CN115043977A - Composition, preparation and application of amphoteric ionic polymer retarder for aluminate cement for well cementation - Google Patents
Composition, preparation and application of amphoteric ionic polymer retarder for aluminate cement for well cementation Download PDFInfo
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- CN115043977A CN115043977A CN202210717771.7A CN202210717771A CN115043977A CN 115043977 A CN115043977 A CN 115043977A CN 202210717771 A CN202210717771 A CN 202210717771A CN 115043977 A CN115043977 A CN 115043977A
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- retarder
- aluminate cement
- well cementation
- polymer retarder
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- 239000004568 cement Substances 0.000 title claims abstract description 93
- 150000004645 aluminates Chemical class 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000831 ionic polymer Polymers 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 125000002091 cationic group Chemical group 0.000 claims abstract description 24
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 38
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 230000008719 thickening Effects 0.000 abstract description 29
- 238000010276 construction Methods 0.000 abstract description 10
- 230000002159 abnormal effect Effects 0.000 abstract description 4
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002002 slurry Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 8
- 235000010338 boric acid Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- 230000000979 retarding effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000005465 channeling Effects 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- -1 alkyl tertiary amine Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- 230000007704 transition Effects 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 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 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a composition, preparation and application of an aluminate cement zwitterionic polymer retarder for well cementation. The synthetic monomer of the amphoteric polymer retarder comprises: 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), Maleic Acid (MA), sodium p-styrenesulfonate (SSS), and a cationic monomer. The zwitterionic polymer retarder contains a constitutional unit A represented by formula 1, a constitutional unit B represented by formula 2, a constitutional unit C represented by formula 3, and a constitutional unit D represented by formula 4. The zwitterionic polymer retarder can obviously prolong the thickening time of aluminate cement paste and thickenThe thickness change is normal in the process, the abnormal gelatinization phenomenon can not occur, meanwhile, the right-angle thickening phenomenon is obvious, the well cementation construction time and safety can be guaranteed, and the problems that the thickening time of the aluminate cement well cementation construction in the prior art is not easy to adjust, the thickness change is unstable, the construction risk is high and the like are effectively solved.
Description
Technical Field
The invention relates to an aluminate cement zwitterionic polymer retarder for well cementation, which has a very good retarding effect and an obvious right-angle thickening phenomenon aiming at aluminate cement, can avoid the problems of low-temperature super-retarding, abnormal gelation and the like while ensuring sufficient thickening time, has no adverse effect on other excellent performances of the aluminate cement, provides guarantee for the safety of aluminate cement well cementation construction, and promotes the large-scale use of the aluminate cement in the field of high-temperature-resistant well cementation.
Background
In recent years, special cement-aluminate cement has come to be used in the field of well cementation, especially in heavy oil thermal recovery wells, by virtue of its advantages of high strength, excellent early strength performance, high temperature resistance and corrosion resistance, and the advantages of aluminate cement can be fully exerted.
Although aluminate cement has the characteristics of early strength, high temperature resistance and the like and is widely applied to the fields of extreme rescue and relief, military construction and the like, the defects of the aluminate cement are not negligible: the later strength is seriously declined, the hydration speed is extremely high, and the like; for the problem of serious strength decline, the problem can be improved by mixing a specially-prepared modified admixture into the aluminate cement according to a proportion, however, the hydration speed of the aluminate cement is very high, the thickening time can be further reduced along with the addition of the admixture, and the conventional retarder, such as boric acid, citric acid and the like, cannot play an obvious role in retarding, so that the short thickening time is the most important reason for limiting the large use of the aluminate cement in the well cementation operation; just because the thickening time is short, the insufficient well cementation construction time can be caused, the construction safety accidents can be caused, meanwhile, the cement slurry pumped between the sleeves does not reach the designated area, the consistency becomes large, the space cannot be completely and tightly filled, hidden dangers are left for the occurrence of the well cementation accidents such as channeling and the like, the problem that the thickening time of the aluminate cement is too short can be successfully solved, and whether the aluminate cement can be applied in the engineering is determined.
