WO2015035280A1 - Foaming of set-delayed cement compositions comprising pumice and hydrated lime - Google Patents
Foaming of set-delayed cement compositions comprising pumice and hydrated lime Download PDFInfo
- Publication number
- WO2015035280A1 WO2015035280A1 PCT/US2014/054496 US2014054496W WO2015035280A1 WO 2015035280 A1 WO2015035280 A1 WO 2015035280A1 US 2014054496 W US2014054496 W US 2014054496W WO 2015035280 A1 WO2015035280 A1 WO 2015035280A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- delayed cement
- cement composition
- delayed
- foaming
- composition
- Prior art date
Links
- 239000004568 cement Substances 0.000 title claims abstract description 224
- 239000000203 mixture Substances 0.000 title claims abstract description 207
- 239000008262 pumice Substances 0.000 title claims abstract description 45
- 238000005187 foaming Methods 0.000 title claims abstract description 30
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 239000000920 calcium hydroxide Substances 0.000 title claims abstract description 26
- 235000011116 calcium hydroxide Nutrition 0.000 title claims abstract description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims description 33
- 239000002270 dispersing agent Substances 0.000 claims description 27
- 239000012190 activator Substances 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 16
- 230000003111 delayed effect Effects 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- -1 borate compound Chemical class 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229960003237 betaine Drugs 0.000 claims description 6
- 150000003007 phosphonic acid derivatives Chemical class 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- ONLRKTIYOMZEJM-UHFFFAOYSA-N n-methylmethanamine oxide Chemical compound C[NH+](C)[O-] ONLRKTIYOMZEJM-UHFFFAOYSA-N 0.000 claims description 4
- 102000011782 Keratins Human genes 0.000 claims description 3
- 108010076876 Keratins Proteins 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 4
- 150000004702 methyl esters Chemical class 0.000 claims 2
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- JNGWKQJZIUZUPR-UHFFFAOYSA-N [3-(dodecanoylamino)propyl](hydroxy)dimethylammonium Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)[O-] JNGWKQJZIUZUPR-UHFFFAOYSA-N 0.000 claims 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical group OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- 238000005755 formation reaction Methods 0.000 description 28
- 239000012530 fluid Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 12
- 230000008901 benefit Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000001066 destructive effect Effects 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000008186 active pharmaceutical agent Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000246 remedial effect Effects 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 229960003010 sodium sulfate Drugs 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 101150082527 ALAD gene Proteins 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 101150071661 SLC25A20 gene Proteins 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 101150102633 cact gene Proteins 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- YIBPLYRWHCQZEB-UHFFFAOYSA-N formaldehyde;propan-2-one Chemical class O=C.CC(C)=O YIBPLYRWHCQZEB-UHFFFAOYSA-N 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PYUBPZNJWXUSID-UHFFFAOYSA-N pentadecapotassium;pentaborate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] PYUBPZNJWXUSID-UHFFFAOYSA-N 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/14—Minerals of vulcanic origin
- C04B14/16—Minerals of vulcanic origin porous, e.g. pumice
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
- C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
-
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/10—Lime cements or magnesium oxide cements
- C04B28/12—Hydraulic lime
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
- C04B40/0658—Retarder inhibited mortars activated by the addition of accelerators or retarder-neutralising agents
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
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- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/473—Density reducing additives, e.g. for obtaining foamed cement compositions
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
Definitions
- cement compositions may be used in a variety of subterranean operations.
- a pipe string e.g., casing, liners, expandable tubulars, etc
- the process of cementing the pipe string in place is commonly referred to as "primary cementing.”
- primary cementing In a typical, primary cementing method, a cement composition may be pumped into an annul us between the walls of the wellbore and the exterior surface of the pipe string disposed therein.
- the cement composition may set in the annular space, thereby Forming an annular sheath of hardened, substantially impermeable cement (i.e., a cement sheath) that may support and position the pipe string in the wellbore and may bond the exterior surface of the pipe string to the subterranean formation.
- a cement sheath the cement sheath surrounding the pipe string functions to prevent the migration of fluids in the annulus, as well as protecting the pipe sirin from corrosion.
- Cement compositions a!so may be used in remedial cementing methods, f r example, to seal crack or holes in pipe strings or cement sheaths, to seal highly permeable formation zones or fractures, to place a cement plug, and the like.
- Set-delayed cement compositions are characterized by remaining in a pumpable fluid state for at least about one day (e.g., at least about 7 days, about 2 weeks, about 2 years or more) at room temperature (e.g., about 80 : ⁇ ! F) in quiescent storage.
- the set- delayed cement compositions should be capable of being activated whereby reasonable compressive strengths are developed.
- a cement set accelerator may be added to a set-delayed cement composition whereby the composition sets into a hardened mass.
- the set-delayed cement composition may be suitable for use in wellbore implications, for example, where it is desired to prepare the cement composition in advance. This may allow, for example, the cement composition to be stored prior to its use. In addition, this may allow, for example, the cement composition to be prepared at a convenient location and then transported to the job site. Accordingly, capital expenditures may be reduced due to a reduction in the need for on-site bulk storage and mixing equipment; This may be particularly useful for offshore cementing operations where space onboard the vessels may be limited.
- set-delayed cement compositions have been developed heretofore, challenges exist with their successful use in subterranean cementing operations.
