US20060169448A1 - Self-degrading cement compositions and methods of using self-degrading cement compositions in subterranean formations - Google Patents
Self-degrading cement compositions and methods of using self-degrading cement compositions in subterranean formations Download PDFInfo
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- US20060169448A1 US20060169448A1 US11/048,591 US4859105A US2006169448A1 US 20060169448 A1 US20060169448 A1 US 20060169448A1 US 4859105 A US4859105 A US 4859105A US 2006169448 A1 US2006169448 A1 US 2006169448A1
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- United States
- Prior art keywords
- poly
- fracturing fluid
- acid
- degradable material
- degradable
- Prior art date
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Links
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000004568 cement Substances 0.000 title claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 title abstract description 24
- 238000005755 formation reaction Methods 0.000 title abstract description 24
- 238000000034 method Methods 0.000 title description 23
- 239000012530 fluid Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- OKIWLDVQGKRUNR-UHFFFAOYSA-L magnesium;hydrogen phosphate;trihydrate Chemical compound O.O.O.[Mg+2].OP([O-])([O-])=O OKIWLDVQGKRUNR-UHFFFAOYSA-L 0.000 claims abstract description 10
- -1 poly(lactide) Polymers 0.000 claims description 73
- 230000015556 catabolic process Effects 0.000 claims description 25
- 238000006731 degradation reaction Methods 0.000 claims description 25
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000395 magnesium oxide Substances 0.000 claims description 21
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 21
- 229920006237 degradable polymer Polymers 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 11
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 11
- 229920003232 aliphatic polyester Polymers 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 229940065514 poly(lactide) Drugs 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 229920002101 Chitin Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 2
- 229920001710 Polyorthoester Polymers 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229920001308 poly(aminoacid) Polymers 0.000 claims description 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- 239000004677 Nylon Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 229920001778 nylon Polymers 0.000 claims 1
- 150000002905 orthoesters Chemical class 0.000 claims 1
- 239000002745 poly(ortho ester) Substances 0.000 claims 1
- 229920002689 polyvinyl acetate Polymers 0.000 claims 1
- 239000011118 polyvinyl acetate Substances 0.000 claims 1
- 230000004936 stimulating effect Effects 0.000 abstract description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 16
- 239000004310 lactic acid Substances 0.000 description 10
- 235000014655 lactic acid Nutrition 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 239000012510 hollow fiber Substances 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007857 degradation product Substances 0.000 description 6
- 230000001747 exhibiting effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011800 void material Substances 0.000 description 6
- 229920002732 Polyanhydride Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 5
- 239000011236 particulate material Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 150000005323 carbonate salts Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000007836 KH2PO4 Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007281 self degradation Effects 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- 0 *C(C)C(=O)OC Chemical compound *C(C)C(=O)OC 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- AOLNDUQWRUPYGE-UHFFFAOYSA-N 1,4-dioxepan-5-one Chemical compound O=C1CCOCCO1 AOLNDUQWRUPYGE-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000004891 communication Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
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- 230000003252 repetitive effect Effects 0.000 description 1
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- 238000009738 saturating Methods 0.000 description 1
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- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1003—Non-compositional aspects of the coating or impregnation
- C04B20/1011—Temporary coatings
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/30—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing magnesium cements or similar cements
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
-
- 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
- C09K8/66—Compositions based on water or polar solvents
-
- 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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- 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
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
Definitions
- the present invention relates to methods of stimulating a subterranean formation. More particularly, the present invention relates to methods of fracturing subterranean formations using a fracturing fluid comprising a self-degrading cement composition.
- Hydraulic fracturing techniques commonly are used to stimulate subterranean formations to enhance the production of hydrocarbons therefrom.
- Conventional hydraulic fracturing operations commonly involve flowing a fracturing fluid down a well bore and into a hydrocarbon-bearing formation at a pressure sufficient to create or enhance at least one fracture therein.
- Conventional fracturing fluids may comprise, inter alia, viscosifying or gelling agents to increase their viscosity, and often may include proppant particulate materials that may be deposited in the fractures. Once deposited in the resultant fractures, conventional proppant particulate materials are intended to prevent the fractures from closing so as to enhance the flow of hydrocarbons to the well bore, and thereafter to the surface.
- Commonly-used proppant particulate materials include, inter alia, sand, walnut shells, glass beads, metal pellets, ceramic beads, and the like.
- the proppant particulate materials undesirably may settle within the fracturing fluid to some degree before the fracture closes. This may cause the proppant pack to form at an interval different than the desired interval. Further, the viscosifying or gelling agents used in conventional fracturing fluids may form residues within the proppant pack and in the areas of the formation adjacent the fracture, which undesirably may reduce well productivity.
- fracturing operation may depend, at least in part, upon fracture porosity and conductivity once the fracturing operation is stopped and production is begun.
- Traditional fracturing operations place a large volume of proppant particulates into a fracture and the porosity of the resultant packed propped fracture is then related to the interconnected interstitial spaces between the abutting proppant particulates.
- the resultant fracture porosity from a traditional fracturing operation may be closely related to the strength of the placed proppant particulates (if the placed particulates crush then the pieces of broken proppant may plug the interstitial spaces) and the size and shape of the placed particulate (larger, more spherical proppant particulates generally yield increased interstitial spaces between the particulates).
- One attempt to address problems that may be inherent in tight proppant particulate packs involves placing a much-reduced volume of proppant particulates in a fracture to create what is referred to herein as a partial monolayer or “high-porosity” fracture.
- the proppant particulates within the fracture may be widely spaced, but still may be sufficient to desirably hold open the fracture and allow for production.
- Such operations may allow for increased fracture conductivity due, at least in part, to the fact the produced fluids may flow around widely spaced proppant particulates rather than merely flow through the relatively small interstitial spaces in a packed proppant bed.
- cement compositions as proppant materials.
- the cement compositions that have been used in such fashion commonly have comprised particulate carbonate salts.
- Such salts were intended to have dissolved out of the cement composition, theoretically enhancing the permeability of the resultant set cement sheath to a degree that may facilitate greater flow of formation fluids (e.g., hydrocarbons) to the well bore.
- Formation fluids e.g., hydrocarbons
- Carbonate salts generally require treatment with an acid before they may dissolve out of the cement composition.
- conventional operations that have employed proppant materials comprising cement compositions generally have not enhanced the permeability of the formation to the extent desired.
- the present invention relates to methods of stimulating a subterranean formation. More particularly, the present invention relates to methods of fracturing subterranean formations using a fracturing fluid comprising a self-degrading cement composition.
- composition of the present invention is a fracturing fluid comprising a self-degrading cement composition that comprises an acid source, a base source, a water source, and a degradable material.
- FIG. 1 illustrates the amount of void space that might be demonstrated in an example of a fracture having a porosity of about 80%.
- FIG. 2 illustrates an exemplary relationship of the time- and temperature-dependence of the degradation of an exemplary degradable material.
- FIG. 3 illustrates an exemplary relationship of the time- and temperature-dependence of the degradation of an exemplary degradable material.
- the present invention relates to methods of stimulating a subterranean formation. More particularly, the present invention relates to methods of fracturing subterranean formations using a fracturing fluid comprising a self-degrading cement composition.
- the self-degrading cement compositions suitable for use in the fracturing fluids of the present invention generally comprise a mixture of a degradable material, an acid source, a base source, and a water source.
- the fracturing fluids may be placed in a subterranean formation at a pressure sufficient to create or enhance at least one fracture therein.
- the self-degrading cement compositions present within the fracturing fluids then may set within the at least one created or enhanced fracture to form a solid mass, and the degradable material within the cement composition then may degrade.
- the degradation of the degradable material may create voids within the solid mass that may permit or enhance fluid communication between the formation and a well bore penetrating the formation.
- the degradable material used may comprise a mixture of fibers and spherical particles, which may, inter alia, enhance the interconnectivity of voids that may be produced in the solid mass.
- the portion of the solid mass that does not degrade may be capable of preventing the at least one created or enhanced fracture from closing (e.g., the portion of the solid mass that does not degrade may form “pillars” within the at least one created or enhanced fracture that may prevent its closure).
- the portion of the solid mass that does not degrade may form a partial monolayer in the at least one created or enhanced fracture.
- Porosity values expressed herein are unstressed porosities (e.g., the porosity before a fracture in the formation has closed or applied any substantial mechanical stress).
- the methods of the present invention may be used, inter alia, to create high-porosity fractures having increased conductivity as compared to a traditional packed propped fracture.
- Certain embodiments of the fracturing fluids and methods of the present invention may achieve such increased conductivity by forming “pillars” within the resultant solid mass within the fracture, which pillars may prevent the fracture from closing.
- the fractures that may be created or enhanced by the fracturing fluids and methods of the present invention may facilitate the formation of a conductive fracture with porosity much greater than about 40% while still maintaining enough conductive channels for production.
- Certain embodiments of the present invention may form fractures exhibiting a porosity of at least about 50%.
- Other embodiments of the present invention may form fractures exhibiting a porosity of at least about 60%, while still other embodiments may form fractures exhibiting a porosity of at least about 70%.
- Other embodiments of the present invention may be used to form fractures exhibiting a porosity of at least about 80%, while still other embodiments may form fractures exhibiting a porosity of at least about 90%.
- FIG. 1 illustrates the degree of void space that may be present in a fracture exhibiting a porosity of about 80%.
- the fracturing fluids and methods of the present invention may achieve increased conductivity within the formation, at least in part, because the high-porosity fractures they form allow for increased levels of open channels. With a high-porosity fracture there may be more open spaces in the propped fracture that may remain open, even under severe closure stresses, than may be found in traditional applications (including, inter alia, those that may involve high proppant loading).
- the methods of the present invention may increase the available space for production.
- a broad variety of acid sources and base sources may be suitable for use in the fracturing fluids of the present invention.
- suitable acid sources include, inter alia, magnesium chloride (MgCl 2 ), potassium phosphate monobasic (KH 2 PO 4 ), phosphoric acid (H 3 PO 4 ), magnesium sulfate (MgSO 4 ), and ammonium phosphate monobasic (NH 2 PO 4 ).
- suitable base sources include, inter alia, magnesium oxide (MgO), and ammonia (NH 3 ).
- An example of a suitable source of magnesium oxide is commercially available from Martin Marietta under the trade name “MagChem 10.”
- An example of a suitable source of potassium phosphate monobasic is commercially available from Fisher Scientific.
- an acid source and base source may be chosen that may react so as to form an acid-base cement.
- magnesium oxide may be chosen as a base source
- potassium phosphate monobasic may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having the chemical formula MgKPO 4 .6H 2 O.
- magnesium oxide may be chosen as a base source, and magnesium chloride may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having three oxychloride phases; one oxychloride phase may have the chemical formula 5 Mg(OH 2 )MgCl 2 .8H 2 O, which may be referred to as “5-form.”