The invention patent of aluminate cement retarder for well cementation of thick oil thermal recovery well in the prior art is disclosed as CN102994058A named as high temperature resistant non-silicate cement slurry system for well cementation of thick oil thermal recovery well, and the cement slurry system disclosed by the patent comprises the following components in percentage by mass: 100 parts of aluminate cement, 1.0-4.0 parts of polyvinyl alcohol, hydrolyzed polyacrylonitrile or carboxymethyl cellulose, 1.0-4.0 parts of melamine formaldehyde resin, calcium lignosulfonate, sodium lignosulfonate or sodium hexametaphosphate, 0.5-3.0 parts of gypsum, limestone, boric acid, sodium borate or a mixture thereof, 60-120 parts of water and 15-80 parts of slag or fly ash; the cement system adopts gypsum, limestone, boric acid and sodium borate as retarders, and is maintained at normal pressure and 50 ℃, the thickening time reaches about 2 hours to the maximum extent, and the normal well cementation requirement can not be met completely.
The retarder suitable for aluminate cement in the prior art is, for example, the authorized bulletin number is CN108585583B, and the retarder comprises: 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), unsaturated carboxylic acid, boric acid and glucose, wherein the initiator is ammonium persulfate, potassium persulfate or sodium hydroxide; the preparation method comprises the following steps: putting AMPS, unsaturated carboxylic acid, boric acid and glucose into a reaction kettle according to mass percentage, adding deionized water, uniformly stirring, keeping the stirring speed of 120r/min, heating to 60-75 ℃, introducing nitrogen or argon to remove air, and finally adding an initiator solution to keep reaction, wherein the mass ratio of the total mass of AMPS, unsaturated carboxylic acid, boric acid and glucose to the mass of the deionized water is 1: 1-1: 2; the retarder in the patent generally has thickening time not exceeding 200min, and meanwhile, the retarder is only applied to aluminate cement with lower strength, and has no value for practical application.
Disclosure of Invention
The invention discloses the composition, preparation and application of an aluminate cement zwitterionic polymer retarder for well cementation, which can ensure that aluminate cement keeps good strength and stability, delay the hydration speed to the maximum extent and increase the thickening time, can optimize the right-angle thickening performance of cement paste, can avoid the occurrence of an over-retarding phenomenon in a low-temperature environment, has no large interference influence on other performances of an aluminate cement paste system, and can solve the technical bottleneck of hindering the use of aluminate cement for well cementation.
In order to perfectly realize the aim of the invention, the technical scheme of the invention is as follows:
the retarder of amphoteric ion polymer of aluminate cement for well cementation comprises the following components: 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), Maleic Acid (MA), sodium p-styrenesulfonate (SSS), and a cationic monomer.
The synthetic monomers comprise the following components in percentage by mass: 45-60 parts of 2-propenyl amido-2-methyl propane sulfonic Acid (AMPS), 10-30 parts of Maleic Acid (MA), 5.0-15 parts of Sodium Styrene Sulfonate (SSS) and 20-40 parts of cationic monomer.
The synthetic process of the zwitterionic polymer retarder is as follows: firstly, removing oxygen in a ground three-neck flask of a reaction container, then adding 10-30 parts of Maleic Acid (MA) into 180-250 parts of deionized water, stirring and mixing in a stirrer, weighing 45-60 parts of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and 5.0-15 parts of Sodium Styrene Sulfonate (SSS), adding into the stirrer, mixing and stirring to obtain a mixed reaction solution, and pouring the mixed reaction solution into the ground three-neck flask completely; leveling the pH value of the reaction solution to 4-5 by using a NaOH solution, keeping stirring at a rotating speed of 200-500 rpm until no precipitate exists; preparing 20-40 parts of cationic monomer, and quickly dropwise adding and mixing by using a dropper when the solution state in the beaker is stable; and finally, preparing an initiator solution, dropwise adding the initiator solution into a ground three-neck flask at the dropwise adding rate of 5-10ml/min, keeping the reaction temperature of 50-60 ℃, and stirring for reacting for 8-10h to obtain the zwitterionic polymer retarder.
