CN115925341B - Flexible self-healing cement slurry for well cementation of salt cavern gas storage and preparation method thereof - Google Patents
Flexible self-healing cement slurry for well cementation of salt cavern gas storage and preparation method thereof Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 149
- 239000002002 slurry Substances 0.000 title claims abstract description 66
- 150000003839 salts Chemical class 0.000 title claims abstract description 62
- 238000003860 storage Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000013005 self healing agent Substances 0.000 claims abstract description 33
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- 239000012745 toughening agent Substances 0.000 claims abstract description 23
- 239000013530 defoamer Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical group C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 238000004132 cross linking Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 9
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 7
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 4
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 4
- 229940083037 simethicone Drugs 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- -1 acrylic ester Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003129 oil well Substances 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000010755 BS 2869 Class G Substances 0.000 claims description 2
- 230000007774 longterm Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 50
- 239000000243 solution Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000012267 brine Substances 0.000 description 30
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011161 development Methods 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000007789 sealing Methods 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000003776 cleavage reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000007017 scission Effects 0.000 description 5
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 4
- 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 description 4
- 238000010276 construction Methods 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009933 burial Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application discloses a toughness self-healing cement paste for salt cavern gas storage well cementation and a preparation method thereof, wherein the toughness self-healing cement paste for salt cavern gas storage well cementation comprises the following components: 100 parts of cement, 4-6 parts of toughening agent, 8-12 parts of self-healing agent, 3-5 parts of fluid loss agent, 0.05-0.2 part of retarder, 1-2 parts of drag reducer, 0.1-0.2 part of defoamer and 30-50 parts of 15% saline water. Wherein, the fluid loss agent is AMPS polymer with salt-resistant low-temperature early strength characteristic. The tough self-healing cement slurry for well cementation of the salt cavern gas storage has the characteristics of good salt resistance, low Wen Zao strength, water loss control, excellent rheological property, excellent mechanical property, self-healing and the like, and can ensure long-term efficient and stable operation of the salt cavern gas storage.
Description
Technical Field
The application relates to the field of oilfield cementing cement, in particular to tough self-healing cement slurry for salt cavern gas storage cementing and a preparation method thereof.
Background
Whether the salt cavern gas storage can run for a long time with high efficiency depends on the sealing performance of the salt cavern cavity and the shaft, and the well cementation quality is most important for guaranteeing the shaft sealing.
The salt cavern type gas storage is generally shallow in salt layer burial depth, low in stratum temperature, and low in winter, and has a maximum temperature of 60 ℃ and a maximum temperature in a well of about 50 ℃ in normal well cementation operation. For a saline cement slurry system, the stability is poor, the water loss is not easy to control, the compressive strength is slow to develop, the thixotropy is strong, the rheological property is poor, and the well cementation quality is difficult to ensure. Meanwhile, the gas injection and production amount of the salt cavern gas storage is large, the shaft is in an alternating stress state of injection and production, and in the service life of the salt cavern gas storage, the alternating stress must be considered so as to ensure the safe operation of the gas storage for at least 30 years. Therefore, in order to ensure long-term safe operation of the gas storage, the stability and long-term sealing performance of the cement sheath strength must be ensured. Therefore, the development of the salt-resistant, low-temperature and early-strength toughness self-healing cement slurry is required, and the long-term efficient and stable operation of the salt cavern type gas storage is ensured.
Disclosure of Invention
The application provides a tough self-healing cement slurry for well cementation of a salt cavern gas storage and a preparation method thereof, which can ensure long-term efficient and stable operation of the salt cavern gas storage.
The application adopts the following technical scheme:
the application provides a tough self-healing cement slurry for salt cavern gas storage well cementation, which comprises the following components: 100 parts of cement, 4-6 parts of toughening agent, 8-12 parts of self-healing agent, 3-5 parts of fluid loss agent, 0.05-0.2 part of retarder, 1-2 parts of drag reducer, 0.1-0.2 part of defoamer and 30-50 parts of 15% saline water. Wherein, the fluid loss agent is AMPS polymer with salt-resistant low-temperature early strength characteristic.
