smaller rod-shaped proppants rather than disintegrating into fines). Surprisingly, many of the rods remained relatively long, up to 15 to 17 mm.
[069] In view of the above, sintered rods in accordance with the present invention possess a unique combination of properties that make them an excellent proppant or anti-flowback additive. Specifically, the high alumina content of the sintered rod ensures superior crush resistance, permeability, and conductivity at high closure pressures. Moreover, the proppant's unique shape enhances crush resistance, permeability, and conductivity by allowing even distribution of pressure throughout the proppant pack. In addition, the proppant's unique breaking behavior prevents deterioration of the pack and lowers the reduction in the pack's efficiency as compared to spherical proppants. The unique rod shape has the added benefit of reducing the non-Darcy flow effect in the well, thereby minimizing equipment wear and tear, maintaining consistent production of gas or oil, and reducing the cost involved in clean up of the flowback. When used in combination with other types of proppants, the presence of the rod-shaped proppant consistent with the present invention provides the unique advantages of increasing the void volume, decreasing proppant flowback, reducing the amount of fines generated at high pressures, and increasing the strength of intermediate and high strength proppants. Consequently, the rod-shaped material in accordance with the present invention may be used separately as a proppant, as a proppant in combination with other proppants, or as an anti-flowback additive when mixed in certain ratios with other proppants.
[070] The preceding description is merely exemplary of various embodiments of the present invention. Those skilled in the art will recognize that various modifications may be made to the disclosed embodiments that would still be within the scope of the invention. For example, it is envisioned that sintered rod-shaped proppants or anti- flowback additives may contain an alumina content from about 40% to about 80% by weight, or may be formed using kaolin or bauxitic kaolin as a component, in addition to those listed above. The scope of the invention is intended to be limited only by the appended claims.
Claims
1. A method of making a proppant or anti-flowback additive comprising a) providing a composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO2; b) forming at least one rod from the composition; and c) sintering the at least one rod.
2. The method of claim 1 wherein the composition is milled prior to forming the at least one rod.
3. The method of claim 1 wherein the provided composition comprises between about 0.3% by weight and about 2.7% by weight TiO2.
4. The method of claim 1 further comprising drying the formed rod or rods.
5. The method of claim 1 wherein the sintered rods comprise between about 0.2% by weight and about 4% by weight aluminum titanate.
6. The method of claim 2 wherein the milling comprises jet milling to achieve a first particle size distribution.
7. The method of claim 6 further comprising jet milling to achieve a second particle size distribution.
8. The method of claim 7 further comprising mixing the jet milled material having the first particle size distribution with the jet milled material having the second particle size distribution.
9. The method of claim 2 wherein the milling comprises ball milling.
10. The method of claim 2 wherein the milling results in a material having a d50 less than 10 microns.
11. The method of claim 10 wherein the milling results in a material having a d50 less than 3 microns. 12. The method of claim 2 wherein the milling results in a material having 95 weight percent of its particles smaller than 30 microns. 13. The method of claim 12 wherein the milling results in a material having 100% of its particles smaller than 30 microns. 14. The method of claim 1 wherein the provided composition has 95 weight percent of its particles smaller than 500 microns. 15. The method of claim 14 wherein the provided composition has 100% of its particles smaller than 500 microns. 16. The method of claim 1 wherein the sintered rod or rods have an average length of less than 15 mm. 17. The method of claim 1 wherein the sintered rod or rods have an average length of less than 5 mm. 18. The method of claim 1 wherein the forming of the at least one rod comprises extruding the composition. 19. The method of claim 2 wherein the milled composition has a multi-modal particle size distribution. 20. The method of claim 1 wherein from about 7% by weight and about 13% by weight of the sintered rods are crushed at 15,000 psi. 21.The method of claim 20 wherein from about 8% by weight to about 12% by weight of the sintered rods are crushed at 15,000 psi.
22. A method of making a proppant or anti-flowback additive comprising sintering a rod-shaped article made from a composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO2.
23. The method of claim 22 wherein the rod-shaped article's composition is milled.
24. The method of claim 22 wherein the milled composition comprises between about 0.4% by weight and about 2.3% by weight TiO2.
25. The method of claim 22 wherein the sintered article comprises between about 0.2% by weight and about 4% by weight aluminum titanate.
26. The method of claim 25 wherein the sintered article comprises between about 1 % by weight and about 2.5% by weight aluminum titanate.
27. The method of claim 23 wherein the milled composition has a multi-modal particle size distribution.
28. The method of claim 23 wherein more than one sintered article is produced.
29. The method of claim 28 wherein from about 7% by weight and about 13% by weight of the sintered articles are crushed at 15,000 psi.
30. The method of claim 29 wherein from about 9% by weight to about 11 % by weight of the sintered articles are crushed at 15,000 psi.
31.A method of fracturing subterranean formations comprising injecting a fluid containing a sintered rod-shaped article made from a composition comprising at least about 80% by weight alumina and between about 0.15% and about 3.5% by weight TiO2.
32. The method of claim 31 wherein the composition is milled prior to sintering.
33. The method of claim 32 wherein the milled composition comprises between about 0.3% by weight and about 2.7% by weight TiO2. 34. The method of claim 31 wherein the sintered article comprises between about
0.2% by weight and about 4% by weight aluminum titanate. 35. The method of claim 34 wherein the sintered article comprises between about
1 % by weight and about 2.5% by weight aluminum titanate. 36. The method of claim 32 wherein the milled composition has a multi-modal particle size distribution.
37. The method of claim 31 wherein more than one sintered article is injected. 38. The method of claim 37 wherein from about 7% by weight and about 13% by weight of the sintered articles are crushed at 15,000 psi.
39. The method of claim 38 wherein from about 9% by weight to about 11 % by weight of the sintered articles are crushed at 15,000 psi.
40. A high strength sintered rod-shaped proppant for fracturing subterranean formations comprising at least about 80% by weight alumina and between about 0.2% by weight and about 4% by weight aluminum titanate.
41.The proppant of claim 40 wherein the proppant comprises between about 1 % by weight and about 2.5% by weight aluminum titanate.
42. The proppant of claim 40 comprising at least about 95% alumina by weight. 43. The proppant of claim 40 wherein the proppant comprises less than about 4%
SiO2 by weight. 44. The proppant of claim 40 wherein the proppant has an average length to width ratio of between about 1.5:1 to about 20:1.
45. The proppant of claim 44 wherein the proppant has an average length to width ratio of between about 1.5:1 to about 7:1.
46. The proppant of claim 40 wherein the proppant is substantially cylindrical.
47. The proppant of claim 40 wherein the proppant has a substantially circular cross- section.
48. The proppant of claim 47 wherein the substantially circular cross-section has an average diameter of between about 0.5 mm and about 2 mm.
49. The proppant of claim 40 wherein the proppant has an average length between about 0.1 mm and about 20 mm.
50. The proppant of claim 49 wherein the proppant has an average length between about 1 mm and about 5 mm.
51.The proppant of claim 40 wherein the proppant has been extruded.
52. The proppant of claim 40 wherein the proppant has an apparent specific gravity less than about 3.98. 53. The proppant of claim 52 wherein the proppant has an apparent specific gravity between about 3.0 and about 3.98. 54. The proppant of claim 40 wherein the proppant has a bulk density of between about 1.5 g/cm3 and about 2.5 g/cm3. 55. The proppant of claim 40 wherein less than about 15% of the proppant is crushed at 10,000 psi. 56. The proppant of claim 40 wherein less than about 20% of the proppant is crushed at 15,000 psi.
57. The proppant of claim 40 wherein the proppant is coated with a natural or synthetic coating.
58. The proppant of claim 57 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.
59.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.
60. The method of claim 59 wherein the rod-shaped proppants comprise between about 0.2% by weight and about 4% by weight aluminum titanate.
61.The method of claim 59 wherein the broken rods are substantially uniform in size.
62. The method of claim 59 wherein the closing pressure breaks at least 65% of the sintered rods into at least two smaller proppants.