- set-delayed cement compositions prepared with Portland cement may have undesired gelation issues which can limit their use and effectiveness in cementing operations.
- Other set-delayed compositions that have been developed, for example, those comprising hydrated lime and quartz, ma he effective in some operations but may have limited use at lower temperatures as they ma not develop sufficient compressive strength when used in subterranean formations having lower bottom hole static temperatures.
- FIG. I illustrates a system for preparation and delivery of a set-delayed Scement composition to a wellbore in accordance with certain embodiments.
- FIG. 2 A illustrates surface equipment that may be used in placement of a set- delayed cement composition in a wellbore in accordance with certain embodiments.
- FIG. 2B illustrates placement of a set-delayed cement composition into a wellbore annulus in accordance with certain embodiments.
- the example embodiments relate to subterranean cementing operations and, more particularly * in certain embodiments, to seKleiayed. cement compositions and methods of using set-delayed cement compositions in subterranean formations.
- Embodiments of the set-delayed cement compositions may generally comprise water, pumice, hydrated lime, and a set retattkr.
- the set-delayed cement compositions may further comprise a dispersant.
- Embodiments of the set-delayed cement compositions may be foamed.
- embodiments of the set-delayed cement compositions may be capable of remaining in a pumpable fluid state for an extended period of time.
- the set-delayed cement compositions may remain in a pumpable fluid state for at least about I day, about 2 weeks, about 2 years, or longer.
- the set-delayed cement compositions may develop reasonable compressive strengths after activation at relatively Sow temperatures.
- the set-delayed cement compositions may be suitable for a number of subterranean cementing operations, they may be particularly suitable for use in subterranean formations, having relatively low bottom hole static temperatures, e.g., temperatures less than about 200° F or ranging from about I00 c f to about 200 a F, In alternative embodiments, the set-delayed cement compositions may be used in subterranean formations having bottom hole static temperatures up to 45( ) °F or higher.
- the water used in embodiments of the set-delayed cement compositions may be from any source provided that ii does not contain an excess of compounds that may undesirably affect other components in the set-delayed cement compositions.
- a set-delayed cement composition may comprise fresh water or salt water.
- Salt water generally may include one or more dissolved salts therein and may be saturated or unsaturated as desired for a particular application. Seawater or brines may be suitable for use in embodiments.
- the water may be present in an amount sufficient to form a pumpable slurry. In certain, embodiments, the water may be present in. the set-delayed cement composition in an amount in the range of from about 33% to about 200% by weight of the pumice.
- the water may be present in the set-delayed cement compositions in. an amount in the range of from about 35% to about 70% by weight of the pumice.
- an amount in the range of from about 35% to about 70% by weight of the pumice is one of ordinary skill in the art with the benefit of this disclosure.
- Embodiments of the set-delayed cement compositions may comprise pumice.
- pumice is a volcanic rock that can exhibit, cemetiiitious properties in that it may set and harden in the presence of hydrated lime and water.
- the pumice may also be ground.
- the pumice may have any particle size distribution as desired for a particular application.
- the pumice may have a mean particle size in a range of from about 1 micron to about 200 microns. The mean particle size corresponds to d50 values as measured by particle size analyzers such a those manufactured by Malvern Instruments, Worcestershire, United Kingdom.
- the pumice may- have a mean particle size in a range of from about I micron to about 200 microns, from about 5 microns to about 100 microns, or from about K) microns to about 50 microns. In one particular embodiment, the pumice may have a mean particle size of less than about 15 .microns.
- An example of a suitable pumice is available from Hess Pumice Products, inc., alad, Idaho, as DS-325 lightweight aggregate, having a particle size of less than about 15 microns. It should be appreciated, that particle sizes too small may have mixability problems while particle sizes too large may not be effectively suspended in the compositions.
- Embodiments of the set-delayed cement compositions may comprise hydrated lime.
- the term "hydrated lime” will be understood to mean calcium hydroxide, in some embodiments, the hydrated lime may be provided as quicklime (calcium oxide) which hydrates when mixed with water to form, the hydrated lime.
- the hydrated lime may be included in embodiments of the set-delayed cement compositions, for example, to form a hydraulic composition, with, the pumice.
- the hydrated lime may be included in a pumice-t.o ⁇ hydrated ⁇ .lime weight ratio of about 10:1 to about 1 : 1 or 3:1 to about 5: 1.
- the hydrated lime may be included in the set-delayed cement compositions in an amount, in the range of from about 10% to about 100% by weight of the pumice, for example, hi some embodiments, the hydrated lime ma be present in an. amount ranging between any of and/or including any o about 10%, about 20%, about 40%, about 60%, about 80%, or about 100% by weight of the pumice, hi some embodiments, the cemeniitious components present in the set-delayed cement composition may consist essentially of the pumice and the hydrated lime.
- the eeniendtious components may primarily comprise the pumice and the hydrated lime without any additional components (e.g., Portland cement, ' fly ash. slag cement) that hydrau!ically set in. the presence of water.
- additional components e.g., Portland cement, ' fly ash. slag cement
- Embodiments of the set-delayed cement compositions may comprise a set retarder,
- a broad variety of set retarders may he suitable for use in the set-delayed cement compositions.
- the set retarder may comprise pfiospbonic acids, such as ethyienedianiine tettai methylene phosphonie acid), diethytenetriamme penta(methyie:ne phosphonic acid), etc.; lignosulfonates, such as sodium Hgnosulfonate.