- magnesium oxide may be chosen as a base source, and phosphoric acid may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having the chemical formula MgHPO 4 .3H 2 O.
- magnesium oxide may be chosen as a base source, and magnesium sulfate may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having four possible oxysulfate phases; one oxysulfate phase may have the chemical formula 3 Mg(OH) 2 MgSO 4 .8H 2 O, which may be referred to as “3-form.”
- magnesium oxide may be chosen as a base source, and ammonium phosphate monobasic may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having the chemical formula Mg(NH) 4 PO 4 .6H 2 O.
- a broad variety of acid sources and base sources may be used, and a broad variety of acid-base cements may be produced, in accordance with the present invention, including, but not limited to, those acid sources, base sources, and acid-base cements that are disclosed in “Acid-Base Cements: Their Biomedical and Industrial Applications,” by Alan D. Wilson and John W. Nicholson (Cambridge Univ. Press, 1993).
- the acid source and base source may be present in a stoichiometric amount.
- magnesium oxide used as a base source
- potassium phosphate monobasic used as an acid source
- their relative concentrations may be illustrated by EQUATION 1 below. 0.15 grams MgO+0.52 grams KH 2 PO 4 +0.33 grams H 2 O ⁇ 1 gram MgKPO 4 .6H 2 O.
- EQUATION 1 is exemplary only, and may be modified as one of ordinary skill in the art will recognize, with the benefit of this disclosure.
- additional quantities of magnesium oxide may be included, in amounts in the range of from about 1% excess by weight to about 25% excess by weight.
- the fracturing fluids of the present invention generally comprise a water source.
- the water source may comprise fresh water, salt water (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated salt water), or seawater.
- salt water e.g., water containing one or more salts dissolved therein
- brine e.g., saturated salt water
- seawater any water source may be used provided that it does not contain an excess of compounds that may adversely affect other components in the fracturing fluid.
- the degradable material may be a degradable polymer.
- a polymer is considered to be “degradable” herein if its degradation may be due to, inter alia, chemical and/or radical processes (e.g., hydrolysis, oxidation, enzymatic degradation, UV radiation, and the like).
- the degradability of a polymer depends at least in part on its backbone structure. For instance, the presence of hydrolyzable and/or oxidizable linkages in the backbone often yields a material that will degrade as described herein.
- the rates at which such polymers degrade are dependent on factors such as, inter alia, the type of repetitive unit, composition, sequence, length, molecular geometry, molecular weight, morphology (e.g., crystallinity, size of spherulites, and orientation), hydrophilicity, hydrophobicity, surface area, and additives.
- the manner in which the polymer degrades also may be affected by the environment to which the polymer is exposed, e.g., temperature, presence of moisture, oxygen, microorganisms, enzymes, pH, and the like.
- Such suitable polymers may be prepared by polycondensation reactions, ring-opening polymerizations, free radical polymerizations, anionic polymerizations, carbocationic polymerizations, coordinative ring-opening polymerizations, as well as by any other suitable process.
- Exemplary polymers suitable for use in the present invention include, but are not limited to, polysaccharides such as dextran or cellulose; chitin; chitosan; proteins; aliphatic polyesters; poly(lactide); poly(glycolide); poly( ⁇ -caprolactone); poly(hydroxy ester ethers); poly(hydroxybutyrate); poly(anhydrides); aliphatic polycarbonates; poly(orthoesters); poly(amino acids); poly(ethylene oxide); polyphosphazenes; poly ether esters; polyester amides; polyamides; and copolymers and blends thereof.
- polysaccharides such as dextran or cellulose
- chitin such as dextran or cellulose
- chitosan proteins
- aliphatic polyesters poly(lactide); poly(glycolide); poly( ⁇ -caprolactone); poly(hydroxy ester ethers); poly(hydroxybutyrate); poly(anhydrides); aliphatic polycarbonates
- the degradable material is a degradable polymer
- the degradable polymer may be an aliphatic polyester or a polyanhydride.
- Other degradable polymers that are subject to hydrolytic degradation also may be used.
- Aliphatic polyesters degrade chemically, inter alia, by hydrolytic cleavage.
- Hydrolysis can be catalyzed by either acids or bases.
- carboxylic end groups may be formed during chain scission, and this may enhance the rate of further hydrolysis. This mechanism is known in the art as “autocatalysis” and is thought to make polyester matrices more bulk-eroding.
- Suitable aliphatic polyesters have the general formula of repeating units shown below: where n is an integer between 75 and 10,000 and R is selected from the group consisting of hydrogen, alkyl, aryl, alkylaryl, acetyl, heteroatoms, and mixtures thereof.
- the aliphatic polyester may be poly(lactide).
- Poly(lactide) is synthesized either from lactic acid by a condensation reaction or, more commonly, by ring-opening polymerization of cyclic lactide monomer.
- poly(lactic acid) refers to writ of formula I without any limitation as to how the polymer was made such as from lactides, lactic acid, or oligomers, and without reference to the degree of polymerization or level of plasticization.
- the lactide monomer exists generally in three different forms: two stereoisomers (L- and D-lactide) and racemic D,L-lactide (meso-lactide).
- the oligomers of lactic acid and the oligomers of lactide are defined by the formula: where m is an integer in the range of from greater than or equal to about 2 to less than or equal to about 75. In certain embodiments, m may be an integer in the range of from greater than or equal to about 2 to less than or equal to about 10. These limits may correspond to number average molecular weights below about 5,400 and below about 720, respectively.
- the chirality of the lactide units provides a means to adjust, inter alia, degradation rates, as well as physical and mechanical properties.
- Poly(L-lactide), for instance, is a semicrystalline polymer with a relatively slow hydrolysis rate. This could be desirable in applications of the present invention where a slower degradation of the degradable material is desired. Poly(D,L-lactide) may be a more amorphous polymer with a resultant faster hydrolysis rate. This may be suitable for other applications where a more rapid degradation may be appropriate.
- the stereoisomers of lactic acid may be used individually, or may be combined in accordance with the present invention. Additionally, they may be copolymerized with, for example, glycolide or other monomers like ⁇ -caprolactone, 1,5-dioxepan-2-one, trimethylene carbonate, or other suitable monomers to obtain polymers with different properties or degradation times.
- the lactic acid stereoisomers can be modified by blending high and low molecular weight polylactide or by blending polylactide with other polyesters.
- polylactide is used as the degradable material
- certain preferred embodiments employ a mixture of the D and L stereoisomers, designed so as to provide a desired degradation time and/or rate.
- Aliphatic polyesters useful in the present invention may be prepared by substantially any of the conventionally known manufacturing methods such as those described in U.S. Pat. Nos. 6,323,307; 5,216,050; 4,387,769; 3,912,692; and 2,703,316, the relevant disclosures of which are incorporated herein by reference.
- Polyanhydrides are another type of degradable polymer that may be suitable for use in the present invention. Polyanhydride hydrolysis proceeds, inter alia, via free carboxylic acid chain-ends to yield carboxylic acids as final degradation products. Their erosion time can be varied over a broad range of changes in the polymer backbone.
- suitable polyanhydrides include poly(adipic anhydride), poly(suberic anhydride), poly(sebacic anhydride), and poly(dodecanedioic anhydride).
- Other suitable examples include, but are not limited to, poly(maleic anhydride) and poly(benzoic anhydride).
- degradable polymers may depend on several factors including, but not limited to, the composition of the repeat units, flexibility of the chain, presence of polar groups, molecular mass, degree of branching, crystallinity, and orientation.
- short chain branches reduce the degree of crystallinity of polymers while long chain branches lower the melt viscosity and impart, inter alia, extensional viscosity with tension-stiffening behavior.
- the properties of the material utilized further may be tailored by blending, and copolymerizing it with another polymer, or by a change in the macromolecular architecture (e.g., hyper-branched polymers, star-shaped, or dendrimers, and the like).
- any such suitable degradable polymers can be tailored by introducing select functional groups along the polymer chains.
- poly(phenyllactide) will degrade at about 1 ⁇ 5th of the rate of racemic poly(lactide) at a pH of 7.4 at 55° C.
- One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine the appropriate functional groups to introduce to the polymer chains to achieve the desired physical properties of the degradable polymers.
- the degradable material may have any shape, including, but not limited to, particles having the physical shape of platelets, shavings, flakes, ribbons, rods, strips, spheroids, toroids, pellets, tablets, or any other physical shape.
- the degradable material used may comprise a mixture of fibers and spherical particles.
- the degradable material used may comprise a self-degrading fiber that comprises an outer shell and a core liquid, wherein the outer shell comprises a degradable polymer and substantially retains the core liquid.
- the outer shell may comprise a degradable polymer that is subject to hydrolytic degradation.
- the core liquid may comprise a liquid that is able to at least partially facilitate or catalyze the hydrolysis of the degradable polymer in the outer shell.
- the self-degrading fiber may comprise a coating on the outer shell and/or a suitable additive within the core liquid, e.g., an additive chosen to interact with the degradable polymer, its degradation products, or the surrounding subterranean environment.
- the outer shell may be non-porous.
- Methods of making the self-degrading fibers described herein include any suitable method for forming hollow fibers.
- One such method involves extruding hollow fibers made from a desired degradable polymer; soaking the hollow fibers in a liquid that will be the core liquid; saturating the hollow fibers with the liquid; and drying the exterior of the outer core of the fibers in such a manner that the liquid is retained in the hollow fibers and becomes a core liquid.
- Another method involves extruding a spinning solution of a chosen degradable polymer from an annular slit of a double pipe orifice to form a sheath solution while simultaneously extruding a liquid through the inside pipe of the double pipe orifice, to form a core liquid within the hollow fibers.
- Another method involves using capillary action to place the core liquid in an already-formed suitable hollow fiber. Other suitable methods may be used as well.
- degradable material In choosing the appropriate degradable material, one should consider the degradation products that will result. Also, these degradation products should not adversely affect other operations or components.
- the choice of degradable material also can depend, at least in part, on the conditions of the well, e.g., well bore temperature. For instance, lactides have been found to be suitable for lower temperature wells, including those within the range of 60° F. to 150° F., and polylactides have been found to be suitable for well bore temperatures above this range.
- the degradation of the degradable material could result in a final degradation product having the potential to affect the pH of the fracturing fluid.
- the degradable material is poly(lactic acid)
- the degradation of the poly(lactic acid) to produce lactic acid may alter the pH of the fracturing fluid.
- a buffer compound may be included within the fracturing fluids of the present invention in an amount sufficient to neutralize the final degradation product. Examples of suitable buffer compounds include, but are not limited to, calcium carbonate, magnesium oxide, ammonium acetate, and the like.
- a buffer compound to include in the fracturing fluid for a particular application.
- An example of a suitable buffer comprises ammonium acetate and is commercially available from Halliburton Energy Services, Inc., under the trade name “BA-20.”
- a preferable result may be achieved if the degradable material degrades slowly over time as opposed to instantaneously.