Further, the fluid loss agent is polymerized by the following components: 100 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 0.1 to 0.5 part by weight of a crosslinking monomer, 1 to 3 parts by weight of a molecular weight regulator, 1 to 3 parts by weight of an alcohol monomer, 8 to 10 parts by weight of an amide monomer, 0.5 to 1.0 part by weight of a carboxylic acid monomer and 300 to 400 parts by weight of water. The crosslinking monomer and the molecular weight regulator are used for controlling the crosslinking structure and molecular weight distribution of the fluid loss agent, and comprehensively improving the water loss control capability of the fluid loss agent in the saline mud prepared by using the fluid loss agent. The alcohol monomer is used for promoting the strength development of the cement-containing slurry under the low-temperature condition.
Further, the cement comprises a class G oil well cement.
Further, the retarder includes a phosphonate.
Further, the drag reducing agent comprises polynaphthalenesulfonic acid.
Further, the defoamer comprises tributyl phosphate and/or simethicone.
Further, the toughening agent is prepared from the following components: 20-60 parts by weight of whisker material, 5-10 parts by weight of surfactant, 5-10 parts by weight of silane coupling agent, 1-5 parts by weight of defoamer, 10-25 parts by weight of stabilizer, 100 parts by weight of water and 250-1000 parts by weight of absolute ethyl alcohol.
Further, the self-healing agent has a core-shell structure. The self-healing agent comprises the following components in percentage by weight: the mass ratio of the styrene-based monomer to the vinyl polymer crosslinking agent to the initiator is 100: 20-40: 2 to 6. The self-healing agent comprises the following components in percentage by weight: the mass ratio of the styrene-based monomer to the acrylic ester to the vinyl polymer crosslinking agent to the initiator is 100: 30-70: 5-10: 2 to 8.
The application also provides a preparation method of the tough self-healing cement slurry for the salt cavern gas storage well cementation, which comprises the following steps: and uniformly mixing cement, a toughening agent, a self-healing agent, a fluid loss agent, a retarder, a drag reducer, a defoaming agent and 15% saline water to obtain the tough self-healing cement slurry for the well cementation of the salt cavern gas storage.
Further, cement, a toughening agent, a self-healing agent, a fluid loss agent, a retarder, a drag reducer, a defoaming agent and 15% saline water are uniformly mixed, and the method comprises the following steps: under the stirring condition, adding cement, a toughening agent, a gas self-healing agent, a fluid loss agent, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform.
Compared with the prior art, the application has the following beneficial effects:
1. the tough self-healing cement slurry for salt cavern gas storage well cementation has the characteristic of good salt resistance, and can be prepared from 15% salt water.
2. The ductile self-healing cement slurry for salt cavern gas storage well cementation has the characteristic of low-temperature early strength, the strength is up to 6 hours, and the strength is more than 30MPa for 24 hours.
3. The tough self-healing cement slurry for the well cementation of the salt cavern gas storage has the characteristic of excellent mechanical properties, all mechanical properties meet the requirements in the industrial standard SY-T7648-2021' technical requirement for well cementation of the gas storage, and the slurry is not damaged when being operated for 50 times under the conditions of 28MPa of confining pressure, 4-24 MPa of alternating internal pressure and 50-65 ℃ of alternating temperature, so that the long-term sealing integrity of the salt cavern gas storage can be ensured.
4. The tough self-healing cement paste for the salt cavern gas storage well cementation has the characteristic of self-healing, and can effectively protect cement rings for the second time.
In conclusion, the toughness self-healing cement slurry for the well cementation of the salt cavern gas storage can ensure long-term efficient and stable operation of the salt cavern gas storage.
Drawings
FIG. 1 is a graph showing the static gelation of cement slurry at 52℃in example 1 of the cement slurry of the present application;
fig. 2 is a triaxial plot of cement slurry in cement slurry example 2 of the present application.