3. The method of claim 62 wherein the closing pressure breaks at least 80% of the sintered rods into at least two smaller proppants.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12156169.0A EP2500395B1 (en) | 2006-09-01 | 2007-08-30 | Method of manufacturing rod-shaped proppants and anti-flowback additives comprising aluminium titanate |
EP07825726A EP2066760A2 (en) | 2006-09-01 | 2007-08-30 | Rod-shaped proppants and anti-flowback additives, methods of manufacturing, and methods of use |
EP11185274.5A EP2407525B1 (en) | 2006-09-01 | 2007-08-30 | Rod-shaped proppants and anti-flowback additives comprising Aluminium Titanate |
EG2009020269A EG26031A (en) | 2006-09-01 | 2009-02-26 | Rod-shaped proppants and anti-flowback additives, methods of manufacturing, and methods of use |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/469,589 | 2006-09-01 | ||
US11/469,589 US20080066910A1 (en) | 2006-09-01 | 2006-09-01 | Rod-shaped proppant and anti-flowback additive, method of manufacture, and method of use |
US11/624,057 US8562900B2 (en) | 2006-09-01 | 2007-01-17 | Method of manufacturing and using rod-shaped proppants and anti-flowback additives |
US11/624,057 | 2007-01-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2008026076A2 true WO2008026076A2 (en) | 2008-03-06 |
WO2008026076A3 WO2008026076A3 (en) | 2008-08-21 |
Family
ID=39133632
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2007/003613 WO2008026076A2 (en) | 2006-09-01 | 2007-08-30 | Rod-shaped proppants and anti-flowback additives, methods of manufacturing, and methods of use |
Country Status (8)
Country | Link |
---|---|
US (5) | US8562900B2 (en) |
EP (3) | EP2407525B1 (en) |
CA (1) | CA2600053C (en) |
DK (2) | DK2500395T3 (en) |
EG (1) | EG26031A (en) |
MX (1) | MX2007010656A (en) |
RU (1) | RU2381253C1 (en) |
WO (1) | WO2008026076A2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009027841A2 (en) * | 2007-08-28 | 2009-03-05 | Imerys | Proppants and anti-flowback additives made from sillimanite minerals, methods of manufacture, and methods of use |
US20160115375A1 (en) * | 2013-06-03 | 2016-04-28 | Imerys Oilfield Minerals, Inc. | Proppants and Anti-Flowback Additives Including Compositions Comprising Calcium, Multi-Foil Cross Sections, and/or Size Ranges |
WO2017074393A1 (en) * | 2015-10-29 | 2017-05-04 | Multi-Chem Group, Llc | Carrier-free treatment particulates for use in subterranean formations |
US9914872B2 (en) | 2014-10-31 | 2018-03-13 | Chevron U.S.A. Inc. | Proppants |
EP3295222A4 (en) * | 2015-05-12 | 2018-05-09 | Conoco Phillips Company | Plastic frack tracer |
US10240449B1 (en) | 2016-08-11 | 2019-03-26 | Keane Frac, Lp | Methods and materials for hydraulic fracturing |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7581590B2 (en) | 2006-12-08 | 2009-09-01 | Schlumberger Technology Corporation | Heterogeneous proppant placement in a fracture with removable channelant fill |
US8763699B2 (en) | 2006-12-08 | 2014-07-01 | Schlumberger Technology Corporation | Heterogeneous proppant placement in a fracture with removable channelant fill |
US9085727B2 (en) | 2006-12-08 | 2015-07-21 | Schlumberger Technology Corporation | Heterogeneous proppant placement in a fracture with removable extrametrical material fill |
US8757259B2 (en) | 2006-12-08 | 2014-06-24 | Schlumberger Technology Corporation | Heterogeneous proppant placement in a fracture with removable channelant fill |
US9080440B2 (en) | 2007-07-25 | 2015-07-14 | Schlumberger Technology Corporation | Proppant pillar placement in a fracture with high solid content fluid |
US8490698B2 (en) | 2007-07-25 | 2013-07-23 | Schlumberger Technology Corporation | High solids content methods and slurries |
US9040468B2 (en) | 2007-07-25 | 2015-05-26 | Schlumberger Technology Corporation | Hydrolyzable particle compositions, treatment fluids and methods |
US8936082B2 (en) | 2007-07-25 | 2015-01-20 | Schlumberger Technology Corporation | High solids content slurry systems and methods |
US10011763B2 (en) | 2007-07-25 | 2018-07-03 | Schlumberger Technology Corporation | Methods to deliver fluids on a well site with variable solids concentration from solid slurries |
US8490699B2 (en) | 2007-07-25 | 2013-07-23 | Schlumberger Technology Corporation | High solids content slurry methods |
US7950455B2 (en) | 2008-01-14 | 2011-05-31 | Baker Hughes Incorporated | Non-spherical well treating particulates and methods of using the same |
SI2174717T1 (en) * | 2008-10-09 | 2020-08-31 | Imertech Sas | Grinding method |
US8662172B2 (en) | 2010-04-12 | 2014-03-04 | Schlumberger Technology Corporation | Methods to gravel pack a well using expanding materials |
WO2011163529A1 (en) | 2010-06-23 | 2011-12-29 | Ecopuro, Llc | Hydraulic fracturing |
US8505628B2 (en) | 2010-06-30 | 2013-08-13 | Schlumberger Technology Corporation | High solids content slurries, systems and methods |
US8511381B2 (en) | 2010-06-30 | 2013-08-20 | Schlumberger Technology Corporation | High solids content slurry methods and systems |
US9029300B2 (en) * | 2011-04-26 | 2015-05-12 | Baker Hughes Incorporated | Composites for controlled release of well treatment agents |
US9976070B2 (en) | 2010-07-19 | 2018-05-22 | Baker Hughes, A Ge Company, Llc | Method of using shaped compressed pellets in well treatment operations |
US10822536B2 (en) | 2010-07-19 | 2020-11-03 | Baker Hughes, A Ge Company, Llc | Method of using a screen containing a composite for release of well treatment agent into a well |
US8607870B2 (en) | 2010-11-19 | 2013-12-17 | Schlumberger Technology Corporation | Methods to create high conductivity fractures that connect hydraulic fracture networks in a well |
US10808497B2 (en) * | 2011-05-11 | 2020-10-20 | Schlumberger Technology Corporation | Methods of zonal isolation and treatment diversion |
US9133387B2 (en) | 2011-06-06 | 2015-09-15 | Schlumberger Technology Corporation | Methods to improve stability of high solid content fluid |
US8813585B2 (en) | 2011-10-03 | 2014-08-26 | Saudi Arabian Oil Company | Automated method for quality control and quality assurance of sized bridging material |
US9803457B2 (en) | 2012-03-08 | 2017-10-31 | Schlumberger Technology Corporation | System and method for delivering treatment fluid |
US9863228B2 (en) | 2012-03-08 | 2018-01-09 | Schlumberger Technology Corporation | System and method for delivering treatment fluid |
US9528354B2 (en) | 2012-11-14 | 2016-12-27 | Schlumberger Technology Corporation | Downhole tool positioning system and method |
US9388335B2 (en) | 2013-07-25 | 2016-07-12 | Schlumberger Technology Corporation | Pickering emulsion treatment fluid |
RU2696908C2 (en) * | 2014-04-23 | 2019-08-07 | ХУВАКИ, ЭлЭлСи | Proppant for hydraulic fracturing fluid |
US10001613B2 (en) | 2014-07-22 | 2018-06-19 | Schlumberger Technology Corporation | Methods and cables for use in fracturing zones in a well |
US10738577B2 (en) | 2014-07-22 | 2020-08-11 | Schlumberger Technology Corporation | Methods and cables for use in fracturing zones in a well |
EP3186331B1 (en) | 2014-07-23 | 2022-05-04 | Baker Hughes Holdings LLC | Composite comprising well treatment agent and/or a tracer adhered onto a calcined substrate of a metal oxide coated core and a method of using the same |
CA2985474C (en) * | 2015-05-12 | 2022-03-01 | Conocophillips Company | Plastic frack tracer |
US9896618B2 (en) * | 2015-11-19 | 2018-02-20 | Schlumberger Technology Corporation | Method of making rod-shaped particles for use as proppant and anti-flowback additive |
US9932519B2 (en) | 2015-11-19 | 2018-04-03 | Schlumberger Technology Corporation | Method of making particles having a ridge portion for use as proppant |