- a suitable source of degradable material is a poly(lactic acid) that is commercially available from Cargill Dow under the trade name “6250D.”
- the mixture of a degradable material and acid/base cements in the fracturing fluids of the present invention When the mixture of a degradable material and acid/base cements in the fracturing fluids of the present invention is placed in a subterranean formation, the mixture may begin to degrade over time in a controllable fashion.
- a synthetic sea water solution was prepared by adding 41.953 grams of sea salt to one liter of deionized water. Next, 1.33 grams of sodium p-toluene sulfonate was added to the sea water solution to form a solution that was 6.919 mM in sodium p-toluene sulfonate. Next, one gram of 6250D or 5639A was placed in a one liter round-bottom flask containing 500 mL of synthetic sea water solution. A reflux condenser then was placed on each flask, and the contents were heated to 75, 85 or 95° C.
- FIG. 2 illustrates the time- and temperature-dependence of the generation of lactic acid caused by the degradation of 6250D
- FIG. 3 illustrates the time- and temperature-dependence of the generation of lactic acid caused by the degradation of 5639A.
- the fracturing fluids of the present invention may be prepared in a variety of ways.
- magnesium oxide and potassium phosphate may be added in dry form to a water source.
- a degradable material then may be added to the mixture to form a fracturing fluid of the present invention.
- the degradable material may be present in the fracturing fluids in an amount sufficient to provide a desired degree of void space in the solid mass that may form in the created or enhanced fracture.
- the void space may result from the degradation of the degradable material, and also may result from subsequent reactions that may occur between the acid-base cement and an acid byproduct that may be produced by degradation of the degradable material.
- Table 1 demonstrates the relationship that may exist between the concentration of poly(lactic acid) in the fracturing fluids and the degree of void space that may result in the solid mass.
- the fracturing fluids of the present invention may include other additives, such as, but not limited to, a set retarder.
- the water source may combine with the dry materials in the fracturing fluid to form what may be referred to as a “hydrate,” e.g., a solid compound comprising water molecules that may combine in a definite ratio.
- the water molecules within the hydrate may provide a hydrolysis source for the degradable material.
- An example of one embodiment of a fracturing fluid of the present invention may be prepared by preparing a two-component dry blend that comprised 22.7% magnesium oxide by weight and 77.3% potassium phosphate by weight. Next, poly(lactic acid) may be added in an amount equal to about 55% by weight of the two-component dry blend, thus forming a three-component dry blend. Water then may be added in a mass ratio of one part water to three parts dry blend.
- sodium borate (among other additives) may be added; in certain embodiments of the present invention, the sodium borate may be added in an amount in the range of from less than about 8% by weight of the magnesium oxide.
- Sample compositions were formed as follows. First, 7.58 grams of magnesium oxide were dry blended with 25.75 grams of potassium phosphate monobasic crystals (KH 2 PO 4 ), and mixed with 16.67 grams of tap water. The mixture was stirred for some time, and poly(lactic acid) (“6250D”) was added, generally in an amount in the range of from about 35% by weight to about 40% by weight. Certain of the sample compositions further comprised an acid-base cement referred to as Newberyite, and having the chemical formula MgH(PO 4 ).3H 2 O. Among other things, Newberyite is thought to impart strength-enhancing properties to the sample composition, and the additional water that Newberyite may supply may facilitate hydrolysis of the degradable material (6250D, in this example).
- Newberyite is thought to impart strength-enhancing properties to the sample composition, and the additional water that Newberyite may supply may facilitate hydrolysis of the degradable material (6250D, in this example).
- Table 2 sets forth the respective amounts of 6250D and Newberyite included in a particular sample composition. TABLE 2 Sample Poly(lactic acid) Composition (“6250D”) Newberyite 1 20 grams Not added 2 20 grams Not added 3 20 grams 10 grams 4 15 grams 10 grams 5 15 grams Not added 6 20 grams 10 grams 7 20 grams Not added 8 20 grams 10 grams
- each sample composition was placed in a 20 mL plastic cylinder, and was allowed to set therein into a hard rod. Each rod then was left for a designated cure time at room temperature. Next, the set rod was taken out of the cylinder and either tested for compressibility or directly placed in a bomb supplied by PARR Instrument Company, Moline, Ill. Among other things, the bomb prevented the escape of water that may have been present in the set rod. The bomb was heated in a stove at 250° F. After a time, usually 24 hours, the bomb was removed from the stove, and its contents were observed to see whether or not degradation occurred.
- sample compositions were tested for compressibility using an apparatus supplied by Tinius Olsen company of Willow Grove, Pa. The procedure was performed as follows. After the sample composition had cured and set into a hard rod, the rod was cut down to a 1 inch diameter and a 3 inch length. Two faces of the rod were smoothed. The rod then was placed under the Tinius Olsen compressibility load cell and subjected to a displacement load at a rate of 0.07 inches per minute. The maximum loading in psi that each rod could withstand until failure was recorded.
- Example 1 demonstrates, inter alia, that the combination of a degradable material and an acid-base cement may be suitable for use in the methods of the present invention.
Abstract
Fracturing fluids for stimulating subterranean formations are provided. More particularly, fracturing fluids comprising self-degrading cement compositions are provided. An example of a composition is a fracturing fluid comprising a self-degrading cement composition that comprises an acid source, a base source, a water source, and a degradable material. Certain embodiments of the fracturing fluids also may comprise Newberyite, among other things.
Description
- The present invention relates to methods of stimulating a subterranean formation. More particularly, the present invention relates to methods of fracturing subterranean formations using a fracturing fluid comprising a self-degrading cement composition.
- Hydraulic fracturing techniques commonly are used to stimulate subterranean formations to enhance the production of hydrocarbons therefrom. Conventional hydraulic fracturing operations commonly involve flowing a fracturing fluid down a well bore and into a hydrocarbon-bearing formation at a pressure sufficient to create or enhance at least one fracture therein.
- Conventional fracturing fluids may comprise, inter alia, viscosifying or gelling agents to increase their viscosity, and often may include proppant particulate materials that may be deposited in the fractures. Once deposited in the resultant fractures, conventional proppant particulate materials are intended to prevent the fractures from closing so as to enhance the flow of hydrocarbons to the well bore, and thereafter to the surface. Commonly-used proppant particulate materials include, inter alia, sand, walnut shells, glass beads, metal pellets, ceramic beads, and the like.
- When the fracturing fluid comprising proppant particulate materials has been placed in the formation, the proppant particulate materials undesirably may settle within the fracturing fluid to some degree before the fracture closes. This may cause the proppant pack to form at an interval different than the desired interval. Further, the viscosifying or gelling agents used in conventional fracturing fluids may form residues within the proppant pack and in the areas of the formation adjacent the fracture, which undesirably may reduce well productivity.
- The success of a fracturing operation may depend, at least in part, upon fracture porosity and conductivity once the fracturing operation is stopped and production is begun. Traditional fracturing operations place a large volume of proppant particulates into a fracture and the porosity of the resultant packed propped fracture is then related to the interconnected interstitial spaces between the abutting proppant particulates. Thus, the resultant fracture porosity from a traditional fracturing operation may be closely related to the strength of the placed proppant particulates (if the placed particulates crush then the pieces of broken proppant may plug the interstitial spaces) and the size and shape of the placed particulate (larger, more spherical proppant particulates generally yield increased interstitial spaces between the particulates).
- One attempt to address problems that may be inherent in tight proppant particulate packs involves placing a much-reduced volume of proppant particulates in a fracture to create what is referred to herein as a partial monolayer or “high-porosity” fracture. In such operations the proppant particulates within the fracture may be widely spaced, but still may be sufficient to desirably hold open the fracture and allow for production. Such operations may allow for increased fracture conductivity due, at least in part, to the fact the produced fluids may flow around widely spaced proppant particulates rather than merely flow through the relatively small interstitial spaces in a packed proppant bed.
- Successful placement of a partial monolayer of proppant particulates presents unique challenges in the relative densities of the particulates versus the carrier fluid. Furthermore, placing a proppant particulate that tends to crush or embed under pressure may allow portions of the fracture to pinch or close once the fracturing pressure is released.
- Conventional attempts to address the problems described above have involved, inter alia, the use of cement compositions as proppant materials. The cement compositions that have been used in such fashion commonly have comprised particulate carbonate salts. Such salts were intended to have dissolved out of the cement composition, theoretically enhancing the permeability of the resultant set cement sheath to a degree that may facilitate greater flow of formation fluids (e.g., hydrocarbons) to the well bore. Carbonate salts, however, generally require treatment with an acid before they may dissolve out of the cement composition. Treating the cement compositions that comprise carbonate salts with an acid, after the cement compositions have been placed within the subterranean formation, has been problematic, because such acids may tend to find the path of least resistance within the cement composition, which may result in uneven contact between the acid and the cement composition, thereby causing uneven removal of carbonate salt particulates therefrom. Thus, conventional operations that have employed proppant materials comprising cement compositions generally have not enhanced the permeability of the formation to the extent desired.
- The present invention relates to methods of stimulating a subterranean formation. More particularly, the present invention relates to methods of fracturing subterranean formations using a fracturing fluid comprising a self-degrading cement composition.
- An example of a composition of the present invention is a fracturing fluid comprising a self-degrading cement composition that comprises an acid source, a base source, a water source, and a degradable material.
- The features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of the embodiments that follows.
- A more complete understanding of the present disclosure and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying figures, wherein:
-
FIG. 1 illustrates the amount of void space that might be demonstrated in an example of a fracture having a porosity of about 80%. -
FIG. 2 illustrates an exemplary relationship of the time- and temperature-dependence of the degradation of an exemplary degradable material. -
FIG. 3 illustrates an exemplary relationship of the time- and temperature-dependence of the degradation of an exemplary degradable material. - While the present invention is susceptible to various modifications and alternative forms, specific exemplary embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
- The present invention relates to methods of stimulating a subterranean formation. More particularly, the present invention relates to methods of fracturing subterranean formations using a fracturing fluid comprising a self-degrading cement composition.
- The self-degrading cement compositions suitable for use in the fracturing fluids of the present invention generally comprise a mixture of a degradable material, an acid source, a base source, and a water source.
- Generally, according to certain embodiments of the present invention, the fracturing fluids may be placed in a subterranean formation at a pressure sufficient to create or enhance at least one fracture therein. The self-degrading cement compositions present within the fracturing fluids then may set within the at least one created or enhanced fracture to form a solid mass, and the degradable material within the cement composition then may degrade. In certain embodiments of the present invention, the degradation of the degradable material may create voids within the solid mass that may permit or enhance fluid communication between the formation and a well bore penetrating the formation. In certain embodiments of the present invention, the degradable material used may comprise a mixture of fibers and spherical particles, which may, inter alia, enhance the interconnectivity of voids that may be produced in the solid mass. In certain embodiments of the present invention, the portion of the solid mass that does not degrade may be capable of preventing the at least one created or enhanced fracture from closing (e.g., the portion of the solid mass that does not degrade may form “pillars” within the at least one created or enhanced fracture that may prevent its closure). In certain embodiments of the present invention, the portion of the solid mass that does not degrade may form a partial monolayer in the at least one created or enhanced fracture.