The zwitterionic polymer retarder contains a constitutional unit A shown in a formula 1, a constitutional unit B shown in a formula 2, a constitutional unit C shown in a formula 3 and a constitutional unit D shown in a formula 4.
R in the constituent unit A, the constituent unit B, the constituent unit C and the constituent unit D 1 、R 2 、R 3 And R 4 The same or different, H, methyl, ethyl, isopropyl or one of the constituent units A, B, C, D, wherein n in the constituent unit D is 6, 8 or 10.
The total mass of the synthetic monomers accounts for 36-80% of the total mass of the deionized water.
The oxygen in the reaction vessel is removed by filling nitrogen into the reaction vessel.
The initiator solution is a combination of an oxidizing agent and a reducing agent, wherein the oxidizing agent is potassium persulfate, ammonium persulfate or hydrogen peroxide, the reducing agent is sodium sulfite, sodium bisulfite or potassium borohydride, and the molar ratio of the using amount of the oxidizing agent to the using amount of the reducing agent is 2-5: 1-3.
The dosage of the initiator is 0.2-1.2% of the total mass of the synthetic monomers.
In terms of the current general technology, the present invention has the following advantages:
1. 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) is a common water-soluble anionic monomer, contains sulfonic groups, keeps stronger resistance in the face of external acid, alkali and salt corrosion, has good hydrolytic stability and excellent thermal stability due to amide groups, and ensures the structural stability of a copolymerization reaction product due to the combined action of the two groups; maleic Acid (MA) is used as a reaction monomer containing carboxyl, so that the adsorption capacity of a molecular chain of the zwitterionic polymer retarder on cement particles is improved, the hydration reaction of the cement particles is hindered, and the thickening time of the aluminate cement paste is prolonged while the right-angle thickening phenomenon is proved to be shown; benzene rings in the molecular structure of Sodium Styrene Sulfonate (SSS) promote excellent high-temperature resistance, the Sodium Styrene Sulfonate (SSS) is not easy to decompose at the temperature of below 300 ℃, the Sodium Styrene Sulfonate (SSS) has a positive effect on the compressive strength of cement, and sulfonic groups in para positions enhance the induction effect of polymerization reaction and can improve the success rate of polymerization reaction.
2. Introducing a cationic monomer which can react with Al in the aluminate cement during the hydration process of the aluminate cement 3+ 、Ca 2+ Forming unstable complex to inhibit Al in liquid phase 3+ 、Ca 2+ The relative concentration generates the retardation effect, improves the pressure bleeding rate of the cement paste, and prevents the problems of cement paste deposition layering and bleeding caused by the increase of the addition of the retarder.
3. The retarder aiming at aluminate cement in the prior art has various problems, such as abnormal gelation, too short thickening time, large influence on strength and the like, the zwitterionic polymer retarder does not have the problems, the whole thickening process is stable and normal, and the influence on set cement is very small.
4. The amphoteric ionic polymer retarder is synthesized by using common raw materials in the market, has wide and rich sources and low price, is suitable for large-scale production and use, and has simple synthesis process and conditions and low equipment requirement.
In conclusion, the invention has clear thought, mature and stable technology, wide material source and low cost, and can be widely applied to the development and the use of aluminate cement.
Drawings
FIG. 1 is the atmospheric 40 ℃ thickening curve for the cement slurry of example 2.
FIG. 2 is a graph showing the thickening time of the slurries of example 1, example 3, and comparative example 5 at 40 ℃ under atmospheric pressure.
FIG. 3 shows the compressive strengths of the set cements of example 3, comparative example 1 and comparative example 3 cured at 40 ℃ for 3d and 7d, respectively.
Detailed Description
Composition, preparation and application of aluminate cement zwitterionic polymer retarder for well cementation
The following specific examples and comparative examples are given to illustrate the specific embodiments of the present invention in detail to facilitate a comprehensive understanding of the technical results of the present invention.