US10369724B2 (en) | 2015-11-19 | 2019-08-06 | Schlumberger Technology Corporation | Method of making spheroidal particles |
US11091396B2 (en) * | 2016-05-23 | 2021-08-17 | Sasol (Usa) Corporation | High strength shaped aluminas and a method of producing such high strength shaped aluminas |
US10641083B2 (en) | 2016-06-02 | 2020-05-05 | Baker Hughes, A Ge Company, Llc | Method of monitoring fluid flow from a reservoir using well treatment agents |
US10413966B2 (en) | 2016-06-20 | 2019-09-17 | Baker Hughes, A Ge Company, Llc | Nanoparticles having magnetic core encapsulated by carbon shell and composites of the same |
US10557079B2 (en) * | 2016-07-22 | 2020-02-11 | Schlumberger Technology Corporation | Method of making rod-shaped particles for use as proppant and anti-flowback additive |
WO2018031915A1 (en) * | 2016-08-11 | 2018-02-15 | Dynamic Material Systems Llc | Fracking proppant and method of manufacture |
US11597872B2 (en) * | 2017-07-05 | 2023-03-07 | Carbo Ceramics Inc. | Micromesh proppant and methods of making and using same |
US11254861B2 (en) | 2017-07-13 | 2022-02-22 | Baker Hughes Holdings Llc | Delivery system for oil-soluble well treatment agents and methods of using the same |
US11053432B2 (en) * | 2017-08-09 | 2021-07-06 | First Bauxite Llc | Ultra high strength proppant and method of preparing the same |
US10385261B2 (en) | 2017-08-22 | 2019-08-20 | Covestro Llc | Coated particles, methods for their manufacture and for their use as proppants |
US11254850B2 (en) | 2017-11-03 | 2022-02-22 | Baker Hughes Holdings Llc | Treatment methods using aqueous fluids containing oil-soluble treatment agents |
US10961444B1 (en) | 2019-11-01 | 2021-03-30 | Baker Hughes Oilfield Operations Llc | Method of using coated composites containing delayed release agent in a well treatment operation |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3497008A (en) | 1968-03-05 | 1970-02-24 | Exxon Production Research Co | Method of propping fractures with ceramic particles |
US4068718A (en) | 1975-09-26 | 1978-01-17 | Exxon Production Research Company | Hydraulic fracturing method using sintered bauxite propping agent |
US4427068A (en) | 1982-02-09 | 1984-01-24 | Kennecott Corporation | Sintered spherical pellets containing clay as a major component useful for gas and oil well proppants |
US5420174A (en) | 1992-11-02 | 1995-05-30 | Halliburton Company | Method of producing coated proppants compatible with oxidizing gel breakers |
US6059034A (en) | 1996-11-27 | 2000-05-09 | Bj Services Company | Formation treatment method using deformable particles |
US6753299B2 (en) | 2001-11-09 | 2004-06-22 | Badger Mining Corporation | Composite silica proppant material |
Family Cites Families (262)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3126056A (en) | 1964-03-24 | Hydraulic fracturing of earth formations | ||
US1942431A (en) | 1934-01-09 | Refractory brick and process of | ||
US1871793A (en) | 1925-03-02 | 1932-08-16 | Aluminum Co Of America | Purified metallic oxide |
US1871792A (en) | 1925-03-02 | 1932-08-16 | Aluminum Co Of America | Treatment of metallic oxides |
GB284131A (en) | 1927-06-07 | 1928-01-26 | Metallbank & Metallurg Ges Ag | Process of disintegrating liquid alumina |
US2261639A (en) | 1937-07-02 | 1941-11-04 | Carborundum Co | Oxide pellet |
US2340194A (en) | 1941-11-14 | 1944-01-25 | Carborundum Co | Refractory of insulating material |
GB578424A (en) | 1943-05-13 | 1946-06-27 | Gen Motors Corp | Improved method of making ceramic materials intended more particularly as insulators for spark plugs |
US2566117A (en) | 1947-06-14 | 1951-08-28 | Babcock & Wilcox Co | Refractory heat transfer bodies and process of manufacture |
US2586818A (en) | 1947-08-21 | 1952-02-26 | Harms Viggo | Progressive classifying or treating solids in a fluidized bed thereof |
US2699212A (en) | 1948-09-01 | 1955-01-11 | Newton B Dismukes | Method of forming passageways extending from well bores |
US2950247A (en) | 1957-05-16 | 1960-08-23 | Atlantic Refining Co | Increasing permeability of subsurface formations |
GB886342A (en) | 1957-08-13 | 1962-01-03 | United States Steel Corp | Refractory body and method of manufacture thereof |
US2986455A (en) | 1958-02-21 | 1961-05-30 | Carborundum Co | Bonded abrasive articles |
US3026938A (en) | 1958-09-02 | 1962-03-27 | Gulf Research Development Co | Propping agent for a fracturing process |
US3079243A (en) | 1959-10-19 | 1963-02-26 | Norton Co | Abrasive grain |
US3075581A (en) | 1960-06-13 | 1963-01-29 | Atlantic Retining Company | Increasing permeability of subsurface formations |
US3245866A (en) | 1961-11-24 | 1966-04-12 | Charles W Schott | Vitreous spheres of slag and slag-like materials and underground propplants |
US3242032A (en) | 1961-11-24 | 1966-03-22 | Charles W Schott | Glass spheres and underground proppants and methods of making the same |
US3241613A (en) | 1962-02-19 | 1966-03-22 | Atlantic Refining Co | Shutting off water in vertical fractures |
BE630290A (en) | 1962-03-28 | |||
US3350482A (en) | 1962-04-18 | 1967-10-31 | Sun Oil Co | Method of producing spherical solids |
BE634464A (en) | 1962-07-03 | |||
DE1278411B (en) | 1963-06-14 | 1968-09-26 | Basf Ag | Process for the production of catalysts or catalyst carriers in the form of hollow spheres |
US3387957A (en) | 1966-04-04 | 1968-06-11 | Carborundum Co | Microcrystalline sintered bauxite abrasive grain |
US3399727A (en) | 1966-09-16 | 1968-09-03 | Exxon Production Research Co | Method for propping a fracture |
US3437148A (en) | 1967-01-06 | 1969-04-08 | Union Carbide Corp | Method and article for increasing the permeability of earth formations |
US3486706A (en) | 1967-02-10 | 1969-12-30 | Minnesota Mining & Mfg | Ceramic grinding media |
US3491492A (en) | 1968-01-15 | 1970-01-27 | Us Industries Inc | Method of making alumina abrasive grains |
CH490110A (en) | 1969-02-28 | 1970-05-15 | Spemag Ag | Mixer |
US3598373A (en) | 1970-03-26 | 1971-08-10 | Coors Porcelanin Co | Method and apparatus for making small ceramic spheres |
US3856441A (en) | 1970-10-30 | 1974-12-24 | Ube Industries | Apparatus for pelletizing powdered solid substance in a fluidized bed |
US3758318A (en) | 1971-03-29 | 1973-09-11 | Kaiser Aluminium Chem Corp | Production of mullite refractory |
US4052794A (en) | 1971-06-18 | 1977-10-11 | Struthers Scientific And International Corporation | Fluidized bed process |
DE2144220C3 (en) | 1971-08-31 | 1974-04-25 | Mannesmann Ag, 4000 Duesseldorf | Method and apparatus for producing low-oxygen metal powders |
GB1421531A (en) | 1971-12-15 | 1976-01-21 | Atomic Energy Authority Uk | Separation of molecules and materials therefor |
DK131326C (en) | 1971-12-29 | 1976-01-05 | Niro Atomizer As | PROCEDURE FOR PRODUCING A ROUGH-GRAIN PRODUCT WITH RELATIVELY HIGH MOISTURE CONTENT |
US3810768A (en) | 1972-04-06 | 1974-05-14 | Chicago Fire Brick Co | Refractory composition comprising coarse particles of clay or bauxite and carbon |
US4051603A (en) | 1973-07-02 | 1977-10-04 | Struthers Scientific And International Corporation | Fluidized bed apparatus |
US3890072A (en) | 1973-09-04 | 1975-06-17 | Norton Co | Apparatus for forming solid spherical pellets |
US3976138A (en) | 1974-08-01 | 1976-08-24 | Union Carbide Corporation | Method of increasing permeability in subsurface earth formation |
US4077908A (en) | 1974-12-27 | 1978-03-07 | Hoechst Aktiengesellschaft | Production of material consisting of solid hollow spheroids |
US4111713A (en) | 1975-01-29 | 1978-09-05 | Minnesota Mining And Manufacturing Company | Hollow spheres |