- I. High-Porosity Propped Fractures
- Porosity values expressed herein are unstressed porosities (e.g., the porosity before a fracture in the formation has closed or applied any substantial mechanical stress).
- The methods of the present invention may be used, inter alia, to create high-porosity fractures having increased conductivity as compared to a traditional packed propped fracture. Certain embodiments of the fracturing fluids and methods of the present invention may achieve such increased conductivity by forming “pillars” within the resultant solid mass within the fracture, which pillars may prevent the fracture from closing.
- The fractures that may be created or enhanced by the fracturing fluids and methods of the present invention may facilitate the formation of a conductive fracture with porosity much greater than about 40% while still maintaining enough conductive channels for production. Certain embodiments of the present invention may form fractures exhibiting a porosity of at least about 50%. Other embodiments of the present invention may form fractures exhibiting a porosity of at least about 60%, while still other embodiments may form fractures exhibiting a porosity of at least about 70%. Other embodiments of the present invention may be used to form fractures exhibiting a porosity of at least about 80%, while still other embodiments may form fractures exhibiting a porosity of at least about 90%.
FIG. 1 illustrates the degree of void space that may be present in a fracture exhibiting a porosity of about 80%. - The fracturing fluids and methods of the present invention may achieve increased conductivity within the formation, at least in part, because the high-porosity fractures they form allow for increased levels of open channels. With a high-porosity fracture there may be more open spaces in the propped fracture that may remain open, even under severe closure stresses, than may be found in traditional applications (including, inter alia, those that may involve high proppant loading).
- By increasing the percentage of open spaces within a propped fracture, the methods of the present invention, inter alia, may increase the available space for production.
- II. Acid Sources, Base Sources and Water Sources
- A broad variety of acid sources and base sources may be suitable for use in the fracturing fluids of the present invention. Examples of suitable acid sources include, inter alia, magnesium chloride (MgCl2), potassium phosphate monobasic (KH2PO4), phosphoric acid (H3PO4), magnesium sulfate (MgSO4), and ammonium phosphate monobasic (NH2PO4). Examples of suitable base sources include, inter alia, magnesium oxide (MgO), and ammonia (NH3). An example of a suitable source of magnesium oxide is commercially available from Martin Marietta under the trade name “
MagChem 10.” An example of a suitable source of potassium phosphate monobasic is commercially available from Fisher Scientific. - Generally, an acid source and base source may be chosen that may react so as to form an acid-base cement. For example, magnesium oxide may be chosen as a base source, and potassium phosphate monobasic may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having the chemical formula MgKPO4.6H2O. As another example, magnesium oxide may be chosen as a base source, and magnesium chloride may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having three oxychloride phases; one oxychloride phase may have the
chemical formula 5 Mg(OH2)MgCl2.8H2O, which may be referred to as “5-form.” As another example, magnesium oxide may be chosen as a base source, and phosphoric acid may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having the chemical formula MgHPO4.3H2O. As still another example, magnesium oxide may be chosen as a base source, and magnesium sulfate may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having four possible oxysulfate phases; one oxysulfate phase may have the chemical formula 3 Mg(OH)2MgSO4.8H2O, which may be referred to as “3-form.” As still another example, magnesium oxide may be chosen as a base source, and ammonium phosphate monobasic may be chosen as an acid source, so that in the presence of water they may react to produce an acid-base cement having the chemical formula Mg(NH)4PO4.6H2O. A broad variety of acid sources and base sources may be used, and a broad variety of acid-base cements may be produced, in accordance with the present invention, including, but not limited to, those acid sources, base sources, and acid-base cements that are disclosed in “Acid-Base Cements: Their Biomedical and Industrial Applications,” by Alan D. Wilson and John W. Nicholson (Cambridge Univ. Press, 1993). - Generally, the acid source and base source may be present in a stoichiometric amount. For example, in certain embodiments of the present invention wherein magnesium oxide is used as a base source and potassium phosphate monobasic is used as an acid source, their relative concentrations may be illustrated by EQUATION 1 below.
0.15 grams MgO+0.52 grams KH2PO4+0.33 grams H2O→1 gram MgKPO4.6H2O. EQUATION 1:
EQUATION 1 is exemplary only, and may be modified as one of ordinary skill in the art will recognize, with the benefit of this disclosure. For example, additional quantities of magnesium oxide may be included, in amounts in the range of from about 1% excess by weight to about 25% excess by weight. - The fracturing fluids of the present invention generally comprise a water source. The water source may comprise fresh water, salt water (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated salt water), or seawater. Generally, any water source may be used provided that it does not contain an excess of compounds that may adversely affect other components in the fracturing fluid.
- III. Degradable Materials
- A broad variety of materials may be suitable as the degradable materials in the fracturing fluids of the present invention. In certain embodiments of the present invention, the degradable material may be a degradable polymer. A polymer is considered to be “degradable” herein if its degradation may be due to, inter alia, chemical and/or radical processes (e.g., hydrolysis, oxidation, enzymatic degradation, UV radiation, and the like). The degradability of a polymer depends at least in part on its backbone structure. For instance, the presence of hydrolyzable and/or oxidizable linkages in the backbone often yields a material that will degrade as described herein. The rates at which such polymers degrade are dependent on factors such as, inter alia, the type of repetitive unit, composition, sequence, length, molecular geometry, molecular weight, morphology (e.g., crystallinity, size of spherulites, and orientation), hydrophilicity, hydrophobicity, surface area, and additives. The manner in which the polymer degrades also may be affected by the environment to which the polymer is exposed, e.g., temperature, presence of moisture, oxygen, microorganisms, enzymes, pH, and the like.
- Suitable examples of degradable polymers that may be used in accordance with the present invention include, but are not limited to, those described in the publication of Advances in Polymer Science, Vol. 157 entitled “Degradable Aliphatic Polyesters,” edited by A. C. Albertsson, pages 1-138. Specific examples include homopolymers, random, block, graft, and star- and hyper-branched aliphatic polyesters. Such suitable polymers may be prepared by polycondensation reactions, ring-opening polymerizations, free radical polymerizations, anionic polymerizations, carbocationic polymerizations, coordinative ring-opening polymerizations, as well as by any other suitable process. Exemplary polymers suitable for use in the present invention include, but are not limited to, polysaccharides such as dextran or cellulose; chitin; chitosan; proteins; aliphatic polyesters; poly(lactide); poly(glycolide); poly(ε-caprolactone); poly(hydroxy ester ethers); poly(hydroxybutyrate); poly(anhydrides); aliphatic polycarbonates; poly(orthoesters); poly(amino acids); poly(ethylene oxide); polyphosphazenes; poly ether esters; polyester amides; polyamides; and copolymers and blends thereof. In certain exemplary embodiments of the present invention wherein the degradable material is a degradable polymer, the degradable polymer may be an aliphatic polyester or a polyanhydride. Other degradable polymers that are subject to hydrolytic degradation also may be used.
- Aliphatic polyesters degrade chemically, inter alia, by hydrolytic cleavage. Hydrolysis can be catalyzed by either acids or bases. Generally, during the hydrolysis, carboxylic end groups may be formed during chain scission, and this may enhance the rate of further hydrolysis. This mechanism is known in the art as “autocatalysis” and is thought to make polyester matrices more bulk-eroding.
- Suitable aliphatic polyesters have the general formula of repeating units shown below:
where n is an integer between 75 and 10,000 and R is selected from the group consisting of hydrogen, alkyl, aryl, alkylaryl, acetyl, heteroatoms, and mixtures thereof. In certain embodiments of the present invention wherein an aliphatic polyester is used, the aliphatic polyester may be poly(lactide). Poly(lactide) is synthesized either from lactic acid by a condensation reaction or, more commonly, by ring-opening polymerization of cyclic lactide monomer. Since both lactic acid and lactide can achieve the same repeating unit, the general term poly(lactic acid) as used herein refers to writ of formula I without any limitation as to how the polymer was made such as from lactides, lactic acid, or oligomers, and without reference to the degree of polymerization or level of plasticization. - The lactide monomer exists generally in three different forms: two stereoisomers (L- and D-lactide) and racemic D,L-lactide (meso-lactide). The oligomers of lactic acid and the oligomers of lactide are defined by the formula:
where m is an integer in the range of from greater than or equal to about 2 to less than or equal to about 75. In certain embodiments, m may be an integer in the range of from greater than or equal to about 2 to less than or equal to about 10. These limits may correspond to number average molecular weights below about 5,400 and below about 720, respectively. The chirality of the lactide units provides a means to adjust, inter alia, degradation rates, as well as physical and mechanical properties. Poly(L-lactide), for instance, is a semicrystalline polymer with a relatively slow hydrolysis rate. This could be desirable in applications of the present invention where a slower degradation of the degradable material is desired. Poly(D,L-lactide) may be a more amorphous polymer with a resultant faster hydrolysis rate. This may be suitable for other applications where a more rapid degradation may be appropriate. The stereoisomers of lactic acid may be used individually, or may be combined in accordance with the present invention. Additionally, they may be copolymerized with, for example, glycolide or other monomers like ε-caprolactone, 1,5-dioxepan-2-one, trimethylene carbonate, or other suitable monomers to obtain polymers with different properties or degradation times. Additionally, the lactic acid stereoisomers can be modified by blending high and low molecular weight polylactide or by blending polylactide with other polyesters. In embodiments wherein polylactide is used as the degradable material, certain preferred embodiments employ a mixture of the D and L stereoisomers, designed so as to provide a desired degradation time and/or rate. - Aliphatic polyesters useful in the present invention may be prepared by substantially any of the conventionally known manufacturing methods such as those described in U.S. Pat. Nos. 6,323,307; 5,216,050; 4,387,769; 3,912,692; and 2,703,316, the relevant disclosures of which are incorporated herein by reference.
- Polyanhydrides are another type of degradable polymer that may be suitable for use in the present invention. Polyanhydride hydrolysis proceeds, inter alia, via free carboxylic acid chain-ends to yield carboxylic acids as final degradation products. Their erosion time can be varied over a broad range of changes in the polymer backbone. Examples of suitable polyanhydrides include poly(adipic anhydride), poly(suberic anhydride), poly(sebacic anhydride), and poly(dodecanedioic anhydride). Other suitable examples include, but are not limited to, poly(maleic anhydride) and poly(benzoic anhydride).