Example 1
The embodiment provides an aluminate cement zwitterionic polymer retarder for well cementation, which comprises the following components in percentage by weight: 48 parts of 2-propenyl amido-2-methyl propane sulfonic Acid (AMPS), 28.8 parts of Maleic Acid (MA), 13 parts of Sodium Styrene Sulfonate (SSS) and 20 parts of cationic monomer in weight ratio; the 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) provides constitutional unit a of formula 5 in the zwitterionic polymer retarder; the Maleic Acid (MA) provides constitutional unit B of formula 6; the sodium p-styrene sulfonate (SSS) provides constitutional unit C of formula 7; the cationic monomer provides constitutional unit D of formula 8, wherein the cationic monomer is homemade by the laboratories of the university of petroleum in china (east of china).
The cationic monomer is synthesized by the following steps: taking out quantitative chloropropene (C) 3 H 5 Cl), N-dimethyl long-chain alkyl tertiary amine (the number of long chain alkyl is 4-10) and a little NaOH solution, carrying out quaternization reaction under the reaction conditions of 75 ℃ and 0.3MPa for 6h, and finally synthesizing to obtain the cationic monomer (preferably, N is 6, 8 and 10), wherein the reaction process is shown as formula 9:
the synthetic process of the zwitterionic polymer retarder is as follows: firstly, removing oxygen in a ground three-neck flask of a reaction container, then adding 28.8 parts of Maleic Acid (MA) into 220 parts of deionized water, stirring and mixing in a stirrer, then weighing 48 parts of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and 13 parts of Sodium Styrene Sulfonate (SSS), adding into the stirrer, continuously stirring to obtain a mixed reaction solution, and completely pouring the mixed reaction solution into the ground three-neck flask; leveling the pH value of the reaction solution to 4-5, preferably, the pH value is 4, keeping stirring at the rotation speed of 200-500 rpm, preferably, 300rpm until no precipitate exists; preparing 20 parts of cationic monomer, and quickly dropwise adding and mixing by using a dropper when the solution state in the beaker is stable; and finally, preparing an initiator solution, wherein the initiator solution is required to be dripped into a ground three-neck flask at a dripping rate of 5-10ml/min, keeping the temperature of 50-60 ℃, preferably, the reaction temperature is 50 ℃, and stirring and reacting for 8-10 hours to obtain the zwitterionic polymer retarder.
The initiator is a mixture of ammonium persulfate and sodium bisulfite, the addition molar ratio is 2: 1, and the addition amount of the initiator is 0.3 percent of the total mass of the monomers.
The aluminate cement comprises the following components: 69.25 parts of aluminum oxide, 0.24 part of silicon dioxide and 0.54 part of ferric oxide.
Example 2
The embodiment provides an aluminate cement zwitterionic polymer retarder for well cementation, which comprises the following components in percentage by weight: 55 parts of 2-propenyl amido-2-methyl propane sulfonic Acid (AMPS), 28.8 parts of Maleic Acid (MA), 6.5 parts of Sodium Styrene Sulfonate (SSS) and 40 parts of cationic monomer.
The cationic monomer synthesis procedure, conditions, drug species and reaction product of example 2 were identical to those of example 1.
The synthetic process of the zwitterionic polymer retarder is as follows: firstly, removing oxygen in a ground three-neck flask of a reaction container, adding 28.8 parts of Maleic Acid (MA) into 220 parts of deionized water, stirring and mixing in a stirrer, then weighing 55 parts of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and 6.5 parts of Sodium Styrene Sulfonate (SSS), adding into the stirrer, continuously stirring to obtain a mixed reaction solution, and completely pouring the mixed reaction solution into the ground three-neck flask; leveling the pH value of the reaction solution to 4-5, preferably, the pH value is 4, keeping stirring at the rotation speed of 200-500 rpm, preferably, 300rpm until no precipitate exists; preparing 40 parts of cationic monomer, and quickly dropwise adding and mixing by using a dropper when the solution state in the beaker is stable; and finally, preparing an initiator solution, wherein the initiator solution is required to be dripped into a ground three-neck flask at a dripping rate of 5-10ml/min, keeping the temperature of 50-60 ℃, preferably, the reaction temperature is 50 ℃, and stirring and reacting for 8-10 hours to obtain the zwitterionic polymer retarder.