FR2306327A1 (en) | 1975-03-19 | 1976-10-29 | Inst Francais Du Petrole | PROCESS FOR SUPPORTING FRACTURES IN THE WALLS OF A WELL THROUGH GEOLOGICAL FORMATIONS |
US4008763A (en) | 1976-05-20 | 1977-02-22 | Atlantic Richfield Company | Well treatment method |
US4053375A (en) | 1976-07-16 | 1977-10-11 | Dorr-Oliver Incorporated | Process for recovery of alumina-cryolite waste in aluminum production |
US4303204A (en) | 1976-10-28 | 1981-12-01 | Reynolds Metals Company | Upgrading of bauxites, bauxitic clays, and aluminum mineral bearing clays |
US4140773A (en) | 1978-02-24 | 1979-02-20 | Continental Oil Company | Production of high pore volume alumina spheres |
JPS5524813A (en) | 1978-08-03 | 1980-02-22 | Showa Denko Kk | Alumina grinding grain |
US5212143A (en) | 1978-08-28 | 1993-05-18 | Torobin Leonard B | Hollow porous microspheres made from dispersed particle compositions |
US4671909A (en) | 1978-09-21 | 1987-06-09 | Torobin Leonard B | Method for making hollow porous microspheres |
JPS5857430B2 (en) | 1978-10-23 | 1983-12-20 | 四国化成工業株式会社 | Process for producing granular dichloroisocyanuric acid alkali metal salt |
CA1117987A (en) | 1978-12-13 | 1982-02-09 | Robert J. Seider | Sintered high density spherical ceramic pellets for gas and oil well proppants and their process of manufacture |
US4371481A (en) | 1979-02-06 | 1983-02-01 | Phillips Petroleum Company | Iron-containing refractory balls for retorting oil shale |
US4407967A (en) | 1979-08-16 | 1983-10-04 | Frenchtown American Corp. | Method for producing spheroidal ceramics |
US4268311A (en) | 1979-11-01 | 1981-05-19 | Anchor Hocking Corporation | High strength cordierite ceramic |
US4442897A (en) | 1980-05-23 | 1984-04-17 | Standard Oil Company | Formation fracturing method |
GB2079261B (en) | 1980-07-07 | 1983-06-08 | Niro Atomizer As | Process for the production of sintered bauxite spheres |
US4440866A (en) | 1980-07-07 | 1984-04-03 | A/S Niro Atomizer | Process for the production of sintered bauxite spheres |
DK155781C (en) | 1982-01-07 | 1989-10-09 | Niro Atomizer As | PROCEDURE FOR MANUFACTURING SINTERED TASTING BULBS OF BAUXITE OR BAUXIT SUBSTANCED BERGART, AND MEANS OF EXERCISING THE PROCEDURE |
US4343751A (en) | 1980-09-15 | 1982-08-10 | Lowe's, Inc. | Clay agglomeration process |
FR2493910A1 (en) | 1980-11-13 | 1982-05-14 | Produits Refractaires | ZIRCONIA AND SILICA BASE AGENT FOR DEEP GEOLOGICAL FRACTURES |
US4392988A (en) | 1981-05-11 | 1983-07-12 | Ga Technologies Inc. | Method of producing stable alumina |
US4547468A (en) | 1981-08-10 | 1985-10-15 | Terra Tek, Inc. | Hollow proppants and a process for their manufacture |
US4522731A (en) | 1982-10-28 | 1985-06-11 | Dresser Industries, Inc. | Hydraulic fracturing propping agent |
AU551409B2 (en) | 1982-01-07 | 1986-05-01 | A/S Niro Atomizer | High strength propping agent |
US4396595A (en) | 1982-02-08 | 1983-08-02 | North American Philips Electric Corp. | Method of enhancing the optical transmissivity of polycrystalline alumina bodies, and article produced by such method |
US4879181B1 (en) | 1982-02-09 | 1994-01-11 | Carbo Ceramics Inc. | Sintered spherical pellets containing clay as a major component useful for gas and oil well proppants |
US4623630A (en) | 1982-02-09 | 1986-11-18 | Standard Oil Proppants Company | Use of uncalcined/partially calcined ingredients in the manufacture of sintered pellets useful for gas and oil well proppants |
US4658899A (en) | 1982-02-09 | 1987-04-21 | Standard Oil Proppants Company, L.P. | Use of uncalcined/partially calcined ingredients in the manufacture of sintered pellets useful for gas and oil well proppants |
US4894285B1 (en) | 1982-02-09 | 1994-01-11 | Carbo Ceramics Inc. | Sintered spherical pellets containing clay as a major component useful for gas and oil well proppants |
US4439489A (en) | 1982-02-16 | 1984-03-27 | Acme Resin Corporation | Particles covered with a cured infusible thermoset film and process for their production |
US4450184A (en) | 1982-02-16 | 1984-05-22 | Metco Incorporated | Hollow sphere ceramic particles for abradable coatings |
US4462466A (en) | 1982-03-29 | 1984-07-31 | Kachnik Joseph E | Method of propping fractures in subterranean formations |
AU547407B2 (en) | 1982-07-23 | 1985-10-17 | Norton Co. | Low density proppant for oil and gas wells |
US5120455A (en) | 1982-10-28 | 1992-06-09 | Carbo Ceramics Inc. | Hydraulic fracturing propping agent |
CA1217319A (en) | 1983-02-07 | 1987-02-03 | Arup K. Khaund | Low density proppant |
US4509598A (en) | 1983-03-25 | 1985-04-09 | The Dow Chemical Company | Fracturing fluids containing bouyant inorganic diverting agent and method of use in hydraulic fracturing of subterranean formations |
US4521475A (en) | 1983-04-01 | 1985-06-04 | Riccio Louis M | Method and apparatus for applying metal cladding on surfaces and products formed thereby |
US4628042A (en) | 1983-06-20 | 1986-12-09 | Engelhard Corporation | Porous mullite |
US4555493A (en) | 1983-12-07 | 1985-11-26 | Reynolds Metals Company | Aluminosilicate ceramic proppant for gas and oil well fracturing and method of forming same |
US4493875A (en) | 1983-12-09 | 1985-01-15 | Minnesota Mining And Manufacturing Company | Proppant for well fractures and method of making same |
US4618504A (en) | 1983-12-20 | 1986-10-21 | Bosna Alexander A | Method and apparatus for applying metal cladding on surfaces and products formed thereby |
US4944905A (en) | 1984-01-18 | 1990-07-31 | Minnesota Mining And Manufacturing Company | Particulate ceramic useful as a proppant |
US4680230A (en) | 1984-01-18 | 1987-07-14 | Minnesota Mining And Manufacturing Company | Particulate ceramic useful as a proppant |
US4652411A (en) | 1984-05-23 | 1987-03-24 | The United States Of America As Represented By The United States Department Of Energy | Method of preparing thin porous sheets of ceramic material |
CA1228226A (en) | 1984-07-05 | 1987-10-20 | Arup K. Khaund | Sintered low density gas and oil well proppants from a low cost unblended clay material of selected compositions |
US4668645A (en) | 1984-07-05 | 1987-05-26 | Arup Khaund | Sintered low density gas and oil well proppants from a low cost unblended clay material of selected composition |
US4744831A (en) | 1984-07-30 | 1988-05-17 | Minnesota Mining And Manufacturing Company | Hollow inorganic spheres and methods for making such spheres |
US4714623A (en) | 1985-02-28 | 1987-12-22 | Riccio Louis M | Method and apparatus for applying metal cladding on surfaces and products formed thereby |
US4713203A (en) | 1985-05-23 | 1987-12-15 | Comalco Aluminium Limited | Bauxite proppant |
US4632876A (en) | 1985-06-12 | 1986-12-30 | Minnesota Mining And Manufacturing Company | Ceramic spheroids having low density and high crush resistance |
US4639427A (en) | 1985-06-28 | 1987-01-27 | Norton Company | Stress-corrosion resistant proppant for oil and gas wells |
US4657754A (en) | 1985-11-21 | 1987-04-14 | Norton Company | Aluminum oxide powders and process |
US4654266A (en) | 1985-12-24 | 1987-03-31 | Kachnik Joseph L | Durable, high-strength proppant and method for forming same |
US4867931A (en) | 1986-02-10 | 1989-09-19 | Materials Technology Corporation | Methods for producing fiber reinforced microspheres made from dispersed particle compositions |
JPS6379777A (en) | 1986-09-24 | 1988-04-09 | 科学技術庁金属材料技術研究所長 | Coating on ceramic substrate and manufacture |
EP0291029B2 (en) | 1987-05-11 | 1996-11-27 | Norton Company | Sintered Alumina-Zirconia Ceramic Bodies and Preparation thereof |
US4869960A (en) | 1987-09-17 | 1989-09-26 | Minnesota Mining And Manufacturing Company | Epoxy novolac coated ceramic particulate |