- The physical properties of degradable polymers may depend on several factors including, but not limited to, the composition of the repeat units, flexibility of the chain, presence of polar groups, molecular mass, degree of branching, crystallinity, and orientation. For example, short chain branches reduce the degree of crystallinity of polymers while long chain branches lower the melt viscosity and impart, inter alia, extensional viscosity with tension-stiffening behavior. The properties of the material utilized further may be tailored by blending, and copolymerizing it with another polymer, or by a change in the macromolecular architecture (e.g., hyper-branched polymers, star-shaped, or dendrimers, and the like). The properties of any such suitable degradable polymers (e.g., hydrophobicity, hydrophilicity, rate of degradation, and the like) can be tailored by introducing select functional groups along the polymer chains. For example, poly(phenyllactide) will degrade at about ⅕th of the rate of racemic poly(lactide) at a pH of 7.4 at 55° C. One of ordinary skill in the art, with the benefit of this disclosure, will be able to determine the appropriate functional groups to introduce to the polymer chains to achieve the desired physical properties of the degradable polymers.
- Whichever degradable material is used in the the present invention, the degradable material may have any shape, including, but not limited to, particles having the physical shape of platelets, shavings, flakes, ribbons, rods, strips, spheroids, toroids, pellets, tablets, or any other physical shape. In certain embodiments of the present invention, the degradable material used may comprise a mixture of fibers and spherical particles. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the specific degradable material that may be used in accordance with the present invention, and the preferred size and shape for a given application.
- In certain embodiments of the present invention, the degradable material used may comprise a self-degrading fiber that comprises an outer shell and a core liquid, wherein the outer shell comprises a degradable polymer and substantially retains the core liquid. In certain embodiments of the present invention, the outer shell may comprise a degradable polymer that is subject to hydrolytic degradation. The core liquid may comprise a liquid that is able to at least partially facilitate or catalyze the hydrolysis of the degradable polymer in the outer shell. Optionally, the self-degrading fiber may comprise a coating on the outer shell and/or a suitable additive within the core liquid, e.g., an additive chosen to interact with the degradable polymer, its degradation products, or the surrounding subterranean environment. In certain embodiments, the outer shell may be non-porous. Methods of making the self-degrading fibers described herein include any suitable method for forming hollow fibers. One such method involves extruding hollow fibers made from a desired degradable polymer; soaking the hollow fibers in a liquid that will be the core liquid; saturating the hollow fibers with the liquid; and drying the exterior of the outer core of the fibers in such a manner that the liquid is retained in the hollow fibers and becomes a core liquid. Another method involves extruding a spinning solution of a chosen degradable polymer from an annular slit of a double pipe orifice to form a sheath solution while simultaneously extruding a liquid through the inside pipe of the double pipe orifice, to form a core liquid within the hollow fibers. Another method involves using capillary action to place the core liquid in an already-formed suitable hollow fiber. Other suitable methods may be used as well.
- In choosing the appropriate degradable material, one should consider the degradation products that will result. Also, these degradation products should not adversely affect other operations or components. The choice of degradable material also can depend, at least in part, on the conditions of the well, e.g., well bore temperature. For instance, lactides have been found to be suitable for lower temperature wells, including those within the range of 60° F. to 150° F., and polylactides have been found to be suitable for well bore temperatures above this range.
- In certain exemplary embodiments, the degradation of the degradable material could result in a final degradation product having the potential to affect the pH of the fracturing fluid. For example, in exemplary embodiments wherein the degradable material is poly(lactic acid), the degradation of the poly(lactic acid) to produce lactic acid may alter the pH of the fracturing fluid. In certain exemplary embodiments, a buffer compound may be included within the fracturing fluids of the present invention in an amount sufficient to neutralize the final degradation product. Examples of suitable buffer compounds include, but are not limited to, calcium carbonate, magnesium oxide, ammonium acetate, and the like. One of ordinary skill in the art, with the benefit of this disclosure, will be able to identify the proper concentration of a buffer compound to include in the fracturing fluid for a particular application. An example of a suitable buffer comprises ammonium acetate and is commercially available from Halliburton Energy Services, Inc., under the trade name “BA-20.”
- Also, a preferable result may be achieved if the degradable material degrades slowly over time as opposed to instantaneously.
- An example of a suitable source of degradable material is a poly(lactic acid) that is commercially available from Cargill Dow under the trade name “6250D.”
- When the mixture of a degradable material and acid/base cements in the fracturing fluids of the present invention is placed in a subterranean formation, the mixture may begin to degrade over time in a controllable fashion.
- Referring now to
FIGS. 2 and 3 , illustrated therein are graphical relationships of the time- and temperature-dependence of the degradation of exemplary degradable materials. A synthetic sea water solution was prepared by adding 41.953 grams of sea salt to one liter of deionized water. Next, 1.33 grams of sodium p-toluene sulfonate was added to the sea water solution to form a solution that was 6.919 mM in sodium p-toluene sulfonate. Next, one gram of 6250D or 5639A was placed in a one liter round-bottom flask containing 500 mL of synthetic sea water solution. A reflux condenser then was placed on each flask, and the contents were heated to 75, 85 or 95° C. - Using a disposable pipette, an aliquot was removed from each flask and placed in a 10 mL beaker. A carefully measured aliquot of 5.00 mL was removed and placed in a 50 mL round-bottom flask. The contents of the flasks were frozen by placing the flasks in liquid nitrogen. The flasks then were placed on a high vacuum line and the samples were allowed to dry overnight. After 24 hours, 1 mL of D2O was added to each flask, and the contents of the flask were stirred until the residue re-dissolved. The freeze drying was repeated to remove D2O and residual water. The remaining materials were dissolved in D2O for NMR measurement.
- The 1H NMR spectrum was collected using a Bruker 300 Avance NMR spectrometer operating at 300 MHz, using a 5 mm QNP probe at various time intervals. The integrated area of the methyl proton peak of lactic acid was compared to the integrated area of the 6.919 mM sodium p-toluene sulfonate internal standard, and the lactic acid concentration for each point displayed in
FIGS. 2 and 3 was calculated from that ratio.FIG. 2 illustrates the time- and temperature-dependence of the generation of lactic acid caused by the degradation of 6250D, whileFIG. 3 illustrates the time- and temperature-dependence of the generation of lactic acid caused by the degradation of 5639A. - IV. Preparation of the Fracturing Fluids of the Present Invention
- The fracturing fluids of the present invention may be prepared in a variety of ways. For example, in certain embodiments of the present invention, magnesium oxide and potassium phosphate may be added in dry form to a water source. A degradable material then may be added to the mixture to form a fracturing fluid of the present invention. Generally, the degradable material may be present in the fracturing fluids in an amount sufficient to provide a desired degree of void space in the solid mass that may form in the created or enhanced fracture. The void space may result from the degradation of the degradable material, and also may result from subsequent reactions that may occur between the acid-base cement and an acid byproduct that may be produced by degradation of the degradable material.
- For certain embodiments of the fracturing fluids of the present invention wherein poly(lactic acid) is used as the degradable material, Table 1 below demonstrates the relationship that may exist between the concentration of poly(lactic acid) in the fracturing fluids and the degree of void space that may result in the solid mass.
TABLE 1 Poly(lactic acid) concentration (volume percent of the fracturing fluid) Resulting void space 8% 20% 11% 30% 13% 40% 15% 50% - Optionally, the fracturing fluids of the present invention may include other additives, such as, but not limited to, a set retarder. After the placement of the fracturing fluids of the present invention within a fracture in the subterranean formation, the water source may combine with the dry materials in the fracturing fluid to form what may be referred to as a “hydrate,” e.g., a solid compound comprising water molecules that may combine in a definite ratio. Furthermore, the water molecules within the hydrate may provide a hydrolysis source for the degradable material.
- An example of one embodiment of a fracturing fluid of the present invention may be prepared by preparing a two-component dry blend that comprised 22.7% magnesium oxide by weight and 77.3% potassium phosphate by weight. Next, poly(lactic acid) may be added in an amount equal to about 55% by weight of the two-component dry blend, thus forming a three-component dry blend. Water then may be added in a mass ratio of one part water to three parts dry blend. In certain embodiments where the fracturing fluid may be placed in a subterranean formation over an extended period of time, sodium borate (among other additives) may be added; in certain embodiments of the present invention, the sodium borate may be added in an amount in the range of from less than about 8% by weight of the magnesium oxide.
- To facilitate a better understanding of the present invention, the following examples of some exemplary embodiments are given. In no way should such examples be read to limit, or to define, the scope of the invention.
- Sample compositions were formed as follows. First, 7.58 grams of magnesium oxide were dry blended with 25.75 grams of potassium phosphate monobasic crystals (KH2PO4), and mixed with 16.67 grams of tap water. The mixture was stirred for some time, and poly(lactic acid) (“6250D”) was added, generally in an amount in the range of from about 35% by weight to about 40% by weight. Certain of the sample compositions further comprised an acid-base cement referred to as Newberyite, and having the chemical formula MgH(PO4).3H2O. Among other things, Newberyite is thought to impart strength-enhancing properties to the sample composition, and the additional water that Newberyite may supply may facilitate hydrolysis of the degradable material (6250D, in this example). Table 2 sets forth the respective amounts of 6250D and Newberyite included in a particular sample composition.
TABLE 2 Sample Poly(lactic acid) Composition (“6250D”) Newberyite 1 20 grams Not added 2 20 grams Not added 3 20 grams 10 grams 4 15 grams 10 grams 5 15 grams Not added 6 20 grams 10 grams 7 20 grams Not added 8 20 grams 10 grams - Generally, each sample composition was placed in a 20 mL plastic cylinder, and was allowed to set therein into a hard rod. Each rod then was left for a designated cure time at room temperature. Next, the set rod was taken out of the cylinder and either tested for compressibility or directly placed in a bomb supplied by PARR Instrument Company, Moline, Ill. Among other things, the bomb prevented the escape of water that may have been present in the set rod. The bomb was heated in a stove at 250° F. After a time, usually 24 hours, the bomb was removed from the stove, and its contents were observed to see whether or not degradation occurred.
- Certain sample compositions were tested for compressibility using an apparatus supplied by Tinius Olsen company of Willow Grove, Pa. The procedure was performed as follows. After the sample composition had cured and set into a hard rod, the rod was cut down to a 1 inch diameter and a 3 inch length. Two faces of the rod were smoothed. The rod then was placed under the Tinius Olsen compressibility load cell and subjected to a displacement load at a rate of 0.07 inches per minute. The maximum loading in psi that each rod could withstand until failure was recorded.
- The results of the testing are set forth in Table 3 below.