- calcium lignosulfonate, etc salts such as stannous sulfate, lead acetate, monobasic calcium phosphate, organic acids, such as citric acid, tartaric acid, etc; cellulose derivatives such as hydroxy! ethyl cellulose (NEC) and earboxymethyl hydroxyethyl cellulose (C HEQ; synthetic co- or ter-polymers comprising sulfonate and carboxylic acid groups such as sulfonate-fonctionalized aerylamide-acrylic acid co-polymers; borate compounds such as alkali borates, sodium metaborate, sodium tetraborate, potassium pentaborate; derivatives thereof, or mixtures thereof.
- salts such as stannous sulfate, lead acetate, monobasic calcium phosphate, organic acids, such as citric acid, tartaric acid, etc
- cellulose derivatives such as hydroxy! ethyl cellulose (NEC) and earboxy
- Suitable set retarders include, among others, phosphonic acid derivatives.
- One example of a suitable set retarder is Micro Matrix* ' cement retarder. available from Halliburton Energy Services, Inc.
- the set retarder may be present in the set-delayed cement compositions in an amount sufficient to delay the setting for a desired time, in some embodiments, the set retarder may be present in the set-delayed cement compositions in an amount in the range of from about 0.01% to about 10% by weight of the pumice. In specific embodiments, the set retarder may be present in an amount ranging between any of and/or including any of about 0.01%, about 0.1%, about 1%. about 2%, about 4%, about 6%, about 8%, or about 10% by weight of the pumice.
- One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the set retarder to include for a chosen application.
- embodiments of the set-delayed cement compositions may optionally comprise a dispersant.
- suitable dispersants include, without: limitation, su!fbnated-fbrmaidehyde-based dispersants (e.g., sulfonated acetone formaldehyde condensate), examples of which may include Daxad * .1 available from Geo Specialty Chemicals, Ambler, Pennsylvania.
- Other suitable dispersants may be poiycarboxylated ether dispersants such as Liqulmenf* 558 I F and Liquimenf* "' S I.4L available from BASF Corporation Houston, Texas; or Ethacryl 0 available from Coatex, Genay, France.
- Liquiment* 514L dispersant comprises 36% by weight of the poiycarboxylated ether in water. While a variety of dispersants may be used in accordance with embodiments, poiycarboxylated ether dispersants may be particularly suitable for use in some embodiments. Without being limited by theory, it is believed that poiycarboxylated ether dispersants may synergistically interact with other components of the set-delayed cement composition,.
- the poiycarboxylated ether dispersants may react with certain set retarders (e.g.. phosphonic acid derivatives) resulting in formation of a gel thai suspends the pumice and hydraied lime- in the composition for an extended period of time.
- certain set retarders e.g.. phosphonic acid derivatives
- the dispersant may be included in the set-delayed cement compositions in an amount in the range of from about 0,01% to about 5% by weight of the pumice.
- the dispersatit may be present in an amount ranging between any of and/or including any of about 0.01%, about 0.1%. 0.5%, about 1%, about 2%, about 3%, about 4%, or about 5% by weight of the pumice.
- One of ordinar skill in the art, with the benefit of this disclosure, will recognize the appropriate amouni of the dispersant to include for a chosen application.
- Embodiments of the set-delayed cement compositions may comprise a mechanical property enhancing additive.
- Mechanical-property-enhancing additives may be included in embodiments of the set-delayed compositions to, for example, ensure adequate compressive strength and long-term structural integrity. These properties can be affected by the strains, stresses, temperature, pressure, and impact effects from a subterranean environment.
- Examples .of mechanical property enhancing additives include fibers, such as graphitic carbon fibers, glass fibers, steel fibers, mineral fibers, silica fibers, polyester fibers, polyamide fibers, and polyolefio fibers, among others. Specific examples of graphitic carbon fibers include fibers derived from polyacrylonitrile. rayon, and petroleum pitch.
- the mechanlcal-property-enhancing additives may be present, in an amount from about 0.01% to about 5% by weight of the pumice, in specific embodiments, the mechahical-property- eohanciog additives may be present, in an amount ranging between any of and/or including an of about 0.01%, about 0.1%, 0.5%, about ⁇ %, about 2%, about 3%, about 4%, or about 5% by weight of the pumice.
- One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the mechanical-property-enhancing additives to include for a chosen application.
- additives suitable for use in subterranean cementing operations also may be included in embodiments of the set-delayed cement compositions.
- additives include, but are not limited to, weighting agents, lightweight additives, gas- generating additives, lost-circulation materials, filtration-control additives, fluid-loss-control additives, defoaming agents, foaming agents, thixotropic additives, and combinations thereof.
- one or more of these additives may be added to the set-delayed cement composition after storing but prior to placement of the set-delayed cement composition into a subterranean formation.
- embodiments of the set- delayed cement compositions generally should have a density suitable tor a particular appl ication.
- the set-delayed cement compositions may have a density in the range of from about 4 pounds per gallon ("lb gal") to about 20 lb gal.
- the set-delayed cement, compositions may have a density in the range of from about 8 lb/gal to about 17 lb/gal.
- Embodiments of the set-delayed cement compositions may be foamed or unfoaraed or may comprise other means to reduce their densities, such, as hollow microspheres, low-density elastic beads, or other density-reducing additives known in the art. in embodiments, the density may be reduced after storing the composition, but prior to placement in a subterranean formation.