The initiator is a mixture of ammonium persulfate and sodium bisulfite, the addition molar ratio is 3: 2, and the addition amount of the initiator is 0.4 percent of the total mass of the monomers.
The aluminate cement comprises the following components: 69.25 parts of aluminum oxide, 0.24 part of silicon dioxide and 0.54 part of ferric oxide.
Example 3
The embodiment provides an aluminate cement zwitterionic polymer retarder for well cementation, which comprises the following components in percentage by weight: by weight, 50 parts of 2-propenyl amido-2-methyl propane sulfonic Acid (AMPS), 14.4 parts of Maleic Acid (MA), 13 parts of Sodium Styrene Sulfonate (SSS) and 30 parts of cationic monomer.
The cation isThe method comprises the following steps: chloropropene, N-dimethyl long-chain alkyl tertiary amine (the number of long chain alkyl groups is an even number of 14-24) and a little Na 2 CO 3 Mixing the solution and an alcohol solvent (isopropanol) and adding the mixture into a reaction vessel, keeping the reaction temperature at 90 ℃ and the reaction pressure at 0.35MPa for 10 hours to obtain a cationic monomer with an alkyl chain length n of 15, 17, 19 or 21, wherein the reaction process is shown as a formula 10:
the synthetic process of the zwitterionic polymer retarder is as follows: firstly, removing oxygen in a ground three-neck flask of a reaction container, adding 14.4 parts of Maleic Acid (MA) into 220 parts of deionized water, stirring and mixing in a stirrer, then weighing 50 parts of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and 13 parts of Sodium Styrene Sulfonate (SSS), adding into the stirrer, continuously stirring to obtain a mixed reaction solution, and completely pouring the mixed reaction solution into the ground three-neck flask; leveling the pH value of the reaction solution to 4-5, preferably, the pH value is 4, keeping stirring at the rotation speed of 200-500 rpm, preferably, 300rpm until no precipitate exists; preparing 30 parts of cationic monomer, and quickly dropwise adding and mixing by using a dropper when the solution state in the beaker is stable; and finally, preparing an initiator solution, wherein the initiator solution is required to be dripped into a ground three-neck flask at a dripping rate of 5-10ml/min, keeping the temperature of 50-60 ℃, preferably, the reaction temperature is 50 ℃, and stirring and reacting for 8-10 hours to obtain the zwitterionic polymer retarder.
The initiator is a mixture of ammonium persulfate and sodium bisulfite, the addition molar ratio is 1:1, and the addition of the initiator is 0.2 percent of the total mass of the monomers.
The aluminate cement comprises the following components: 69.25 parts of aluminum oxide, 0.24 part of silicon dioxide and 0.54 part of ferric oxide.
Comparative example 1
Comparative example 1 consists of: 100 parts of aluminate cement and 44 parts of water.
Comparative example 2
Comparative example 2 consists of: 100 parts of aluminate cement, a plurality of parts of citric acid and 44 parts of water.
Comparative example 3
Comparative example 3 consists of: 100 parts of aluminate cement, a plurality of parts of boric acid and 44 parts of water.
Comparative example 4
Comparative example 4 consists of: 100 parts of aluminate cement, a plurality of parts of sodium lignosulphonate and 44 parts of water.
Comparative example 5
Comparative example 5 consists of: 100 parts of aluminate cement, a plurality of parts of cane sugar and 44 parts of water.
Secondly, comparing the performance test of the retarder of the amphoteric ionic polymer of aluminate cement for well cementation
The retarder is prepared from the embodiments 1, 2 and 3 and the comparative examples 1, 2, 3, 4 and 5 according to the cement slurry API experimental standard, the performances of the cement slurry system such as low-temperature compressive strength, thickening time and the like are tested and compared according to the GB/T19139-.
The influence of different temperatures and pressures on the retarding effect of the zwitterionic polymer retarder is explored; with examples 1, 2 and 3 and comparative examples 1, 2, 3, 4 and 5 as test objects, 8 groups of aluminate cement slurries were prepared, a retarder was added to each group in an amount of 0.6% by mass of the aluminate cement, and the thickening time and the final setting time were measured under normal pressure and high pressure at different temperatures.