FIG. 3 is a graph of the integrity check of cement sheath under alternating loading conditions obtained from cement slurry of example 3 of the present application.
Detailed Description
The technical methods in the embodiments of the present application will be clearly and completely described below. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
The application provides a tough self-healing cement slurry for salt cavern gas storage well cementation, which comprises the following components: 100 parts of cement, 4-6 parts of toughening agent, 8-12 parts of self-healing agent, 3-5 parts of fluid loss agent, 0.05-0.2 part of retarder, 1-2 parts of drag reducer, 0.1-0.2 part of defoamer and 30-50 parts of 15% saline water. Preferably, 100 parts of cement, 5 parts of toughening agent, 8 parts of self-healing agent, 4 parts of fluid loss agent, 0.2 part of retarder, 1 part of drag reducer, 0.2 part of defoamer and 50 parts of 15% brine.
Wherein the cement may be a G-class oil well cement.
The retarder may be a phosphonate. Retarder may be used in an amount of 0.05, 0.1, 0.15, 0.2 parts by weight.
The drag reducing agent may be polynaphthalenesulfonic acid. The drag reducer may be used in an amount of 1, 1.5, 2 parts by weight.
The defoamer can be tributyl phosphate and/or simethicone, for example, the defoamer can be tributyl phosphate or a mixture of tributyl phosphate and simethicone. The defoamer may be used in an amount of 0.1, 0.15, 0.2 parts by weight.
The brine with the concentration of 15% can be brine prepared by adopting industrial NaCl and tap water according to the mass fraction of 15%.
In addition, the toughening agent can be prepared from the following components: 20-60 parts by weight of whisker material, 5-10 parts by weight of surfactant, 5-10 parts by weight of silane coupling agent, 1-5 parts by weight of defoamer, 10-25 parts by weight of stabilizer, 100 parts by weight of water and 250-1000 parts by weight of absolute ethyl alcohol, wherein the toughening agent can be prepared according to the embodiment 1 in the patent application No. 201611089451.2, namely the fiber toughening agent for well cementing slurry and the preparation method thereof, and the model can be BCE-310S.
The self-healing agent (or called gas self-healing agent) can have a core-shell structure, and the proportion of the components of the core structure in the self-healing agent can be as follows: the mass ratio of the styrene-based monomer to the vinyl polymer crosslinking agent to the initiator is 100: 20-40: 2 to 6, the proportion of the components of the shell structure in the self-healing agent can be as follows: the mass ratio of the styrene-based monomer to the acrylic ester to the vinyl polymer crosslinking agent to the initiator is 100: 30-70: 5-10: 2-8, such as self-healing agent, can be prepared according to example 1 in the application of 201310426597.1, a core-shell polymer microsphere and its preparation and application, and the model can be BCY-201S.
In addition, the fluid loss agent is an AMPS polymer with salt-resistant low-temperature early strength characteristics. The fluid loss agent can be polymerized from the following components: 100 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 0.1 to 0.5 part by weight of a crosslinking monomer, 1 to 3 parts by weight of a molecular weight regulator, 1 to 3 parts by weight of an alcohol monomer, 8 to 10 parts by weight of an amide monomer, 0.5 to 1.0 part by weight of a carboxylic acid monomer and 300 to 400 parts by weight of water.
Wherein, the 2-acrylamide-2-methylpropanesulfonic acid has good water solubility, and the molecule of the 2-acrylamide-2-methylpropanesulfonic acid has hydrophilic sulfonic acid groups and polymerizable vinyl groups, and can carry out copolymerization reaction with other components under certain conditions.
The cross-linking monomer can be at least one of ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate, for example, the cross-linking monomer can be ethylene glycol dimethacrylate, or can be a mixture of the ethylene glycol dimethacrylate and the polyethylene glycol dimethacrylate.