- embodiments of the set-delayed cement compositions may be foamed.
- Embodiments of the set-delayed cement compositions may be foamed to provide a lightweight composition that does not exert excessive force on formations penetrated by the wetlbore, in addition to being lightweight, a foamed composition may also improve the ability of the composition to maintain pressure and prevent the flow of formation fluids into and through the composition during its transition time.
- Foamed compositions may also be advantageous because they have low fluid loss properties, thus limiting loss of fluid circulation.
- foamed compositions when set ma also have a lower modulus of elasticity than non-foamed compositions, which is often desirable as it enables the resultant set cement composition to resist stresses exerted on the composition in situ,
- the set-delayed cement composition may be foamed at the well site.
- the set-delayed cement compositions may be foamed immediately prior to use.
- Embodiments may be foamed with a foaming additive and by entraining gas into the set-delayed cement compositions, hi particular embodiments, the foaming additi ve and gas may be introduced after combination of the composition with an activator.
- the set-delayed cement compositions may be foamed, for example, to provide a set-delayed cement composition with a reduced density.
- the gas used for foaming the composition may be any suitable, gas for foaming, including, but not limited to: air, nitrogen, and combinations thereof Generally, the gas should be in an amount sufficient to form the desired foam.
- Foaming additives may be included in embodiments to, for example, facilitate foaming and/or stabilize the resultant foam formed therewith.
- the foaming additive may include a surfactant or combination of surfactants that reduce the surface tension of the water.
- the foaming agent may comprise an anionic, nonionic, amphoteric (including zwitterionic surfactants), anionic surfactant, or mixtures thereof
- suitable foaming additives include, but are not limited to: betaines; anionic surfactants such as hydroiyzed keratin: amine oxides such as a alkyl or a!fcene dimethyl amine oxides; eocoamidopropyl dimethylamine oxide; methyl ester sulfonates; alkyl or alkene araidobeiaines such as eocoamidopropyl betaine; aipha-oleiln sulfonates; quaternary surfactants such as trimethyltallowammonium chloride and trimeth lcocoammonium chloride; C8 to C22 alkytethoxylate sulfates; and combinations thereof
- suitable foaming agents include mixtures of an ammonium salt of an alkyl ether sul
- foaming additives examples include ZON ES E A L ANTTM 2000 agent and Foaraer 1026"', both available from Halliburton Energy Services Inc., Houston, Texas.
- Embodiments may be foamed within a foam quality range of between about 5% to about 80% and, more particularly, from about 1 8% to about 38%.
- Foam quality refers to the volume of entrained gas and is defined by the following formula: Foam Quality :::: (Total Foam Volume - Liquid Volume / Total Foam Volume.
- the cement compositions may have a delayed set in that they remain in a pumpable fluid state for at least one day (e.g., at least about 1 day, about 2 weeks, about. 2 years, or longer) at room temperature in quiescent storage.
- the set-delayed cement compositions may remain in a pumpable. fluid state tor a period of time from about ! day, about 2 weeks, about 2 years, or longer, in some embodiments, the set-delayed cement compositions may remain in a pumpable fluid state for at least about 1 day, about 7 days, about 10 days, about 20 days, about 30 days, about 40 days, about 50 days, about 60 days, about 2 years, or longer.
- a fluid is considered to be in a pumpable fluid state where the fluid has consistency of less than 70 Bearden units of consistency ("Be"), as measured on a high-temperature high-pressure consistometer at room temperature (e.g., about 80° ) in accordance with the procedure for determining cement thickening times set forth in API F Practice 10B-2, Recommended Practice for Testing Well Cements, First Edition, July 2005,
- Be Bearden units of consistency
- embodiments of the set-delayed cement compositions may be activated (e.g., by combination with an activator) to thereby set into a hardened mass.
- embodiments of the set-delayed cement compositions may be activated to set to form a hardened mass in a time period in the range of from about 1 hour to about 12 hours.
- embodiments of the set-delayed cement compositions may set to form a hardened mass in a time period ranging between any of and/or including any of about 1 day, about 2 days, about 4 days, about 6 days, about 8 days, about .10 days, or about 12 days,
- the set-delayed cement composition may set to have a desirable compressive strength after activation.
- Compressive strength is generally the capacity of a material or structure to withstand axially directed pushing forces.
- the compressive strength may be measured at a specified time after the set-delayed cement composition has been activated and the resultant composition is maintained under specific temperature and pressure controls.
- Compressive strength can be measured by either a ' destructive method or non-destructive method. The destructive method physically tests the strength of treatment, fluid samples at various points in time by crushing the samples in a compression-testing machine.
- the compressive strength is calculated from the failure load divided by the cros -sectional area -resisting the load and is reported in units of pound-force per square inch (psi).
- Non-destructive methods typically may employ an Ultrasonic Cement Analyzer (“UCA”), available from Fann Instrument Company, Houston, TX. Compressive strengths may be determined in accordance with API RP IOB-2, Recommended Practice for Testing Weil Cements, First Edition, July 2005.
- UCA Ultrasonic Cement Analyzer
- the set-delayed cement composition may develop a. 24- hour compressive strength in the range of from about 50 psi to about 5000 psi, alternatively, from about 100 psi to about 4500 psi or alternatively from about 500 psi to about 4000 psi.