US4923714A (en) | 1987-09-17 | 1990-05-08 | Minnesota Mining And Manufacturing Company | Novolac coated ceramic particulate |
CA1311911C (en) | 1987-10-22 | 1992-12-29 | Alcan International Limited | Process for producing shaped refractory products |
US4874726A (en) | 1987-11-18 | 1989-10-17 | Dresser Industries, Inc. | Lightweight fused silica refractory compositions |
US4892147A (en) | 1987-12-28 | 1990-01-09 | Mobil Oil Corporation | Hydraulic fracturing utilizing a refractory proppant |
US4921821A (en) | 1988-08-02 | 1990-05-01 | Norton-Alcoa Proppants | Lightweight oil and gas well proppants and methods for making and using same |
US4921820A (en) | 1989-01-17 | 1990-05-01 | Norton-Alcoa Proppants | Lightweight proppant for oil and gas wells and methods for making and using same |
US5030603A (en) | 1988-08-02 | 1991-07-09 | Norton-Alcoa | Lightweight oil and gas well proppants |
US5192339A (en) | 1988-08-25 | 1993-03-09 | Showa Denko K.K. | Abrasive grain and method for manufacturing the same |
US4960737A (en) | 1988-09-06 | 1990-10-02 | Corning Incorporated | Calcium dialuminate/hexaluminate ceramic structures |
USRE34371E (en) | 1989-01-17 | 1993-09-07 | Norton-Alcoa | Lightweight proppant for oil and gas wells and methods for making and using same |
US4977116A (en) | 1989-01-17 | 1990-12-11 | Norton-Alcoa | Method for making lightweight proppant for oil and gas wells |
EP0406874B1 (en) | 1989-07-06 | 1994-12-14 | Toshiba Kikai Kabushiki Kaisha | Control apparatus for an injection molding machine |
US5076815A (en) * | 1989-07-07 | 1991-12-31 | Lonza Ltd. | Process for producing sintered material based on aluminum oxide and titanium oxide |
US5045506A (en) | 1989-07-31 | 1991-09-03 | Alcan International Limited | Process for producing mineral fibers incorporating an alumina-containing residue from a metal melting operation and fibers so produced |
US5188175A (en) | 1989-08-14 | 1993-02-23 | Carbo Ceramics Inc. | Method of fracturing a subterranean formation with a lightweight propping agent |
US5160678A (en) | 1989-12-15 | 1992-11-03 | United States Surgical Corporation | Pressurized powder support for treating processes |
US5240654A (en) | 1989-12-22 | 1993-08-31 | Comalco Aluminium Limited | Method of making ceramic microspheres |
ES2056394T3 (en) | 1989-12-22 | 1994-10-01 | Comalco Alu | CERAMIC MICROSPHERES. |
US5243190A (en) | 1990-01-17 | 1993-09-07 | Protechnics International, Inc. | Radioactive tracing with particles |
US5182051A (en) | 1990-01-17 | 1993-01-26 | Protechnics International, Inc. | Raioactive tracing with particles |
EP0463437B2 (en) | 1990-06-22 | 1998-12-02 | Bayer Ag | Sintered bodies based on aluminium titanate, process for their production and use thereof |
WO1993008138A1 (en) | 1991-10-16 | 1993-04-29 | Showa Denko Kabushiki Kaisha | Sintered alumina abrasive grain and abrasive product |
US5339902A (en) | 1993-04-02 | 1994-08-23 | Halliburton Company | Well cementing using permeable cement |
CA2119316C (en) | 1993-04-05 | 2006-01-03 | Roger J. Card | Control of particulate flowback in subterranean wells |
US5330005A (en) | 1993-04-05 | 1994-07-19 | Dowell Schlumberger Incorporated | Control of particulate flowback in subterranean wells |
JP2778423B2 (en) | 1993-04-28 | 1998-07-23 | 昭和電工株式会社 | Coated fused alumina particles and method for producing the same |
US5422183A (en) | 1993-06-01 | 1995-06-06 | Santrol, Inc. | Composite and reinforced coatings on proppants and particles |
US5396805A (en) | 1993-09-30 | 1995-03-14 | Halliburton Company | Force sensor and sensing method using crystal rods and light signals |
US5837656A (en) | 1994-07-21 | 1998-11-17 | Santrol, Inc. | Well treatment fluid compatible self-consolidating particles |
US5431225A (en) | 1994-09-21 | 1995-07-11 | Halliburton Company | Sand control well completion methods for poorly consolidated formations |
USRE36466E (en) | 1995-01-06 | 1999-12-28 | Dowel | Sand control without requiring a gravel pack screen |
GB9503949D0 (en) | 1995-02-28 | 1995-04-19 | Atomic Energy Authority Uk | Oil well treatment |
US5839510A (en) | 1995-03-29 | 1998-11-24 | Halliburton Energy Services, Inc. | Control of particulate flowback in subterranean wells |
US5833000A (en) | 1995-03-29 | 1998-11-10 | Halliburton Energy Services, Inc. | Control of particulate flowback in subterranean wells |
US5787986A (en) | 1995-03-29 | 1998-08-04 | Halliburton Energy Services, Inc. | Control of particulate flowback in subterranean wells |
US6047772A (en) | 1995-03-29 | 2000-04-11 | Halliburton Energy Services, Inc. | Control of particulate flowback in subterranean wells |
US6209643B1 (en) | 1995-03-29 | 2001-04-03 | Halliburton Energy Services, Inc. | Method of controlling particulate flowback in subterranean wells and introducing treatment chemicals |
US5582249A (en) | 1995-08-02 | 1996-12-10 | Halliburton Company | Control of particulate flowback in subterranean wells |
US5501274A (en) | 1995-03-29 | 1996-03-26 | Halliburton Company | Control of particulate flowback in subterranean wells |
US5775425A (en) | 1995-03-29 | 1998-07-07 | Halliburton Energy Services, Inc. | Control of fine particulate flowback in subterranean wells |
BR9501449C1 (en) | 1995-04-05 | 2000-12-05 | Mineracao Curimbaba Ltda | Process for preparing a bauxite propellant for hydraulic fracturing of oil wells, sintered bauxite propellant and process for extracting oil and gas from an oil well |
BR9501450A (en) | 1995-04-05 | 1997-08-19 | Mineracao Curimbaba Ltda | Process for preparing a clay-mineral propellant for hydraulic fracturing of oil wells sintered clay-mineral propandant and process for extracting oil and gas from an oil well |
US5604184A (en) | 1995-04-10 | 1997-02-18 | Texaco, Inc. | Chemically inert resin coated proppant system for control of proppant flowback in hydraulically fractured wells |
US5833361A (en) | 1995-09-07 | 1998-11-10 | Funk; James E. | Apparatus for the production of small spherical granules |
US5972835A (en) | 1995-09-13 | 1999-10-26 | Research Triangle Institute | Fluidizable particulate materials and methods of making same |
FR2739864B1 (en) | 1995-10-16 | 1998-01-09 | Pechiney Electrometallurgie | ALUMINA-BASED ABRASIVE GRAINS AND PROCESS FOR THE PREPARATION THEREOF |
US6528157B1 (en) | 1995-11-01 | 2003-03-04 | Borden Chemical, Inc. | Proppants with fiber reinforced resin coatings |
US5582250A (en) | 1995-11-09 | 1996-12-10 | Dowell, A Division Of Schlumberger Technology Corporation | Overbalanced perforating and fracturing process using low-density, neutrally buoyant proppant |
US5697440A (en) | 1996-01-04 | 1997-12-16 | Halliburton Energy Services, Inc. | Control of particulate flowback in subterranean wells |
US5699860A (en) | 1996-02-22 | 1997-12-23 | Halliburton Energy Services, Inc. | Fracture propping agents and methods |
US5893935A (en) | 1997-01-09 | 1999-04-13 | Minnesota Mining And Manufacturing Company | Method for making abrasive grain using impregnation, and abrasive articles |
US5782300A (en) | 1996-11-13 | 1998-07-21 | Schlumberger Technology Corporation | Suspension and porous pack for reduction of particles in subterranean well fluids, and method for treating an underground formation |
DE19647037A1 (en) | 1996-11-14 | 1998-05-28 | Degussa | Spherical color pigments, process for their preparation and their use |
DE19647038B4 (en) | 1996-11-14 | 2007-02-22 | Ferro Gmbh | Spherical pigments, process for their preparation and their use |
US20050028979A1 (en) | 1996-11-27 | 2005-02-10 | Brannon Harold Dean | Methods and compositions of a storable relatively lightweight proppant slurry for hydraulic fracturing and gravel packing applications |