When the water loss reducing agent is added to prepare the brine slurry, the water loss reducing agent is crosslinked to form a space network structure in the brine slurry, so that the water loss control capability of the brine slurry can be controlled even under the condition of reducing the carboxylic acid strong adsorption monomer, and meanwhile, the strength development of the brine slurry at low temperature is promoted.
When the amount of the crosslinking monomer exceeds 0.5 parts by weight, the consistency of the brine slurry prepared by the fluid loss agent of the present application is high and the rheological property is deteriorated, and thus the amount of the crosslinking monomer does not exceed 0.5 parts by weight. Preferably, the crosslinking monomer is used in an amount of 0.1 to 0.5 parts by weight. The crosslinking monomer may be used in an amount of 0.1, 0.2, 0.3, 0.4, 0.5, etc. parts by weight.
The molecular weight regulator may be at least one of isopropanol and dodecyl mercaptan, and may be isopropanol or a mixture of isopropanol and dodecyl mercaptan. The molecular weight regulator may be used in an amount of 1, 1.3, 1.5, 2, 2.3, 2.5, 3, etc. parts by weight.
When the molecular weight regulator is added to prepare the brine slurry, the molecular weight of the fluid loss agent can be reduced, the dosage of the crosslinking monomer is controlled in a matched manner, and the fluid loss agent is ensured to form a micro-crosslinking state, so that the fluid loss of the brine slurry can be controlled, the rheological property of the brine slurry is not affected too much, and a certain suspension stabilizing effect can be achieved on the brine slurry.
In conclusion, the crosslinking monomer and the molecular weight regulator control the crosslinking structure and molecular weight distribution of the fluid loss agent, and comprehensively improve the water loss control capability of the fluid loss agent in the brine slurry prepared by using the fluid loss agent on the basis of basically not influencing the rheological property of the brine slurry.
The alcohol monomer can be at least one of methallyl alcohol and vinyl alcohol, for example, the alcohol monomer can be methallyl alcohol, or can be a mixture of methallyl alcohol and vinyl alcohol. The amount of the alcohol monomer may be 1, 1.2, 1.5, 2, 2.3, 2.5, 3, etc. parts by weight.
When the alcohol monomer is added to prepare the brine slurry by the fluid loss agent, the molecular chain of the fluid loss agent contains hydroxyl, so that the concentration of the liquid phase calcium hydroxide of the brine slurry can be increased, and the C is accelerated 3 S, the hydration speed of the cement paste promotes the strength development of the saline cement paste at low temperature. From this, it is known that the above-mentioned alcohol monomer is used to promote strength development of brine slurry under low temperature conditions.
In the fluid loss agent, the crosslinking monomer, the molecular weight regulator and the alcohol monomer are added and are matched with other components to act, so that the water loss of the brine cement paste can be reduced when the brine cement paste is prepared, the sedimentation stability and rheological property of the brine cement paste are improved, and the thickening phenomenon of the brine cement paste is avoided. Meanwhile, the hydration of the brine cement paste under the low-temperature condition can be effectively promoted, and the effect of low-temperature early strength is achieved. The brine cement slurry prepared by the fluid loss agent has the advantages of good stability at low temperature, excellent water loss, quick development of compressive strength, excellent rheological property, high well cementation quality and high operation efficiency.
The amide monomer can be at least one of N, N-dimethylacrylamide and acrylamide, for example, the amide monomer can be N, N-dimethylacrylamide, or a mixture of N, N-dimethylacrylamide and acrylamide. Wherein, the N, N-dimethyl acrylamide and the acrylamide are easy to generate polymers with high polymerization degree, which can reduce the water loss of the brine cement slurry.
The amount of the amide monomer may be 8, 8.2, 8.5, 9, 9.3, 9.5, 10, etc. parts by weight.
The carboxylic acid monomer can be at least one of itaconic acid and acrylic acid, for example, the carboxylic acid monomer can be itaconic acid, or can be a mixture of itaconic acid and acrylic acid. The itaconic acid and the acrylic acid have strong adsorption characteristics and can be adsorbed around cement particles, so that the water loss of the brine cement paste is reduced, but the thickening time of the brine cement paste can be prolonged and the strength development of the brine cement paste at low temperature can be delayed due to the excessive addition.