TABLE 3 Rod Compressive Sample Cure Time Strength PARR Time Degradation Composition (75° F.) (psi) (250° F.) Comments 1 24 hours — 24 hours Flowable liquid with particulates about 1 mm in diameter. 2 24 hours 290 72 hours Chunks (5-10 mm in diameter) with some liquid. 3 24 hours 1560 24 hours Small chunks (1-3 mm with some liquid); very ″sandy.″ 4 24 days 2040 24 hours No self- degradation observed 5 24 days 510 48 hours No self- degradation observed 6 44 hours 2470 (High) 72 hours No self- 490 (Low) degradation observed 7 24 hours 630 24 hours @ No self- 180° F. degradation observed 24 hours @ Large chunks 250° F. (>1 cm in diameter) with some liquid. 8 24 hours 1180 24 hours @ No self- 180° F. degradation observed 24 hours @ Large chunks 250° F. (>1 cm in diameter) with some liquid. - Example 1 demonstrates, inter alia, that the combination of a degradable material and an acid-base cement may be suitable for use in the methods of the present invention.
- Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. While the invention has been described with reference to embodiments of the invention, such a reference does not imply a limitation on the invention, and no such limitation is to be inferred. The invention is capable of considerable modification, alternation, and equivalents in form and function, as will occur to those ordinarily skilled in the pertinent arts and having the benefit of this disclosure. The described embodiments of the invention are exemplary only, and are not exhaustive of the scope of the invention. Consequently, the invention is intended to be limited only by the spirit and scope of the appended claims, giving full cognizance to equivalents in all respects.
Claims (20)
1. A fracturing fluid comprising a self-degrading cement composition that comprises an acid source, a base source, a water source, and a degradable material.
2. The fracturing fluid of claim 1 wherein the acid source comprises at least one of the following: magnesium chloride, potassium phosphate monobasic, ammonium phosphate monobasic, and phosphoric acid.
3. The fracturing fluid of claim 1 wherein the base source comprises at least one of the following: magnesium oxide and ammonia.
4. The fracturing fluid of claim 1 wherein the degradable material comprises at least one of the following: an aliphatic polyester; a polysaccharide; a poly(lactide); a poly(glycolide); a poly(ε-caprolactone); a protein; a poly(hydroxybutyrate); a poly(anhydride); an aliphatic polycarbonate; an ortho ester; a poly(orthoester); a poly(vinylacetate); a poly(hydroxy ester ether); a poly(amino acid); poly(ethylene oxide); chitin; chitosan; a polyphosphazene; a poly ether ester; a polyester amide; or a copolymer or blend thereof.
5. The fracturing fluid of claim 1 wherein the degradable material comprises polyamide.
6. The fracturing fluid of claim 1 wherein the degradable material comprises at least one of the following: a nylon, a poly(caprolactam), or a mixture thereof.
7. The fracturing fluid of claim 1 wherein the degradable material comprises poly(lactic) acid.
8. The fracturing fluid of claim 1 wherein the acid source comprises potassium phosphate monobasic, the base source comprises magnesium oxide, and the degradable material comprises poly(lactic acid).
9. The fracturing fluid of claim 1 , further comprising Newberyite, wherein the acid source comprises potassium phosphate monobasic, the base source comprises magnesium oxide, the degradable material comprises poly(lactic acid).
10. The fracturing fluid of claim 1 wherein the acid source comprises ammonium phosphate monobasic, the base source comprises magnesium oxide, and the degradable material comprises poly(lactic acid).
11. The fracturing fluid of claim 10 further comprising Newberyite.
12. The fracturing fluid of claim 1 wherein the acid source comprises magnesium sulfate, the base source comprises magnesium oxide, and the degradable material comprises poly(lactic acid).
13. The fracturing fluid of claim 12 further comprising Newberyite.
14. The fracturing fluid of claim 1 wherein the degradable material comprises a fiber that comprises an outer shell and a core liquid.
15. The fracturing fluid of claim 14 wherein the outer shell comprises a degradable polymer that is susceptible to hydrolytic degradation.
16. The fracturing fluid of claim 15 wherein the core liquid is capable of at least partially facilitating the hydrolysis of the degradable polymer.
17. The fracturing fluid of claim 15 wherein the degradable polymer comprises poly(lactic acid).
18. The fracturing fluid of claim 14 wherein the degradable material comprises a coating on the outer shell.
19. The fracturing fluid of claim 14 wherein the outer shell is non-porous.
20. The fracturing fluid of claim 14 , further comprising Newberyite.
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US11/188,238 US7640985B2 (en) | 2005-02-01 | 2005-07-22 | Methods of directional drilling and forming kickoff plugs using self-degrading cement in subterranean well bores |
US11/188,280 US7497258B2 (en) | 2005-02-01 | 2005-07-22 | Methods of isolating zones in subterranean formations using self-degrading cement compositions |
US11/188,262 US7637319B2 (en) | 2005-02-01 | 2005-07-22 | Kickoff plugs comprising a self-degrading cement in subterranean well bores |
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Cited By (27)
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WO2015065575A1 (en) * | 2013-10-29 | 2015-05-07 | Halliburton Energy Services, Inc. | Wellbore servicing methods and compositions comprising degradable polymers |
US9410076B2 (en) | 2012-10-25 | 2016-08-09 | Halliburton Energy Services, Inc. | Wellbore servicing methods and compositions comprising degradable polymers |
US9702238B2 (en) | 2012-10-25 | 2017-07-11 | Halliburton Energy Services, Inc. | Wellbore servicing methods and compositions comprising degradable polymers |
RU2638667C2 (en) * | 2013-08-23 | 2017-12-15 | Шлюмбергер Текнолоджи Б.В. | Direct channeling method and system for increasing fracture conductivity |
US9896903B2 (en) | 2014-05-21 | 2018-02-20 | Shell Oil Company | Methods of making and using cement coated substrate |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007067668A1 (en) * | 2005-12-08 | 2007-06-14 | Hercules Incorporated | Solvent free fluidized polymer suspensions for oilfield servicing fluids |
Citations (95)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2238671A (en) * | 1940-02-09 | 1941-04-15 | Du Pont | Method of treating wells |
US2703316A (en) * | 1951-06-05 | 1955-03-01 | Du Pont | Polymers of high melting lactide |
US3173484A (en) * | 1958-09-02 | 1965-03-16 | Gulf Research Development Co | Fracturing process employing a heterogeneous propping agent |
US3302719A (en) * | 1965-01-25 | 1967-02-07 | Union Oil Co | Method for treating subterranean formations |
US3364995A (en) * | 1966-02-14 | 1968-01-23 | Dow Chemical Co | Hydraulic fracturing fluid-bearing earth formations |
US3366178A (en) * | 1965-09-10 | 1968-01-30 | Halliburton Co | Method of fracturing and propping a subterranean formation |
US3784585A (en) * | 1971-10-21 | 1974-01-08 | American Cyanamid Co | Water-degradable resins containing recurring,contiguous,polymerized glycolide units and process for preparing same |
US3868998A (en) * | 1974-05-15 | 1975-03-04 | Shell Oil Co | Self-acidifying treating fluid positioning process |
US3948672A (en) * | 1973-12-28 | 1976-04-06 | Texaco Inc. | Permeable cement composition and method |
US4010071A (en) * | 1974-10-10 | 1977-03-01 | Merck & Co., Inc. | Clarification of xanthan gum |
US4068718A (en) * | 1975-09-26 | 1978-01-17 | Exxon Production Research Company | Hydraulic fracturing method using sintered bauxite propping agent |
US4083407A (en) * | 1977-02-07 | 1978-04-11 | The Dow Chemical Company | Spacer composition and method of use |
US4252421A (en) * | 1978-11-09 | 1981-02-24 | John D. McCarry | Contact lenses with a colored central area |
US4498995A (en) * | 1981-08-10 | 1985-02-12 | Judith Gockel | Lost circulation drilling fluid |
US4502540A (en) * | 1981-06-01 | 1985-03-05 | Mobil Oil Corporation | Tertiary oil recovery |
US4506734A (en) * | 1983-09-07 | 1985-03-26 | The Standard Oil Company | Fracturing fluid breaker system which is activated by fracture closure |
US4716964A (en) * | 1981-08-10 | 1988-01-05 | Exxon Production Research Company | Use of degradable ball sealers to seal casing perforations in well treatment fluid diversion |
US4797262A (en) * | 1986-06-16 | 1989-01-10 | Shell Oil Company | Downflow fluidized catalytic cracking system |
US4809783A (en) * | 1988-01-14 | 1989-03-07 | Halliburton Services | Method of dissolving organic filter cake |
US4817721A (en) * | 1987-12-14 | 1989-04-04 | Conoco Inc. | Reducing the permeability of a rock formation |
US4822500A (en) * | 1988-02-29 | 1989-04-18 | Texas United Chemical Corporation | Saturated brine well treating fluids and additives therefore |
US4894231A (en) * | 1987-07-28 | 1990-01-16 | Biomeasure, Inc. | Therapeutic agent delivery system |
US4986353A (en) * | 1988-09-14 | 1991-01-22 | Conoco Inc. | Placement process for oil field chemicals |
US4986355A (en) * | 1989-05-18 | 1991-01-22 | Conoco Inc. | Process for the preparation of fluid loss additive and gel breaker |
US4986354A (en) * | 1988-09-14 | 1991-01-22 | Conoco Inc. | Composition and placement process for oil field chemicals |
US5082056A (en) * | 1990-10-16 | 1992-01-21 | Marathon Oil Company | In situ reversible crosslinked polymer gel used in hydrocarbon recovery applications |
US5203834A (en) * | 1990-12-21 | 1993-04-20 | Union Oil Company Of California | Foamed gels having selective permeability |
US5295542A (en) * | 1992-10-05 | 1994-03-22 | Halliburton Company | Well gravel packing methods |
US5304620A (en) * | 1992-12-21 | 1994-04-19 | Halliburton Company | Method of crosslinking cellulose and guar derivatives for treating subterranean formations |
US5386874A (en) * | 1993-11-08 | 1995-02-07 | Halliburton Company | Perphosphate viscosity breakers in well fracture fluids |
US5396957A (en) * | 1992-09-29 | 1995-03-14 | Halliburton Company | Well completions with expandable casing portions |