- the set-delayed cement composition may develop a compressive strength in 24 hours of at least about 50 pss, at least about 100 psi, at least about 500 psi, or more.
- the- compressive strength values may be determined using destructive or non-destructive methods at a temperature ranging from t00 s F to 200°F.
- Embodiments ma include the addition of a cement set activator to the set- delayed cement compositions.
- suitable cement -set activators include, but are not limited to: amines such as trtethanolamine, dieihanolarame; silicates such as sodium silicate; sdnc formate; calcium acetate; Groups IA and HA hydroxides such as sodium hydroxide, magnesium hydroxide, and calcium hydroxide; monovalent salts such as sodium, chloride; divalent sails such as calcium chloride; nanosilica (i.e., silica having a particle size of less than or equal to about 100 nanometers); polyphosphates; and combinations thereof.
- amines such as trtethanolamine, dieihanolarame
- silicates such as sodium silicate
- sdnc formate calcium acetate
- Groups IA and HA hydroxides such as sodium hydroxide, magnesium hydroxide, and calcium hydroxide
- monovalent salts such as sodium, chloride
- a combination of the polyphosphate and a monovalent salt may be used for activation.
- the monovalent salt may be any sail that dissociates to form a monovalent cation, such as sodium and potassium salts.
- suitable monovalent salts include potassium sulfate, and sodium sul fate,
- a variety of di fferent polyphosphates may be used in combination with the monovalent salt for activation of the set-delayed cement compositions, including polymeric metaphosphate salts, phosphate salts, and combinations thereof.
- polymeric metaphosphate salts that may be used include sodium hexametaphosphate, sodium trinietaphosphate, sodium tetramelaphosphate, sodium peniametaphosphate, sodium heptamefaphosphate, sodium octametaphosphate, and combinations thereof.
- a specific example of a suitable cement set activator comprises a combination of sodium sulfate and sodium hexametaphosphate.
- the activator may be provided and added to the set-delayed cement composition, as a liquid additive, for example, a liquid additive comprising a monovalent salt, a polyphosphate, and optionally a dispersant,
- the cement set activator should be added to embodiments of the set-delayed cement composition in an amount sufficient to activate the set-delayed cement composition to set into a hardened mass.
- the cement set activator may be added to the set-delayed cement composition in an amount in the range of about 1% to about 20% by weight of the pumice.
- the cement set activator may b present, in an amount ranging between any of and/or including an of about S.%, about 5%. about .10%, about 1 5%, or about 20% by weight of the pumice.
- One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the cement set activator to include for a chosen application,
- a set-delayed cement composition may be provided that comprises water, pumice, hydrated lime, a set reiarder, and optionally a dispersant.
- the set-delayed cement composition may be introduced into a subterranean formation and allowed to set therein.
- introducing the set- delayed cement composition into a subterranean formation includes introduction into any portion of the subterranean formation, Including, without limitation, into a wellbore drilled into the subterranean formation, into a.
- Embodiments may further include activation of the set-delayed cement composition.
- the activation of the set-delayed cement composition may comprise, for example, the addition of a cement set activator to the set-delayed cement composition.
- a set-delayed ' cement composition may be provided that comprises water, pumice, hydrated lime, a set retarder, and optionally a dispersant.
- the set-delayed cement composition may be stored, for example, in a vessel or other suitable container.
- the set-delayed cement composition may be permitted to remain in storage for a desired time period. For example, the set-delayed cement composition may remain in storage for a time period of about I day, about 2 weeks, about 2 years, or longer.
- the set-delayed cement composition may remain in storage for a time period of about 1 day, about 2 days, about: 5 days, about 7 days, about 10 days, about 20 days, about 30 days, about 40 days, about 50 days, about 60 days, about 2 years, or longer.
- the set-delayed cement composition may remain in storage for a time period in a range of from about 1 day to about 2 years or longer.
- the set-delayed cement composition may be activated, for example, by addition of a cement set acts valor, introduced into a subterranean formation, and allowed to set therein.
- the set-delayed cement composition may be foamed prior to introduction into the subterranean formation.
- a set-delayed cement composition may be used, for example, in squeeze-cementing operations or in the placement of cement plugs.
- the set-delayed composition may be placed in a wellbore to plug an opening such as a void or crack that is in the formation, in a gravel pack, in the conduit, in the cement sheath, and/or between the cement sheath and the conduit (e.g., a microannulus).
- An example embodiment comprises a method of cementing in a subterranean formation comprising; providing a set-delayed cement composition comprising water, pumice, hydrated lime, and a set retarder; foaming the set-delayed cement com position: activating the foamed set-delayed cement composition; introducing the foamed set-delayed cement composition into a subterranean formation; and allowing the foamed set-delayed cement composition to set in the subterranean formation.
- An example embodiment comprises a foamed set-delayed cement composition comprising: water, pumice, hydrated lime, a foaming additive, entrained gas, and a set retarder,
- An example embodiment comprises a system for cementing comprising: a set-delayed cement composition, comprising: water, pumice, hydrated lime, a set retarder, a foaming additive for foaming the set-delayed cement composition; a gas for foaming the set- delayed cement composition; and a cement set activator for activation of the set-delayed cement composition.