Table 1 shows the thickening time of the aluminate cement zwitterionic polymer retarder for well cementation under different temperatures and pressures:
as can be seen from Table 1: compared with the comparative example, the zwitterionic polymer retarder has the advantages that the retarder has the effect on aluminate cement under the conditions of different temperatures and different pressuresThe retarding effect of a larger degree ensures sufficient safe construction time for well cementation, on the other hand, the application range of the aluminate cement is directly expanded, and the aluminate cement can be applied to both shallow wells and medium-deep wells; the length n of the cationic monomer alkyl chain used in examples 1 and 2 is within 10, the cationic monomer alkyl chain used in example 3 is relatively longer, and the larger the length n of the alkyl chain, the longer the monomer chain is, the stronger the hydrophobicity is, and the stronger hydrophobicity can influence the retarding effect of the synthesized zwitterionic polymer retarder on aluminate cement, so that the cationic monomer with shorter chain length is preferentially adopted for synthesis; 2-acrylamide-2-methyl propanesulfonic Acid (AMPS) is used as a main body frame of a zwitterionic polymer retarder group, and the stability and integrity of the retarder macromolecular group at a higher temperature can be promoted by utilizing the advantage of good thermal stability of the retarder macromolecular group; sodium Styrene Sulfonate (SSS) also has a promoting effect on the structural stability of a retarder macromolecular group, and more importantly, sulfonic groups on para positions of benzene rings play an inducing effect, so that the success rate of copolymerization is improved to a great extent; the absorption and complexation of the macromolecular groups of the retarder delay the hydration speed of the modified aluminate cement, increase the thickening time, and the surface of the cement particles is provided with a large amount of Al 3+ 、Ca 2+ With which, on the one hand, the cationic monomer groups form unstable complexes and, on the other hand, the-SO groups in the macromolecular groups 3- ，－COO - The negative ions can be adsorbed on cement particles due to the principle of opposite attraction, the surfaces of the cement particles are occupied by a large number of polymer macromolecular groups, the contact and exchange between the cement particles and external substances are isolated, the spatial repulsion force repels the condensation of the cement particles, and meanwhile, due to the adsorption of the active molecular groups of the amphoteric ion polymer retarder, the limited space between the cement particles is occupied, so that the steric hindrance effect is generated, the cement particles are further kept stable in dispersion, the slurry fluidity is improved, the slurry consistency is reduced, the field filling construction is very facilitated, the space of a filled casing can be filled with cement slurry, and the inter-well channeling is avoided.
The influence of different addition amounts on the retarding effect of the zwitterionic polymer retarder is explored; the thickening time and the cement paste thickening transition time are tested by taking the example 2 and the comparative example 5 with good retarding effect as test objects.
Table 2 shows the effect of different amounts of zwitterionic polymer retarder and conventional retarder:
as can be seen from Table 2: the zwitterionic polymer retarder of the invention prolongs the thickening time in a positive proportion along with the increase of the addition, and the slight increase and decrease of the addition does not cause the great change of the thickening time, which indicates that the retarder is not particularly sensitive to the addition, improves the addition fault-tolerant rate, and the addition of the raw materials on a well cementation construction site is not necessarily as accurate as that under the laboratory condition, so the amphoteric polymer retarder is very beneficial to regulating and controlling the thickening time according to the conditions on the site; meanwhile, the transition time of the aluminate cement paste is short, namely the right-angle thickening phenomenon is obvious, once the cement paste is poured in place between the casings, the fluidity of the cement paste can be rapidly lost, the early strength is formed, and the possibility of accidents is reduced.
The influence of the zwitterionic polymer retarder on the strength of the set cement is researched; the retarder addition amounts of the examples and comparative examples were 0.6%.