US5402846A (en) * | 1993-11-15 | 1995-04-04 | Mobil Oil Corporation | Unique method of hydraulic fracturing |
US5484881A (en) * | 1992-10-02 | 1996-01-16 | Cargill, Inc. | Melt-stable amorphous lactide polymer film and process for manufacturing thereof |
US5487897A (en) * | 1989-07-24 | 1996-01-30 | Atrix Laboratories, Inc. | Biodegradable implant precursor |
US5492177A (en) * | 1994-12-01 | 1996-02-20 | Mobil Oil Corporation | Method for consolidating a subterranean formation |
US5496557A (en) * | 1990-01-30 | 1996-03-05 | Akzo N.V. | Article for the controlled delivery of an active substance, comprising a hollow space fully enclosed by a wall and filled in full or in part with one or more active substances |
US5497830A (en) * | 1995-04-06 | 1996-03-12 | Bj Services Company | Coated breaker for crosslinked acid |
US5499678A (en) * | 1994-08-02 | 1996-03-19 | Halliburton Company | Coplanar angular jetting head for well perforating |
US5501276A (en) * | 1994-09-15 | 1996-03-26 | Halliburton Company | Drilling fluid and filter cake removal methods and compositions |
US5505787A (en) * | 1993-02-01 | 1996-04-09 | Total Service Co., Inc. | Method for cleaning surface of external wall of building |
US5591700A (en) * | 1994-12-22 | 1997-01-07 | Halliburton Company | Fracturing fluid with encapsulated breaker |
US5594095A (en) * | 1993-07-30 | 1997-01-14 | Cargill, Incorporated | Viscosity-modified lactide polymer composition and process for manufacture thereof |
US5602083A (en) * | 1995-03-31 | 1997-02-11 | Baker Hughes Inc. | Use of sized salts as bridging agent for oil based fluids |
US5604186A (en) * | 1995-02-15 | 1997-02-18 | Halliburton Company | Encapsulated enzyme breaker and method for use in treating subterranean formations |
US5607905A (en) * | 1994-03-15 | 1997-03-04 | Texas United Chemical Company, Llc. | Well drilling and servicing fluids which deposit an easily removable filter cake |
US5613558A (en) * | 1995-06-02 | 1997-03-25 | Bj Services Company | Method for controlling the set time of cement |
US5723416A (en) * | 1997-04-01 | 1998-03-03 | Liao; W. Andrew | Well servicing fluid for trenchless directional drilling |
US6024170A (en) * | 1998-06-03 | 2000-02-15 | Halliburton Energy Services, Inc. | Methods of treating subterranean formation using borate cross-linking compositions |
US6028113A (en) * | 1995-09-27 | 2000-02-22 | Sunburst Chemicals, Inc. | Solid sanitizers and cleaner disinfectants |
US6169058B1 (en) * | 1997-06-05 | 2001-01-02 | Bj Services Company | Compositions and methods for hydraulic fracturing |
US6172011B1 (en) * | 1993-04-05 | 2001-01-09 | Schlumberger Technolgy Corporation | Control of particulate flowback in subterranean wells |
US6189615B1 (en) * | 1998-12-15 | 2001-02-20 | Marathon Oil Company | Application of a stabilized polymer gel to an alkaline treatment region for improved hydrocarbon recovery |
US6203213B1 (en) * | 1999-03-15 | 2001-03-20 | Superior Modular Products Incorporated | Splice module for use in fiber optic cable alignment and splicing devices |
US6202751B1 (en) * | 2000-07-28 | 2001-03-20 | Halliburton Energy Sevices, Inc. | Methods and compositions for forming permeable cement sand screens in well bores |
US6357527B1 (en) * | 2000-05-05 | 2002-03-19 | Halliburton Energy Services, Inc. | Encapsulated breakers and method for use in treating subterranean formations |
US20020036088A1 (en) * | 2000-08-01 | 2002-03-28 | Todd Bradley L. | Well drilling and servicing fluids and methods of removing filter cake deposited thereby |
US6509301B1 (en) * | 1999-08-26 | 2003-01-21 | Daniel Patrick Vollmer | Well treatment fluids and methods for the use thereof |
US6508305B1 (en) * | 1999-09-16 | 2003-01-21 | Bj Services Company | Compositions and methods for cementing using elastic particles |
US6527051B1 (en) * | 2000-05-05 | 2003-03-04 | Halliburton Energy Services, Inc. | Encapsulated chemicals for use in controlled time release applications and methods |
US20030054962A1 (en) * | 2001-08-14 | 2003-03-20 | England Kevin W. | Methods for stimulating hydrocarbon production |
US20030060374A1 (en) * | 2001-09-26 | 2003-03-27 | Cooke Claude E. | Method and materials for hydraulic fracturing of wells |
US20040014607A1 (en) * | 2002-07-16 | 2004-01-22 | Sinclair A. Richard | Downhole chemical delivery system for oil and gas wells |
US20040014606A1 (en) * | 2002-07-19 | 2004-01-22 | Schlumberger Technology Corp | Method For Completing Injection Wells |
US6681856B1 (en) * | 2003-05-16 | 2004-01-27 | Halliburton Energy Services, Inc. | Methods of cementing in subterranean zones penetrated by well bores using biodegradable dispersants |
US6686328B1 (en) * | 1998-07-17 | 2004-02-03 | The Procter & Gamble Company | Detergent tablet |
US6691780B2 (en) * | 2002-04-18 | 2004-02-17 | Halliburton Energy Services, Inc. | Tracking of particulate flowback in subterranean wells |
US20040040706A1 (en) * | 2002-08-28 | 2004-03-04 | Tetra Technologies, Inc. | Filter cake removal fluid and method |
US6702023B1 (en) * | 1999-07-02 | 2004-03-09 | Cleansorb Limited | Method for treatment of underground reservoirs |
US6710019B1 (en) * | 1998-07-30 | 2004-03-23 | Christopher Alan Sawdon | Wellbore fluid |
US20040055747A1 (en) * | 2002-09-20 | 2004-03-25 | M-I Llc. | Acid coated sand for gravel pack and filter cake clean-up |
US6837309B2 (en) * | 2001-09-11 | 2005-01-04 | Schlumberger Technology Corporation | Methods and fluid compositions designed to cause tip screenouts |
US20050006095A1 (en) * | 2003-07-08 | 2005-01-13 | Donald Justus | Reduced-density proppants and methods of using reduced-density proppants to enhance their transport in well bores and fractures |
US20050028976A1 (en) * | 2003-08-05 | 2005-02-10 | Nguyen Philip D. | Compositions and methods for controlling the release of chemicals placed on particulates |
US20050034868A1 (en) * | 2003-08-14 | 2005-02-17 | Frost Keith A. | Orthoester compositions and methods of use in subterranean applications |
US20050034865A1 (en) * | 2003-08-14 | 2005-02-17 | Todd Bradley L. | Compositions and methods for degrading filter cake |
US20050034861A1 (en) * | 2003-08-14 | 2005-02-17 | Saini Rajesh K. | On-the fly coating of acid-releasing degradable material onto a particulate |
US20050045328A1 (en) * | 2001-06-11 | 2005-03-03 | Frost Keith A. | Orthoester compositions and methods for reducing the viscosified treatment fluids |
US20050051330A1 (en) * | 2003-09-05 | 2005-03-10 | Nguyen Philip D. | Methods for forming a permeable and stable mass in a subterranean formation |
US20050051363A1 (en) * | 2003-09-09 | 2005-03-10 | Trinidad Munoz | Treatment fluids comprising starch and ceramic particulate bridging agents and methods of using these fluids to provide fluid loss control |
US20050059558A1 (en) * | 2003-06-27 | 2005-03-17 | Blauch Matthew E. | Methods for improving proppant pack permeability and fracture conductivity in a subterranean well |
US20050059557A1 (en) * | 2003-09-17 | 2005-03-17 | Todd Bradley L. | Subterranean treatment fluids and methods of treating subterranean formations |
US20050056423A1 (en) * | 2003-09-11 | 2005-03-17 | Todd Bradey L. | Methods of removing filter cake from well producing zones |
US6981552B2 (en) * | 2003-03-21 | 2006-01-03 | Halliburton Energy Services, Inc. | Well treatment fluid and methods with oxidized polysaccharide-based polymers |
US6983801B2 (en) * | 2001-01-09 | 2006-01-10 | Bj Services Company | Well treatment fluid compositions and methods for their use |
US6987083B2 (en) * | 2003-04-11 | 2006-01-17 | Halliburton Energy Services, Inc. | Xanthan gels in brines and methods of using such xanthan gels in subterranean formations |
US20060016596A1 (en) * | 2004-07-23 | 2006-01-26 | Pauls Richard W | Treatment fluids and methods of use in subterranean formations |
US20060032633A1 (en) * | 2004-08-10 | 2006-02-16 | Nguyen Philip D | Methods and compositions for carrier fluids comprising water-absorbent fibers |
US20060046938A1 (en) * | 2004-09-02 | 2006-03-02 | Harris Philip C | Methods and compositions for delinking crosslinked fluids |
US7007752B2 (en) * | 2003-03-21 | 2006-03-07 | Halliburton Energy Services, Inc. | Well treatment fluid and methods with oxidized polysaccharide-based polymers |
US20060065397A1 (en) * | 2004-09-24 | 2006-03-30 | Nguyen Philip D | Methods and compositions for inducing tip screenouts in frac-packing operations |
US7156174B2 (en) * | 2004-01-30 | 2007-01-02 | Halliburton Energy Services, Inc. | Contained micro-particles for use in well bore operations |
US7165617B2 (en) * | 2004-07-27 | 2007-01-23 | Halliburton Energy Services, Inc. | Viscosified treatment fluids and associated methods of use |
US7172022B2 (en) * | 2004-03-17 | 2007-02-06 | Halliburton Energy Services, Inc. | Cement compositions containing degradable materials and methods of cementing in subterranean formations |
US7195068B2 (en) * | 2003-12-15 | 2007-03-27 | Halliburton Energy Services, Inc. | Filter cake degradation compositions and methods of use in subterranean operations |
US7322412B2 (en) * | 2004-08-30 | 2008-01-29 | Halliburton Energy Services, Inc. | Casing shoes and methods of reverse-circulation cementing of casing |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2857543C2 (en) * | 1977-09-06 | 1985-07-04 | E.I. Du Pont De Nemours And Co., Wilmington, Del. | Inorganic mortar systems, suitable for anchoring a bolt in a hole and for anchoring a reinforcement element in a hole |
US5311945A (en) * | 1992-10-22 | 1994-05-17 | Shell Oil Company | Drilling and cementing with phosphate |
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 |
US7036586B2 (en) * | 2004-01-30 | 2006-05-02 | Halliburton Energy Services, Inc. | Methods of cementing in subterranean formations using crack resistant cement compositions |
-
2005
- 2005-02-01 US US11/048,591 patent/US20060169448A1/en not_active Abandoned
-
2006
- 2006-01-10 WO PCT/GB2006/000094 patent/WO2006082356A1/en not_active Application Discontinuation
Patent Citations (99)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2238671A (en) * | 1940-02-09 | 1941-04-15 | Du Pont | Method of treating wells |
US2703316A (en) * | 1951-06-05 | 1955-03-01 | Du Pont | Polymers of high melting lactide |