- a set-delayed cement composition comprising: water, pumice, hydrated lime, a set retarder, a foaming additive for foaming the set-delayed cement composition; a gas for foaming the set- delayed cement composition; and a cement set activator for activation of the set-delayed cement composition.
- FIG. I illustrates a system 2 for preparation of a set-delayed cement composition and delivery to a wellbore in accordance with certain embodiments.
- the set-delayed cement composition may be mixed in mixing equipment 4, such as a jet mixer, re-circulating mixer, or a batch mixer, for example, and then pumped via pumping equipment 6 to the wellbore, in some embodiments, the mixing equipment 4 and the pumping equipment 6 may be disposed on one or more cement trucks as will be apparent to those of ordinary skill in the art.
- a jet mixer may be used, for example, to continuously mix the lime/settable material with the water as it i being pumped to the wellbore,
- FIG. 2A illustrates surface equipment 10 that may be used in placement of a set-delayed cement composition in accordance with certain embodiments.
- FIG. 2A generally depicts a land-based operation, those skilled in the art will readily recognize thai the principles described herein are equally applicable to subsea operations that employ floating or sea-based platforms and rigs, without departing from the scope of the disclosure.
- the surface equipment 10 may include a cementing unit 1 2, which may include one or more cement trucks.
- the cementing unit 12 may include mixing equipment 4 and pumping equipment 6 (e.g., FIG. 1 ) as will be apparent to those of ordinary skill in the art.
- the cementing unit 12 may pump a set-delayed cement composition 14 through feed pipe 16 and to a cementing head 18 which conveys the set-delayed, cement composition 1 downhole.
- the set-delayed cement composition 14 may be placed into a subterranean formation 20 in accordance with example embodiments.
- a wellbore 22 may be drilled into the subterranean formation 20, While we!lbore 22 is sho n extending generally verticall into the subterranean formation 20, the principles described herein are also applicable to weiibores that extend at an angle through the subterranean formation 20, such as horizontal and slanted weiibores.
- the wellbore 22 comprises walls 24, In the illustrated embodiment, a surface easing 26 has been inserted into the wellbore 22, The surface casing 26 may be cemented to the walls 24 of the wellbore 22 b cement sheath 28, In the illustrated embodiment, one or more additional conduits (e.g., intermediate casing, production casing, liners, etc.), shown here as casing 30 may also be disposed in the wellbore 22. As illustrated, there is a wellbore annulus 32 formed between the casing 30 and the walls 24 of the wellbore 22 and/or the surface casing 26. One or more centralizers 34 may be attached to the casing 30, for example, to centralize the casing 30 in the wellbore 22 prior to and. during the cementing operation.
- additional conduits e.g., intermediate casing, production casing, liners, etc.
- the set-delayed cement composition 1.4 may be pumped down the interior of the easing 30,
- the set-delayed cement composition 14 may be allowed to flow down the interior of the casing 30 through the casing shoe 42 at the bottom of the casing 30 and up around the casing 30 into the wellbore annulus 32
- the set- delayed cement composition 14 may be allowed to set in the wellbore annulus 32, for example, to form a cement sheath that supports and positions the easing 30 in the wellbore 22.
- other techniques may also be utilized for introduction of the set- delayed cement composition 14. B way of example, reverse circulation techniques may be used that include introducing the set-delayed cement composition 14 into the subterranean formation. 20 by way of the wellbore annulus 32 instead of through the casing 30,
- the set -delayed cement composition 14 may displace other fluids 36, such as drilling fluids and/or spacer fluids that may be present in the interior of the casing 30 and/or the wellbore annulus 32. At least a portion of the displaced fluids 36 may exit the wellbore annulus 32 via a flow line 38 and be deposited, for example, in one or more retention pits 40 (e.g., a mud pit), as shown on FIG. 2 A.
- a bottom plug 44 may be introduced into the wellbore 22 ahead of the set-delayed cement composition 14, lor example, to separate the set-delayed cement composition 14 from the fluids 36 that may be inside the casing 30 prior to cementing.
- a diaphragm or other suitable device should rupture to allow the set-delayed cement composition 14 through the bottom plug 44, In FIG, 2B. the bottom plug 44 is shown on the landing collar 46.
- a top plug 48 may be introduced into the wellbore 22 behind the set-delayed cement composition .14. The top plug 48 may separate the set-delayed cement composition 14 from a displacement fluid 50 and also push the set-delayed cement composition 1 through the bottom plug 44.
- the exemplar)' set-delayed cement compositions disclosed herein may directly or indirectly affect one or more components or pieces of equipment associated with the preparation, delivery, recapture, recycling, reuse, and/or disposal of the disclosed set- delayed ceraeni compositions.
- the disclosed set-de!ayed ceraeni compositions may directly or indirectly affect one or more .mixers, related mixing equipment, mud pits, storage facilities or units, composition separators, heat exchangers, sensors, gauges, pumps, compressors, and the like used generate, store, monitor, regulate, and/or recondition the exemplary set-delayed cement compositions.
- the disclosed set-delayed cement compositions may also directly or indirectly affect any transport or delivery equipment used to convey the set-delayed cement compositions to a well site or downhole such as, for example, any transport vessels, -conduits, pipelines, trucks, lobulars, and/or pipes used to compos ItSonally move the set-delayed cement compositions from one location to another, any pumps, compressors, or motors (e.g., topside or downhole) used to drive the set-delayed cement compositions into motion, any valves or related joints used to regulate the pressure or flow rate of the set-delayed cement compositions, and any sensors (i.e., pressure and temperature), gauges, and/or combinations thereof and the like.