US6772838B2 (en) | 1996-11-27 | 2004-08-10 | Bj Services Company | Lightweight particulate materials and uses therefor |
US6749025B1 (en) | 1996-11-27 | 2004-06-15 | Bj Services Company | Lightweight methods and compositions for sand control |
US6364018B1 (en) | 1996-11-27 | 2002-04-02 | Bj Services Company | Lightweight methods and compositions for well treating |
US6330916B1 (en) | 1996-11-27 | 2001-12-18 | Bj Services Company | Formation treatment method using deformable particles |
US7426961B2 (en) | 2002-09-03 | 2008-09-23 | Bj Services Company | Method of treating subterranean formations with porous particulate materials |
GB2325260B (en) | 1997-05-14 | 2000-06-07 | Sofitech Nv | Abrasives for well cleaning |
US6152227A (en) | 1997-10-24 | 2000-11-28 | Baroid Technology, Inc. | Drilling and cementing through shallow waterflows |
RU2129987C1 (en) | 1998-01-09 | 1999-05-10 | Открытое акционерное общество "Боровичский комбинат огнеупоров" | Method of processing alumino-silicon crude |
US6582819B2 (en) | 1998-07-22 | 2003-06-24 | Borden Chemical, Inc. | Low density composite proppant, filtration media, gravel packing media, and sports field media, and methods for making and using same |
AR019461A1 (en) | 1998-07-22 | 2002-02-20 | Borden Chem Inc | A COMPOSITE PARTICLE, A METHOD TO PRODUCE, A METHOD TO TREAT A HYDRAULICALLY INDUCED FRACTURE IN A UNDERGROUND FORMATION, AND A METHOD FOR WATER FILTRATION. |
US6406789B1 (en) | 1998-07-22 | 2002-06-18 | Borden Chemical, Inc. | Composite proppant, composite filtration media and methods for making and using same |
RU2140875C1 (en) | 1998-10-02 | 1999-11-10 | ОАО "Боровичский комбинат огнеупоров" | Aluminosilicate mixture for production of granules |
RU2140874C1 (en) | 1998-10-02 | 1999-11-10 | ОАО "Боровичский комбинат огнеупоров" | Method of processing of alumosilicon raw materials |
US6419019B1 (en) | 1998-11-19 | 2002-07-16 | Schlumberger Technology Corporation | Method to remove particulate matter from a wellbore using translocating fibers and/or platelets |
US6192985B1 (en) | 1998-12-19 | 2001-02-27 | Schlumberger Technology Corporation | Fluids and techniques for maximizing fracture fluid clean-up |
FR2789688B1 (en) | 1999-02-15 | 2001-03-23 | Pem Abrasifs Refractaires | ABRASIVE GRAINS CONSISTING OF POLYCRYSTALLINE ALUMINA |
US6599863B1 (en) | 1999-02-18 | 2003-07-29 | Schlumberger Technology Corporation | Fracturing process and composition |
US6217646B1 (en) | 1999-04-26 | 2001-04-17 | Daubois Inc. | Sculptable and breathable wall coating mortar compound |
RU2166079C1 (en) | 1999-12-23 | 2001-04-27 | Закрытое акционерное общество "Уралсервис" | Proppant |
DE10019184A1 (en) | 2000-04-17 | 2001-10-25 | Treibacher Schleifmittel Gmbh | Production of sintered microcrystalline molded body used as an abrasive body comprises mixing alpha-alumina with a binder and a solvent to form a mixture, extruding the mixture to an extrudate, processing to molded bodies, and sintering |
DE60120553T2 (en) | 2000-04-28 | 2007-06-06 | Ricoh Co., Ltd. | Toner, external additive, and imaging process |
US6372678B1 (en) | 2000-09-28 | 2002-04-16 | Fairmount Minerals, Ltd | Proppant composition for gas and oil well fracturing |
US6659179B2 (en) | 2001-05-18 | 2003-12-09 | Halliburton Energy Serv Inc | Method of controlling proppant flowback in a well |
RU2196889C1 (en) | 2001-05-21 | 2003-01-20 | Открытое акционерное общество "Научно-производственное объединение Восточный институт огнеупоров" | Proppants and method of their production |
WO2002098796A1 (en) | 2001-05-30 | 2002-12-12 | Showa Denko K.K. | Spherical alumina particles and production process thereof |
WO2002098795A1 (en) | 2001-05-30 | 2002-12-12 | Showa Denko K.K. | Spherical alumina particles and production process thereof |
US7080688B2 (en) | 2003-08-14 | 2006-07-25 | Halliburton Energy Services, Inc. | Compositions and methods for degrading filter cake |
DE10138574A1 (en) | 2001-08-06 | 2003-02-27 | Degussa | Granules based on pyrogenically produced aluminum oxide, process for their production and their use |
DE60135322D1 (en) | 2001-08-06 | 2008-09-25 | Schlumberger Technology Bv | Low density fiber reinforced cement composition |
US6837309B2 (en) | 2001-09-11 | 2005-01-04 | Schlumberger Technology Corporation | Methods and fluid compositions designed to cause tip screenouts |
AU2002327694A1 (en) | 2001-09-26 | 2003-04-07 | Claude E. Cooke Jr. | Method and materials for hydraulic fracturing of wells |
RU2211198C2 (en) | 2001-11-13 | 2003-08-27 | Открытое акционерное общество "Боровичский комбинат огнеупоров" | Blend for manufacturing refractory high-strength spherical granules and a method for fabrication thereof |
US6725931B2 (en) | 2002-06-26 | 2004-04-27 | Halliburton Energy Services, Inc. | Methods of consolidating proppant and controlling fines in wells |
US7267171B2 (en) | 2002-01-08 | 2007-09-11 | Halliburton Energy Services, Inc. | Methods and compositions for stabilizing the surface of a subterranean formation |
US6668926B2 (en) | 2002-01-08 | 2003-12-30 | Halliburton Energy Services, Inc. | Methods of consolidating proppant in subterranean fractures |
US6962200B2 (en) | 2002-01-08 | 2005-11-08 | Halliburton Energy Services, Inc. | Methods and compositions for consolidating proppant in subterranean fractures |
FR2836472B1 (en) | 2002-02-28 | 2004-05-21 | Pem Abrasifs Refractaires | ABRASIVE GRAINS BASED ON ALUMINUM OXYNITRIDE |
US6830105B2 (en) | 2002-03-26 | 2004-12-14 | Halliburton Energy Services, Inc. | Proppant flowback control using elastomeric component |
US20030195121A1 (en) | 2002-04-11 | 2003-10-16 | Fitzgerald Michael Dylon | Sulphur based proppants and process therefor |
US6691780B2 (en) | 2002-04-18 | 2004-02-17 | Halliburton Energy Services, Inc. | Tracking of particulate flowback in subterranean wells |
US6725930B2 (en) | 2002-04-19 | 2004-04-27 | Schlumberger Technology Corporation | Conductive proppant and method of hydraulic fracturing using the same |
US20030205376A1 (en) | 2002-04-19 | 2003-11-06 | Schlumberger Technology Corporation | Means and Method for Assessing the Geometry of a Subterranean Fracture During or After a Hydraulic Fracturing Treatment |
US6732800B2 (en) | 2002-06-12 | 2004-05-11 | Schlumberger Technology Corporation | Method of completing a well in an unconsolidated formation |
RU2229458C2 (en) | 2002-06-28 | 2004-05-27 | Открытое акционерное общество "Свердловский научно-исследовательский институт химического машиностроения" | Method of strengthening and hydrophobization of ceramic granules |
US7036591B2 (en) | 2002-10-10 | 2006-05-02 | Carbo Ceramics Inc. | Low density proppant |
RU2215712C1 (en) | 2003-01-05 | 2003-11-10 | Закрытое акционерное общество "Тригорстроймонтаж" | Blend for manufacturing light-weight high-strength ceramic propping members |
US6752208B1 (en) | 2003-01-08 | 2004-06-22 | Halliburton Energy Services, Inc. | Methods of reducing proppant flowback |
US6780804B2 (en) | 2003-01-24 | 2004-08-24 | Saint-Gobain Ceramics & Plastics, Inc. | Extended particle size distribution ceramic fracturing proppant |
US6892813B2 (en) | 2003-01-30 | 2005-05-17 | Halliburton Energy Services, Inc. | Methods for preventing fracture proppant flowback |
US7220454B2 (en) | 2003-02-06 | 2007-05-22 | William Marsh Rice University | Production method of high strength polycrystalline ceramic spheres |
US6866099B2 (en) | 2003-02-12 | 2005-03-15 | Halliburton Energy Services, Inc. | Methods of completing wells in unconsolidated subterranean zones |
US7119039B2 (en) | 2003-03-24 | 2006-10-10 | Carbo Ceramics Inc. | Titanium dioxide scouring media and method of production |