When the amount of the carboxylic acid monomer exceeds 1.5 parts by weight, the thickening time of the brine slurry prepared by the fluid loss agent can be prolonged, and the strength development at low temperature is slow. Thus, in the examples herein, the carboxylic acid monomer is used in an amount of not more than 1.0 parts by weight. Preferably, the carboxylic acid monomer is used in an amount of 0.5 to 1.0 parts by weight. The carboxylic acid monomer may be used in an amount of 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, etc. parts by weight.
The water may be used in an amount of 300, 320, 340, 350, 370, 380, 400, etc. parts by weight.
The salt cavern type gas storage is generally shallow in salt layer burial depth, low in stratum temperature, and low in winter, and has a maximum temperature of 60 ℃ and a maximum temperature in a well of about 50 ℃ in normal well cementation operation. For a saline cement slurry system, the stability is poor, the water loss is not easy to control, the compressive strength is slow to develop, the thixotropy is strong, the rheological property is poor, and the well cementation quality is difficult to ensure. Therefore, the fluid loss agent added for well cementation of the salt cavern type gas storage needs to have good water loss control performance, salt resistance and low-temperature early strength performance. The fluid loss agent has good salt resistance and low-temperature early strength performance, can avoid the phenomenon of thickening of cement paste, and improves the rheological property of the cement paste. In particular, the fluid loss agent also has good low-temperature early strength performance, the cement paste prepared by the fluid loss agent has strength after 6 hours at 52 ℃, the compressive strength after 24 hours is more than 30MPa, and the comprehensive performance is good.
The fluid loss agent can be polymerized under the action of 0.5 to 0.7 weight part of initiator.
The initiator is used for initiating each component of the fluid loss agent to carry out polymerization reaction to obtain the fluid loss agent. The initiator may be at least one of ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride and azobisiso Ding Mi hydrochloride, for example, the initiator may be ammonium persulfate, a mixture of potassium persulfate and azobisisobutylamidine hydrochloride, or a mixture of azobisisobutylamidine hydrochloride and azobisiso Ding Mi hydrochloride, which is not particularly limited in the embodiment of the present application.
The initiator may be used in an amount of 0.5, 0.6, 0.7, etc. parts by weight.
The preparation method of the fluid loss agent comprises the following steps:
step 1: adding water, 2-acrylamide-2-methylpropanesulfonic acid, a crosslinking monomer, a molecular weight regulator, an alcohol monomer, an amide monomer and a carboxylic acid monomer into a reactor to obtain a reaction solution.
In the above step, water, 2-acrylamide-2-methylpropanesulfonic acid, a crosslinking monomer, a molecular weight regulator, an alcohol monomer, an amide monomer, and a carboxylic acid monomer may be sequentially added to the reactor.
The reactor may be a four-necked flask with thermometer, stirrer, reflux condenser.
Step 2: stirring the reaction liquid, regulating the hydrogen ion concentration index (pH value) of the reaction liquid to 6-7, raising the temperature of the reaction liquid to 50-60 ℃, adding an initiator into the reaction liquid after all components in the reaction liquid are dissolved, reacting for 2-3 hours, and cooling to room temperature to obtain the fluid loss agent.
In the above step, the reaction solution may be stirred at a speed of 200 rpm.
The pH of the reaction solution can be adjusted by NaOH solution. The concentration of the NaOH solution may be set and changed as needed, for example, the concentration of the NaOH solution may be 0.05mol/L, 0.1mol/L, or 0.2mol/L, which is not particularly limited in the embodiments of the present application.
The fluid loss agent is light yellow liquid with certain viscosity.