- any transport or delivery equipment used to convey the set-delayed cement compositions to a well site or downhole
- the disclosed set-delayed cement compositions may also directly or indirectly affect the various downhole equipment and tools that may come into contact with the set-delayed cement compositions such as, but not limited to, wellbore casing, wellbore liner, completion string, insert strings, drill string, coiled tubing, s!iekline, wireline, drill pipe, drill collars, mud motors, downhole motors and/or pumps, cement pumps, surface-mounted motors and/or pumps, ce.niraiize.rs, turbolizers, scratc!iers, floats (e.g., shoes, collars, valves, etc.), logging tools and related telemetry equipment, actuators (e.g., electromechanical devices, hydromeehanical devices, etc.), sliding sleeves, production sleeves, plugs, screens, filters, flow control devices (e.g., inflow control devices, autonomous inflow control devices, outflow control devices, etc.), couplings (e.g., electro-hydraulic wet connect, dry connect, inductive
- a sample set-delayed cement composition was prepared with the following components: pumice (DS-325 lightweight aggregate), hydrated lime, dispersant (Liquimeot* 558 I F), primary retarder (Micro Matrix*" ' cement retarder), weighting additive ⁇ MieroMax* Weight Additive, available from Halliburton ' Energy Services, inc., Houston, Texas), secondary retarder (HR*»5 cement retarder, available from Halliburton Energ Services, Inc., Houston, Texas), Class H Portland cement, and water.
- Each component, with the exception of the primary retarder (Micro Matrix* cement retarder) is presented as a percentage of the weight of pumice (bwoP).
- the primary retarder is measured in units of gallons per 46 pound sack of pumice (gal/sk).
- the compositional makeup is listed in Table I below.
- Example 1 The sample in Example 1 remained fluid, mixabie, pumpable, and stabl with no solids settling or gelation for greater than 40 days.
- the sample had a measured density of ! 3.5 pounds per gallon. Minimal doses of dispersant were added during the storage perio to maintain the slurry's optimal rheology.
- This exemplary sample serves as the base slurry for the remaining examples provided below.
- the destructive compressive strength was measured using a mechanical press hi accordance with API RP Practice 10B-2, Recommended Practice for Jesting Weil Cements, Additionally,, the destructive compressive strength was measured by allowing the samples to cure in a 2" by 4" plastic cylinder thai was placed in a water bath at ⁇ 90 ⁇ to form set cylinders. Immediately after removal from the water bath, destructive compressive strength were determined using a mechanical press i accordance with API RP !OJB-2, Recommende Practice for Testing Well Cements, The results of this test are set forth below. The reported compressive strengths are an average tor two cylinders of each sample. The samples and controls were cured at 1 atmosphere, 190*F; compressive strength measurements were taken at 72 hours.
- Example 3 thus indicates that the teamed slurries exhibit good compressive strength while maintaining suitable rheologies and uniform densities.
- Two .sample set-delayed cement compositions samples 4 and 5, were prepared from the base slurry described in Example 3 .
- a cement set activator, CaCl 2 was added to the samples i an amount sufficient to deliver a 5% by weight of pumice activator amount to the set-delayed cement composition.
- Sample 5 further included graphitic carbon fibers in an amount of about 0.18% by weight of the pumice.
- the graphitic carbon fibers were PAN carbon fibers derived from polyacryionitrile.
- Foamer 1026' a foaming additive, was added to each of the samples in an amount of 0. 18% by weight of the pumice.
- the destructive compressive strength was measured by allowing the samples to cure in a 2" by 4" plastic cylinder that was placed in a water bath at 190°P to form set cylinders, immediately after removal from the water bath, destructive compressive strengths were determined using a mechanical press in accordance with API RF 10B-2, Recommended Practice for Testing Weil Cements, The results of this test are set forth below.
- the reported compressive strengths are an average for three cylinders of each sample. The samples and controls were cured at 1 atmosphere, 1 0°F; compressive strength measurements were taken at 72 hours. Table 7
- compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of * or “consist of the various components and steps.
- indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces,
- ranges from any lower limit may be combined with any upper limit to recite a range not. explicitly recited, as well as, ranges from any lower limit may be combined with an other Sower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
- any number and any included range falling within the range are specifically disclosed, in particular, every range of values (of the form, "from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a ⁇ b”> disclosed herein is to be understood to set forth every number and range encompassed within, the broade range of values even if not explicitly recited.