CN1839034A (en) | 2003-04-15 | 2006-09-27 | 氦克逊特种化学品公司 | Particulate material containing thermoplastic elastomer and methods for making and using same |
CA2525090C (en) | 2003-05-08 | 2009-04-07 | Otkrytoe Aktsionernoe Obschestvo "Borovichsky Kombinat Ogneuporov" | Aluminosilicate mixture for fabrication of fireproof, high-strength granules, fireproof high-strength spherical granules and the method of their manufacture |
US7032664B2 (en) | 2004-06-02 | 2006-04-25 | Halliburton Energy Services, Inc. | Nanocomposite particulates and methods of using nanocomposite particulates |
US7036592B2 (en) | 2003-05-22 | 2006-05-02 | Halliburton Energy Services, Inc. | High strength particles and methods of their use in subterranean operations |
US6983797B2 (en) | 2003-05-22 | 2006-01-10 | Halliburton Energy Services, Inc. | Lightweight high strength particles and methods of their use in wells |
US7004255B2 (en) | 2003-06-04 | 2006-02-28 | Schlumberger Technology Corporation | Fracture plugging |
US7228904B2 (en) | 2003-06-27 | 2007-06-12 | Halliburton Energy Services, Inc. | Compositions and methods for improving fracture conductivity in a subterranean well |
US20050130848A1 (en) | 2003-06-27 | 2005-06-16 | Halliburton Energy Services, Inc. | Compositions and methods for improving fracture conductivity in a subterranean well |
US7044224B2 (en) | 2003-06-27 | 2006-05-16 | Halliburton Energy Services, Inc. | Permeable cement and methods of fracturing utilizing permeable cement in subterranean well bores |
US7178596B2 (en) | 2003-06-27 | 2007-02-20 | Halliburton Energy Services, Inc. | Methods for improving proppant pack permeability and fracture conductivity in a subterranean well |
US7044220B2 (en) | 2003-06-27 | 2006-05-16 | Halliburton Energy Services, Inc. | Compositions and methods for improving proppant pack permeability and fracture conductivity in a subterranean well |
US7135231B1 (en) | 2003-07-01 | 2006-11-14 | Fairmont Minerals, Ltd. | Process for incremental coating of proppants for hydraulic fracturing and proppants produced therefrom |
US7066258B2 (en) | 2003-07-08 | 2006-06-27 | Halliburton Energy Services, Inc. | Reduced-density proppants and methods of using reduced-density proppants to enhance their transport in well bores and fractures |
US7086460B2 (en) | 2003-07-14 | 2006-08-08 | Halliburton Energy Services, Inc. | In-situ filters, method of forming same and systems for controlling proppant flowback employing same |
US6832652B1 (en) | 2003-08-22 | 2004-12-21 | Bj Services Company | Ultra low density cementitious slurries for use in cementing of oil and gas wells |
US7040403B2 (en) | 2003-08-27 | 2006-05-09 | Halliburton Energy Services, Inc. | Methods for controlling migration of particulates in a subterranean formation |
BRPI0303442B1 (en) | 2003-09-03 | 2016-05-31 | Mineração Curimbaba Ltda | process for preparing a low density bauxite proppant |
US7032667B2 (en) | 2003-09-10 | 2006-04-25 | Halliburtonn Energy Services, Inc. | Methods for enhancing the consolidation strength of resin coated particulates |
CA2447928C (en) | 2003-11-04 | 2007-09-04 | Global Synfrac Inc. | Proppants and their manufacture |
US7081439B2 (en) | 2003-11-13 | 2006-07-25 | Schlumberger Technology Corporation | Methods for controlling the fluid loss properties of viscoelastic surfactant based fluids |
US7063150B2 (en) | 2003-11-25 | 2006-06-20 | Halliburton Energy Services, Inc. | Methods for preparing slurries of coated particulates |
US20050145385A1 (en) | 2004-01-05 | 2005-07-07 | Nguyen Philip D. | Methods of well stimulation and completion |
US20050173116A1 (en) | 2004-02-10 | 2005-08-11 | Nguyen Philip D. | Resin compositions and methods of using resin compositions to control proppant flow-back |
US20060166834A1 (en) | 2004-02-10 | 2006-07-27 | Halliburton Energy Services, Inc. | Subterranean treatment fluids comprising substantially hydrated cement particulates |
US7341104B2 (en) | 2004-02-10 | 2008-03-11 | Halliburton Energy Services, Inc. | Methods of using substantially hydrated cement particulates in subterranean applications |
US7244492B2 (en) | 2004-03-04 | 2007-07-17 | Fairmount Minerals, Ltd. | Soluble fibers for use in resin coated proppant |
US7789330B2 (en) | 2004-03-15 | 2010-09-07 | Showa Denko K.K. | Roundish fused alumina particles, production process thereof, and resin composition containing the particles |
WO2005103446A1 (en) | 2004-04-05 | 2005-11-03 | Carbo Ceramics, Inc. | Tagged propping agents and related methods |
CN1984769A (en) | 2004-04-12 | 2007-06-20 | 卡博陶粒有限公司 | Coating and/or treating hydraulic fracturing proppants to improve wettability, proppant lubrication, and/or to reduce damage by fracturing fluids and reservoir fluids |
WO2005110942A2 (en) | 2004-05-18 | 2005-11-24 | Services Petroliers Schlumberger | Adaptive cementitious composites for well completions |
US7128158B2 (en) | 2004-05-25 | 2006-10-31 | Halliburton Energy Services, Inc. | Lightweight composite particulates and methods of using such particulates in subterranean applications |
US7213651B2 (en) | 2004-06-10 | 2007-05-08 | Bj Services Company | Methods and compositions for introducing conductive channels into a hydraulic fracturing treatment |
US20060157244A1 (en) | 2004-07-02 | 2006-07-20 | Halliburton Energy Services, Inc. | Compositions comprising melt-processed inorganic fibers and methods of using such compositions |
EA010944B1 (en) | 2004-07-09 | 2008-12-30 | Карбо Керамикс, Инк. | Method for producing solid sintered ceramic particles and particles produced by said method |
US20060016598A1 (en) | 2004-07-21 | 2006-01-26 | Urbanek Thomas W | Lightweight proppant and method of making same |
WO2006023172A2 (en) | 2004-08-16 | 2006-03-02 | Fairmount Minerals, Ltd. | Control of particulate flowback in subterranean formations using elastomeric resin coated proppants |
US7255169B2 (en) * | 2004-09-09 | 2007-08-14 | Halliburton Energy Services, Inc. | Methods of creating high porosity propped fractures |
US7665522B2 (en) | 2004-09-13 | 2010-02-23 | Schlumberger Technology Corporation | Fiber laden energized fluids and methods of use |
AU2005284787A1 (en) | 2004-09-14 | 2006-03-23 | Carbo Ceramics Inc. | Sintered spherical pellets |
WO2006034298A2 (en) | 2004-09-20 | 2006-03-30 | Hexion Specialty Chemicals Inc. | Particles for use as proppants or in gravel packs, methods for making and using the same |
US20060073980A1 (en) | 2004-09-30 | 2006-04-06 | Bj Services Company | Well treating composition containing relatively lightweight proppant and acid |
US7726399B2 (en) | 2004-09-30 | 2010-06-01 | Bj Services Company | Method of enhancing hydraulic fracturing using ultra lightweight proppants |
US7461696B2 (en) | 2004-11-30 | 2008-12-09 | Halliburton Energy Services, Inc. | Methods of fracturing using fly ash aggregates |
US7281581B2 (en) | 2004-12-01 | 2007-10-16 | Halliburton Energy Services, Inc. | Methods of hydraulic fracturing and of propping fractures in subterranean formations |
US7883740B2 (en) | 2004-12-12 | 2011-02-08 | Halliburton Energy Services, Inc. | Low-quality particulates and methods of making and using improved low-quality particulates |
US7322411B2 (en) | 2005-01-12 | 2008-01-29 | Bj Services Company | Method of stimulating oil and gas wells using deformable proppants |
US7334635B2 (en) * | 2005-01-14 | 2008-02-26 | Halliburton Energy Services, Inc. | Methods for fracturing subterranean wells |
US20060162929A1 (en) | 2005-01-26 | 2006-07-27 | Global Synfrac Inc. | Lightweight proppant and method of making same |
US7334636B2 (en) | 2005-02-08 | 2008-02-26 | Halliburton Energy Services, Inc. | Methods of creating high-porosity propped fractures using reticulated foam |