US3173484A (en) * | 1958-09-02 | 1965-03-16 | Gulf Research Development Co | Fracturing process employing a heterogeneous propping agent |
US3302719A (en) * | 1965-01-25 | 1967-02-07 | Union Oil Co | Method for treating subterranean formations |
US3366178A (en) * | 1965-09-10 | 1968-01-30 | Halliburton Co | Method of fracturing and propping a subterranean formation |
US3364995A (en) * | 1966-02-14 | 1968-01-23 | Dow Chemical Co | Hydraulic fracturing fluid-bearing earth formations |
US3784585A (en) * | 1971-10-21 | 1974-01-08 | American Cyanamid Co | Water-degradable resins containing recurring,contiguous,polymerized glycolide units and process for preparing same |
US3948672A (en) * | 1973-12-28 | 1976-04-06 | Texaco Inc. | Permeable cement composition and method |
US3868998A (en) * | 1974-05-15 | 1975-03-04 | Shell Oil Co | Self-acidifying treating fluid positioning process |
US4010071A (en) * | 1974-10-10 | 1977-03-01 | Merck & Co., Inc. | Clarification of xanthan gum |
US4068718A (en) * | 1975-09-26 | 1978-01-17 | Exxon Production Research Company | Hydraulic fracturing method using sintered bauxite propping agent |
US4083407A (en) * | 1977-02-07 | 1978-04-11 | The Dow Chemical Company | Spacer composition and method of use |
US4252421A (en) * | 1978-11-09 | 1981-02-24 | John D. McCarry | Contact lenses with a colored central area |
US4502540A (en) * | 1981-06-01 | 1985-03-05 | Mobil Oil Corporation | Tertiary oil recovery |
US4498995A (en) * | 1981-08-10 | 1985-02-12 | Judith Gockel | Lost circulation drilling fluid |
US4716964A (en) * | 1981-08-10 | 1988-01-05 | Exxon Production Research Company | Use of degradable ball sealers to seal casing perforations in well treatment fluid diversion |
US4506734A (en) * | 1983-09-07 | 1985-03-26 | The Standard Oil Company | Fracturing fluid breaker system which is activated by fracture closure |
US4797262A (en) * | 1986-06-16 | 1989-01-10 | Shell Oil Company | Downflow fluidized catalytic cracking system |
US4894231A (en) * | 1987-07-28 | 1990-01-16 | Biomeasure, Inc. | Therapeutic agent delivery system |
US4817721A (en) * | 1987-12-14 | 1989-04-04 | Conoco Inc. | Reducing the permeability of a rock formation |
US4809783A (en) * | 1988-01-14 | 1989-03-07 | Halliburton Services | Method of dissolving organic filter cake |
US4822500A (en) * | 1988-02-29 | 1989-04-18 | Texas United Chemical Corporation | Saturated brine well treating fluids and additives therefore |
US4986354A (en) * | 1988-09-14 | 1991-01-22 | Conoco Inc. | Composition and placement process for oil field chemicals |
US4986353A (en) * | 1988-09-14 | 1991-01-22 | Conoco Inc. | Placement process for oil field chemicals |
US4986355A (en) * | 1989-05-18 | 1991-01-22 | Conoco Inc. | Process for the preparation of fluid loss additive and gel breaker |
US5487897A (en) * | 1989-07-24 | 1996-01-30 | Atrix Laboratories, Inc. | Biodegradable implant precursor |
US5496557A (en) * | 1990-01-30 | 1996-03-05 | Akzo N.V. | Article for the controlled delivery of an active substance, comprising a hollow space fully enclosed by a wall and filled in full or in part with one or more active substances |
US5082056A (en) * | 1990-10-16 | 1992-01-21 | Marathon Oil Company | In situ reversible crosslinked polymer gel used in hydrocarbon recovery applications |
US5203834A (en) * | 1990-12-21 | 1993-04-20 | Union Oil Company Of California | Foamed gels having selective permeability |
US5396957A (en) * | 1992-09-29 | 1995-03-14 | Halliburton Company | Well completions with expandable casing portions |
US5484881A (en) * | 1992-10-02 | 1996-01-16 | Cargill, Inc. | Melt-stable amorphous lactide polymer film and process for manufacturing thereof |
US5295542A (en) * | 1992-10-05 | 1994-03-22 | Halliburton Company | Well gravel packing methods |
US5304620A (en) * | 1992-12-21 | 1994-04-19 | Halliburton Company | Method of crosslinking cellulose and guar derivatives for treating subterranean formations |
US5505787A (en) * | 1993-02-01 | 1996-04-09 | Total Service Co., Inc. | Method for cleaning surface of external wall of building |
US6172011B1 (en) * | 1993-04-05 | 2001-01-09 | Schlumberger Technolgy Corporation | Control of particulate flowback in subterranean wells |
US5594095A (en) * | 1993-07-30 | 1997-01-14 | Cargill, Incorporated | Viscosity-modified lactide polymer composition and process for manufacture thereof |
US5386874A (en) * | 1993-11-08 | 1995-02-07 | Halliburton Company | Perphosphate viscosity breakers in well fracture fluids |
US5402846A (en) * | 1993-11-15 | 1995-04-04 | Mobil Oil Corporation | Unique method of hydraulic fracturing |
US5607905A (en) * | 1994-03-15 | 1997-03-04 | Texas United Chemical Company, Llc. | Well drilling and servicing fluids which deposit an easily removable filter cake |
US5499678A (en) * | 1994-08-02 | 1996-03-19 | Halliburton Company | Coplanar angular jetting head for well perforating |
US5501276A (en) * | 1994-09-15 | 1996-03-26 | Halliburton Company | Drilling fluid and filter cake removal methods and compositions |
US5492177A (en) * | 1994-12-01 | 1996-02-20 | Mobil Oil Corporation | Method for consolidating a subterranean formation |
US5591700A (en) * | 1994-12-22 | 1997-01-07 | Halliburton Company | Fracturing fluid with encapsulated breaker |
US5604186A (en) * | 1995-02-15 | 1997-02-18 | Halliburton Company | Encapsulated enzyme breaker and method for use in treating subterranean formations |
US5602083A (en) * | 1995-03-31 | 1997-02-11 | Baker Hughes Inc. | Use of sized salts as bridging agent for oil based fluids |
US5497830A (en) * | 1995-04-06 | 1996-03-12 | Bj Services Company | Coated breaker for crosslinked acid |
US5613558A (en) * | 1995-06-02 | 1997-03-25 | Bj Services Company | Method for controlling the set time of cement |
US6028113A (en) * | 1995-09-27 | 2000-02-22 | Sunburst Chemicals, Inc. | Solid sanitizers and cleaner disinfectants |
US5723416A (en) * | 1997-04-01 | 1998-03-03 | Liao; W. Andrew | Well servicing fluid for trenchless directional drilling |
US6169058B1 (en) * | 1997-06-05 | 2001-01-02 | Bj Services Company | Compositions and methods for hydraulic fracturing |
US6024170A (en) * | 1998-06-03 | 2000-02-15 | Halliburton Energy Services, Inc. | Methods of treating subterranean formation using borate cross-linking compositions |
US6686328B1 (en) * | 1998-07-17 | 2004-02-03 | The Procter & Gamble Company | Detergent tablet |
US6710019B1 (en) * | 1998-07-30 | 2004-03-23 | Christopher Alan Sawdon | Wellbore fluid |
US6189615B1 (en) * | 1998-12-15 | 2001-02-20 | Marathon Oil Company | Application of a stabilized polymer gel to an alkaline treatment region for improved hydrocarbon recovery |
US6203213B1 (en) * | 1999-03-15 | 2001-03-20 | Superior Modular Products Incorporated | Splice module for use in fiber optic cable alignment and splicing devices |
US6702023B1 (en) * | 1999-07-02 | 2004-03-09 | Cleansorb Limited | Method for treatment of underground reservoirs |
US6509301B1 (en) * | 1999-08-26 | 2003-01-21 | Daniel Patrick Vollmer | Well treatment fluids and methods for the use thereof |
US6508305B1 (en) * | 1999-09-16 | 2003-01-21 | Bj Services Company | Compositions and methods for cementing using elastic particles |
US6527051B1 (en) * | 2000-05-05 | 2003-03-04 | Halliburton Energy Services, Inc. | Encapsulated chemicals for use in controlled time release applications and methods |
US6357527B1 (en) * | 2000-05-05 | 2002-03-19 | Halliburton Energy Services, Inc. | Encapsulated breakers and method for use in treating subterranean formations |
US6202751B1 (en) * | 2000-07-28 | 2001-03-20 | Halliburton Energy Sevices, Inc. | Methods and compositions for forming permeable cement sand screens in well bores |
US20020036088A1 (en) * | 2000-08-01 | 2002-03-28 | Todd Bradley L. | Well drilling and servicing fluids and methods of removing filter cake deposited thereby |
US6983801B2 (en) * | 2001-01-09 | 2006-01-10 | Bj Services Company | Well treatment fluid compositions and methods for their use |
US20050045328A1 (en) * | 2001-06-11 | 2005-03-03 | Frost Keith A. | Orthoester compositions and methods for reducing the viscosified treatment fluids |
US7168489B2 (en) * | 2001-06-11 | 2007-01-30 | Halliburton Energy Services, Inc. | Orthoester compositions and methods for reducing the viscosified treatment fluids |
US20030054962A1 (en) * | 2001-08-14 | 2003-03-20 | England Kevin W. | Methods for stimulating hydrocarbon production |
US6837309B2 (en) * | 2001-09-11 | 2005-01-04 | Schlumberger Technology Corporation | Methods and fluid compositions designed to cause tip screenouts |
US20030060374A1 (en) * | 2001-09-26 | 2003-03-27 | Cooke Claude E. | Method and materials for hydraulic fracturing of wells |
US6691780B2 (en) * | 2002-04-18 | 2004-02-17 | Halliburton Energy Services, Inc. | Tracking of particulate flowback in subterranean wells |
US20040014607A1 (en) * | 2002-07-16 | 2004-01-22 | Sinclair A. Richard | Downhole chemical delivery system for oil and gas wells |
US20040014606A1 (en) * | 2002-07-19 | 2004-01-22 | Schlumberger Technology Corp | Method For Completing Injection Wells |
US20040040706A1 (en) * | 2002-08-28 | 2004-03-04 | Tetra Technologies, Inc. | Filter cake removal fluid and method |
US20040055747A1 (en) * | 2002-09-20 | 2004-03-25 | M-I Llc. | Acid coated sand for gravel pack and filter cake clean-up |
US7007752B2 (en) * | 2003-03-21 | 2006-03-07 | Halliburton Energy Services, Inc. | Well treatment fluid and methods with oxidized polysaccharide-based polymers |
US6981552B2 (en) * | 2003-03-21 | 2006-01-03 | Halliburton Energy Services, Inc. | Well treatment fluid and methods with oxidized polysaccharide-based polymers |
US6987083B2 (en) * | 2003-04-11 | 2006-01-17 | Halliburton Energy Services, Inc. | Xanthan gels in brines and methods of using such xanthan gels in subterranean formations |
US6681856B1 (en) * | 2003-05-16 | 2004-01-27 | Halliburton Energy Services, Inc. | Methods of cementing in subterranean zones penetrated by well bores using biodegradable dispersants |
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 |
US20050059558A1 (en) * | 2003-06-27 | 2005-03-17 | Blauch Matthew E. | Methods for improving proppant pack permeability and fracture conductivity in a subterranean well |
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