Table 3 shows the early low-temperature curing strength:
as can be seen from the data in Table 3: one of the stable products of low-temperature hydration of aluminate cement is C 3 AH 6 A substance with a loose crystal structure, which causes the strength of the set cement to decline, and for the retarder, the requirement cannot cause great adverse effect on the strength of the set cement; referring to comparative example 1, it was found that the strength was minimally affected by the zwitterionic polymer retarder of example 3, which had a strength reduction rate of only between 0.71% and 4.69%, and examples 1 and 2, although having a slightly greater strength reduction rate, still maintained a higher compressive strength, the prior art retarders, like boric acid and citric acidThe strength of the aluminate cement stone is greatly reduced by sodium lignosulfonate and sucrose, and potential safety well cementation quality hazards exist.
In conclusion, the retarder for the amphoteric ionic polymer of the aluminate cement for well cementation completely meets the engineering time requirement of aluminate cement well cementation, does not generate great adverse effect on the strength and other properties of a set cement, does not generate phenomena of super retardation, abnormal gelation and the like in a low-temperature environment, solves the technical problem which is difficult to overcome by the existing aluminate cement well cementation technology, reduces the damage of a cement ring and a casing, prevents accidents of water channeling, air channeling and the like, improves the production safety of an oil well, and has great commercial engineering use potential and value.
Claims (5)
1. The retarder of amphoteric ion polymer of aluminate cement for well cementation comprises the following components: 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), Maleic Acid (MA), Sodium Styrene Sulfonate (SSS), cationic monomers;
the synthetic monomers comprise the following components in percentage by mass: 45-60 parts of 2-propenyl amido-2-methyl propane sulfonic Acid (AMPS), 10-30 parts of Maleic Acid (MA), 5.0-15 parts of Sodium Styrene Sulfonate (SSS) and 20-40 parts of cationic monomer;
the synthetic process of the zwitterionic polymer retarder is as follows: firstly, removing oxygen in a ground three-neck flask of a reaction container, then adding 10-30 parts of Maleic Acid (MA) into 180-250 parts of deionized water, stirring and mixing in a stirrer, weighing 45-60 parts of 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) and 5.0-15 parts of Sodium Styrene Sulfonate (SSS), adding into the stirrer, mixing and stirring to obtain a mixed reaction solution, and pouring the mixed reaction solution into the ground three-neck flask completely; leveling the pH value of the reaction solution to 4-5 by using a NaOH solution, keeping stirring at a rotating speed of 200-500 rpm until no precipitate exists; preparing 20-40 parts of cationic monomer, and quickly dropwise adding and mixing by using a dropper when the solution state in the beaker is stable; finally, preparing an initiator solution, dropwise adding the initiator solution into a ground three-neck flask at the dropwise adding rate of 5-10ml/min, keeping the reaction temperature of 50-60 ℃, and stirring for reacting for 8-10h to obtain the zwitterionic polymer retarder;
the zwitterionic polymer retarder contains a constitutional unit A shown in a formula 1, a constitutional unit B shown in a formula 2, a constitutional unit C shown in a formula 3 and a constitutional unit D shown in a formula 4;
wherein R in the constituent unit A, the constituent unit B, the constituent unit C and the constituent unit D 1 、R 2 、R 3 And R 4 The same or different, H, methyl, ethyl, isopropyl or one of the constituent units A, B, C, D, wherein n in the constituent unit D is 6, 8 or 10.
2. The composition and preparation of the amphoteric ionic polymer retarder for well cementation according to claim 1, wherein the total mass of the synthetic monomers is 36-80% of the total mass of deionized water.
3. The composition and preparation of the cement-cementing aluminate cement zwitterionic polymer retarder as claimed in claim 1, wherein the oxygen in the reaction vessel is removed by charging nitrogen into the reaction vessel.
4. The composition and preparation of the amphoteric ionic polymer retarder for well cementation according to claim 1, wherein the initiator solution is a redox system combination, wherein the oxidizing agent is potassium persulfate, ammonium persulfate or hydrogen peroxide, the reducing agent is sodium sulfite, sodium bisulfite or potassium borohydride, and the molar ratio of the using amount of the oxidizing agent to the reducing agent is 2-5: 1-3.
5. The composition and preparation of the cement-cementing aluminate cement zwitterionic polymer retarder as claimed in claim 1, wherein the amount of the initiator is 0.2-1.2% of the total mass of the synthetic monomer.
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