MX2007010667A (en) | 2005-03-01 | 2007-11-08 | Carbo Ceramics Inc | Methods for producing sintered particles from a slurry of an alumina-containing raw material. |
CA2599977C (en) | 2005-03-07 | 2011-01-25 | Baker Hughes Incorporated | Use of coated proppant to minimize abrasive erosion in high rate fracturing operations |
US7308939B2 (en) | 2005-03-09 | 2007-12-18 | Halliburton Energy Services, Inc. | Methods of using polymer-coated particulates |
US7528096B2 (en) | 2005-05-12 | 2009-05-05 | Bj Services Company | Structured composite compositions for treatment of subterranean wells |
US20060272816A1 (en) | 2005-06-02 | 2006-12-07 | Willberg Dean M | Proppants Useful for Prevention of Scale Deposition |
BRPI0502622A (en) | 2005-06-24 | 2007-02-13 | Mineracao Curimbaba Ltda | spherical ceramic propellant for hydraulic fracturing of oil or gas wells and process for forming cavities on the surface of spherical ceramic propellants |
US20070023187A1 (en) | 2005-07-29 | 2007-02-01 | Carbo Ceramics Inc. | Sintered spherical pellets useful for gas and oil well proppants |
-
2007
- 2007-01-17 US US11/624,057 patent/US8562900B2/en active Active
- 2007-08-30 RU RU2008119812/03A patent/RU2381253C1/en active
- 2007-08-30 DK DK12156169.0T patent/DK2500395T3/en active
- 2007-08-30 WO PCT/IB2007/003613 patent/WO2008026076A2/en active Application Filing
- 2007-08-30 DK DK11185274.5T patent/DK2407525T3/en active
- 2007-08-30 EP EP11185274.5A patent/EP2407525B1/en active Active
- 2007-08-30 EP EP12156169.0A patent/EP2500395B1/en active Active
- 2007-08-30 EP EP07825726A patent/EP2066760A2/en not_active Withdrawn
- 2007-08-31 CA CA2600053A patent/CA2600053C/en active Active
- 2007-08-31 MX MX2007010656A patent/MX2007010656A/en active IP Right Grant
-
2009
- 2009-02-26 EG EG2009020269A patent/EG26031A/en active
- 2009-12-09 US US12/633,911 patent/US20100087341A1/en not_active Abandoned
-
2013
- 2013-09-23 US US14/034,169 patent/US20140021659A1/en not_active Abandoned
-
2016
- 2016-05-23 US US15/162,595 patent/US10344206B2/en active Active
-
2019
- 2019-06-07 US US16/434,881 patent/US11732184B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3497008A (en) | 1968-03-05 | 1970-02-24 | Exxon Production Research Co | Method of propping fractures with ceramic particles |
US4068718A (en) | 1975-09-26 | 1978-01-17 | Exxon Production Research Company | Hydraulic fracturing method using sintered bauxite propping agent |
US4427068A (en) | 1982-02-09 | 1984-01-24 | Kennecott Corporation | Sintered spherical pellets containing clay as a major component useful for gas and oil well proppants |
US4427068B1 (en) | 1982-02-09 | 1992-03-24 | Carbo Ceramics Inc | |
US5420174A (en) | 1992-11-02 | 1995-05-30 | Halliburton Company | Method of producing coated proppants compatible with oxidizing gel breakers |
US6059034A (en) | 1996-11-27 | 2000-05-09 | Bj Services Company | Formation treatment method using deformable particles |
US6753299B2 (en) | 2001-11-09 | 2004-06-22 | Badger Mining Corporation | Composite silica proppant material |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009027841A3 (en) * | 2007-08-28 | 2009-08-13 | Imerys | Proppants and anti-flowback additives made from sillimanite minerals, methods of manufacture, and methods of use |
US7737091B2 (en) | 2007-08-28 | 2010-06-15 | Imerys | Proppants and anti-flowback additives made from sillimanite minerals, methods of manufacture, and methods of use |
US7790656B2 (en) | 2007-08-28 | 2010-09-07 | Imerys | Proppants and anti-flowback additives made from sillimanite minerals, methods of manufacture, and methods of use |
WO2009027841A2 (en) * | 2007-08-28 | 2009-03-05 | Imerys | Proppants and anti-flowback additives made from sillimanite minerals, methods of manufacture, and methods of use |
US20200148944A1 (en) * | 2013-06-03 | 2020-05-14 | Imerys Oilfield Minerals, Inc. | Proppants and anti-flowback additives including compositions comprising calcium, multi-foil cross sections, and/or size ranges |
US20160115375A1 (en) * | 2013-06-03 | 2016-04-28 | Imerys Oilfield Minerals, Inc. | Proppants and Anti-Flowback Additives Including Compositions Comprising Calcium, Multi-Foil Cross Sections, and/or Size Ranges |
EP3004422A4 (en) * | 2013-06-03 | 2017-01-11 | Imerys Oilfield Minerals, Inc. | Proppants and anti-flowback additives including compositions comprising calcium, multi-foil cross sections, and/or size ranges |
US9914872B2 (en) | 2014-10-31 | 2018-03-13 | Chevron U.S.A. Inc. | Proppants |
EP3295222A4 (en) * | 2015-05-12 | 2018-05-09 | Conoco Phillips Company | Plastic frack tracer |
WO2017074393A1 (en) * | 2015-10-29 | 2017-05-04 | Multi-Chem Group, Llc | Carrier-free treatment particulates for use in subterranean formations |
GB2556754A (en) * | 2015-10-29 | 2018-06-06 | Multi Chem Group Llc | Carrier-free treatment particulates for use in subterranean formations |
GB2556754B (en) * | 2015-10-29 | 2022-02-09 | Halliburton Energy Services Inc | Carrier-free treatment particulates for use in subterranean formations |
US10240449B1 (en) | 2016-08-11 | 2019-03-26 | Keane Frac, Lp | Methods and materials for hydraulic fracturing |
US10995597B1 (en) | 2016-08-11 | 2021-05-04 | Nextier Completion Solutions Inc. | Methods and materials for hydraulic fracturing |
Also Published As
Publication number | Publication date |
---|---|
RU2008119812A (en) | 2009-11-27 |
EP2407525A1 (en) | 2012-01-18 |
EG26031A (en) | 2012-12-12 |
US10344206B2 (en) | 2019-07-09 |
EP2407525B1 (en) | 2018-10-10 |
US20160264854A1 (en) | 2016-09-15 |
MX2007010656A (en) | 2009-02-19 |
EP2500395A3 (en) | 2013-07-10 |
DK2500395T3 (en) | 2019-02-04 |
US20200123438A1 (en) | 2020-04-23 |
EP2066760A2 (en) | 2009-06-10 |
US20140021659A1 (en) | 2014-01-23 |
US20080053657A1 (en) | 2008-03-06 |
US20100087341A1 (en) | 2010-04-08 |
RU2381253C1 (en) | 2010-02-10 |
WO2008026076A3 (en) | 2008-08-21 |
US8562900B2 (en) | 2013-10-22 |
DK2407525T3 (en) | 2019-01-28 |
CA2600053A1 (en) | 2008-03-01 |
US11732184B2 (en) | 2023-08-22 |
EP2500395A2 (en) | 2012-09-19 |
CA2600053C (en) | 2014-05-13 |
EP2500395B1 (en) | 2018-10-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11732184B2 (en) | Method of manufacture and using rod-shaped proppants and anti-flowback additives | |
EP2197976B1 (en) | Proppants and anti-flowback additives made from sillimanite minerals, methods of manufacture, and methods of use | |
US20100087342A1 (en) | Rod-shaped proppant and anti-flowback additive, method of manufacture, and method of use | |
US20200148944A1 (en) | Proppants and anti-flowback additives including compositions comprising calcium, multi-foil cross sections, and/or size ranges | |
MXPA05011664A (en) | Proppant for hydraulic fracturing of oil and gas wells and process for decreasing or eliminating "flow-back" effect in oil and gas wells". | |
US20090227480A1 (en) | Angular abrasive proppant, process for the preparation thereof and process for hydraulic fracturing of oil and gas wells | |
US10093849B2 (en) | Proppants and anti-flowback additives comprising flash calcined clay, methods of manufacture, and methods of use | |
US20170121592A1 (en) | Method of making proppants and anti-flowback additives using gear pelletizers | |
CA2597880C (en) | Electrofused proppant, method of manufacture, and method of use |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2008119812 Country of ref document: RU |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007825726 Country of ref document: EP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07825726 Country of ref document: EP Kind code of ref document: A2 |