- ever point or individual value may serve as its own. lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
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Abstract
Description
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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AU2014317923A AU2014317923B2 (en) | 2013-09-09 | 2014-09-08 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
RU2016103916A RU2655669C2 (en) | 2013-09-09 | 2014-09-08 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
MX2016001651A MX2016001651A (en) | 2013-09-09 | 2014-09-08 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime. |
BR112016002545A BR112016002545A2 (en) | 2013-09-09 | 2014-09-08 | method for cementing in an underground formation, delayed curing cement composition, and system for cementing |
CA2920756A CA2920756C (en) | 2013-09-09 | 2014-09-08 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
GB1600816.1A GB2535857B (en) | 2013-09-09 | 2014-09-08 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
NO20160086A NO20160086A1 (en) | 2013-09-09 | 2016-01-15 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
AU2016222404A AU2016222404B2 (en) | 2013-09-09 | 2016-08-31 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
AU2018232978A AU2018232978B2 (en) | 2013-09-09 | 2018-09-20 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
Applications Claiming Priority (4)
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US201361875410P | 2013-09-09 | 2013-09-09 | |
US61/875,410 | 2013-09-09 | ||
US14/032,734 | 2013-09-20 | ||
US14/032,734 US9328281B2 (en) | 2012-03-09 | 2013-09-20 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
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WO2015035280A1 true WO2015035280A1 (en) | 2015-03-12 |
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PCT/US2014/054496 WO2015035280A1 (en) | 2013-09-09 | 2014-09-08 | Foaming of set-delayed cement compositions comprising pumice and hydrated lime |
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AU (3) | AU2014317923B2 (en) |
BR (1) | BR112016002545A2 (en) |
CA (1) | CA2920756C (en) |
GB (1) | GB2535857B (en) |
MX (1) | MX2016001651A (en) |
NO (1) | NO20160086A1 (en) |
RU (1) | RU2655669C2 (en) |
WO (1) | WO2015035280A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3127886A1 (en) * | 2015-08-03 | 2017-02-08 | CellConTec GmbH | Foaming agent and method for foaming and stabilization of a construction material mash for low-pore building materials |
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US20040211342A1 (en) * | 2003-04-25 | 2004-10-28 | Mbt Holding Ag | Rheology stabilizer for cementitious compositions |
US20040226484A1 (en) * | 2002-11-19 | 2004-11-18 | Jiten Chatterji | Methods and cement compositions for cementing in subterranean zones |
US20090011207A1 (en) * | 2007-07-05 | 2009-01-08 | United States Gypsum Company | Lightweight cementitious compositions and building products and methods for making same |
US20100044043A1 (en) * | 2005-09-09 | 2010-02-25 | Halliburton Energy Services, Inc. | Methods of Cementing in Subterranean Formations Using Cement Kiln Dust in Compositions Having Reduced Portland Cement Content |
WO2011161411A1 (en) * | 2010-06-23 | 2011-12-29 | Halliburton Energy Services, Inc | Weighted elastomers, cement compositions comprising weighted elastomers, and methods of use |
Family Cites Families (1)
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US7631692B2 (en) * | 2005-09-09 | 2009-12-15 | Halliburton Energy Services, Inc. | Settable compositions comprising a natural pozzolan and associated methods |
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2014
- 2014-09-08 GB GB1600816.1A patent/GB2535857B/en active Active
- 2014-09-08 WO PCT/US2014/054496 patent/WO2015035280A1/en active Application Filing
- 2014-09-08 RU RU2016103916A patent/RU2655669C2/en active
- 2014-09-08 BR BR112016002545A patent/BR112016002545A2/en not_active Application Discontinuation
- 2014-09-08 AU AU2014317923A patent/AU2014317923B2/en active Active
- 2014-09-08 CA CA2920756A patent/CA2920756C/en active Active
- 2014-09-08 MX MX2016001651A patent/MX2016001651A/en unknown
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2016
- 2016-01-15 NO NO20160086A patent/NO20160086A1/en unknown
- 2016-08-31 AU AU2016222404A patent/AU2016222404B2/en active Active
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2018
- 2018-09-20 AU AU2018232978A patent/AU2018232978B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040226484A1 (en) * | 2002-11-19 | 2004-11-18 | Jiten Chatterji | Methods and cement compositions for cementing in subterranean zones |
US20040211342A1 (en) * | 2003-04-25 | 2004-10-28 | Mbt Holding Ag | Rheology stabilizer for cementitious compositions |
US20100044043A1 (en) * | 2005-09-09 | 2010-02-25 | Halliburton Energy Services, Inc. | Methods of Cementing in Subterranean Formations Using Cement Kiln Dust in Compositions Having Reduced Portland Cement Content |
US20090011207A1 (en) * | 2007-07-05 | 2009-01-08 | United States Gypsum Company | Lightweight cementitious compositions and building products and methods for making same |
WO2011161411A1 (en) * | 2010-06-23 | 2011-12-29 | Halliburton Energy Services, Inc | Weighted elastomers, cement compositions comprising weighted elastomers, and methods of use |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3127886A1 (en) * | 2015-08-03 | 2017-02-08 | CellConTec GmbH | Foaming agent and method for foaming and stabilization of a construction material mash for low-pore building materials |
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AU2018232978B2 (en) | 2020-02-27 |
BR112016002545A2 (en) | 2017-08-01 |
GB201600816D0 (en) | 2016-03-02 |
CA2920756C (en) | 2019-04-02 |
RU2655669C2 (en) | 2018-05-29 |
AU2018232978A1 (en) | 2018-10-11 |
AU2016222404B2 (en) | 2018-07-05 |
GB2535857A (en) | 2016-08-31 |
AU2016222404A1 (en) | 2016-09-22 |
RU2016103916A (en) | 2017-10-16 |
AU2014317923B2 (en) | 2016-06-09 |
NO20160086A1 (en) | 2016-01-15 |
AU2014317923A1 (en) | 2016-02-04 |
GB2535857B (en) | 2020-06-24 |
CA2920756A1 (en) | 2015-03-12 |
MX2016001651A (en) | 2016-11-07 |
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