The preparation method of the fluid loss agent is simple, and the prepared fluid loss agent has the characteristics of salt resistance and low-temperature early strength, is particularly suitable for well cementation construction operation of a salt cavern type gas storage cover layer, can ensure that the stability of saline cement slurry at low temperature is good, the fluid loss is excellent, the compression strength development is quick, the rheological property is excellent, and further the well cementation quality is ensured. The toughness self-healing cement slurry prepared by the fluid loss agent has the advantages of excellent fluid loss, good rheological property, good stability, quick strength development under the low-temperature salt-containing condition, strength starting at 52 ℃ for 6 hours, compressive strength of more than 30MPa for 24 hours and good comprehensive performance, thereby effectively ensuring the safety of well cementation construction and improving the well cementation quality.
The application also provides a preparation method of the tough self-healing cement slurry for the salt cavern gas storage well cementation, which comprises the following steps:
and uniformly mixing cement, a toughening agent, a self-healing agent, a fluid loss agent, a retarder, a drag reducer, a defoaming agent and 15% saline water to obtain the tough self-healing cement slurry for the well cementation of the salt cavern gas storage.
Wherein cement, a toughening agent, a self-healing agent, a fluid loss agent, a retarder, a drag reducer, a defoaming agent and 15% saline water are uniformly mixed, and the method can be as follows: under the stirring condition, adding cement, a toughening agent, a gas self-healing agent, a fluid loss agent, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform. The specific parameters such as stirring speed and stirring time can be referred to the API10A specification.
The tough self-healing cement slurry for the well cementation of the salt cavern gas storage has the characteristics of good salt resistance, excellent water loss control and rheological property, good stability, quick development of low-temperature compressive strength and the like, and each property meets the well cementation construction requirement of the salt cavern gas storage; meanwhile, the cement sheath has good mechanical properties, and ensures the sealing integrity of the cement sheath under alternating load conditions; more importantly, the self-healing cement sheath has the characteristic of self-healing when meeting gas, secondary protection is added, and the cement sheath can be self-repaired even if the cement sheath is damaged with small probability, so that the effect of long-term sealing integrity is achieved.
The following describes the technical scheme of the present application in detail with reference to specific embodiments:
fluid loss agent example 1
Step 1: to a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser were successively added 300 parts by weight of water, 100 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 0.1 part by weight of ethylene glycol dimethacrylate, 1 part by weight of isopropyl alcohol, 1 part by weight of methallyl alcohol, 8 parts by weight of acrylamide and 0.5 part by weight of itaconic acid per 1g by weight of the mixture, to obtain a reaction solution.
Step 2: stirring the reaction solution at the speed of 200 revolutions per minute, adding a NaOH solution into the reaction solution, adjusting the hydrogen ion concentration index (pH value) of the reaction solution to 6, raising the temperature of the reaction solution to 60 ℃, adding 0.5 part by weight of ammonium persulfate into the reaction solution after all components in the reaction solution are dissolved, reacting at constant temperature for 2 hours, and naturally cooling to room temperature to obtain the fluid loss agent.
Fluid loss agent example 2
Step 1: to a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser were successively added 300 parts by weight of water, 100 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 0.5 part by weight of polyethylene glycol dimethacrylate, 3 parts by weight of dodecylmercaptan, 3 parts by weight of vinyl alcohol, 10 parts by weight of N, N-dimethylacrylamide and 1 part by weight of acrylic acid per 1g of the mixture to obtain a reaction solution.
Step 2: stirring the reaction solution at the speed of 200 revolutions per minute, adding a NaOH solution into the reaction solution, adjusting the hydrogen ion concentration index (pH value) of the reaction solution to 7, raising the temperature of the reaction solution to 60 ℃, adding 0.5 part by weight of ammonium persulfate into the reaction solution after all components in the reaction solution are dissolved, reacting at constant temperature for 2 hours, and naturally cooling to room temperature to obtain the fluid loss agent.
Fluid loss agent example 3
Step 1: 400 parts by weight of water, 100 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 0.3 part by weight of ethylene glycol dimethacrylate, 0.2 part by weight of polyethylene glycol dimethacrylate, 1 part by weight of isopropyl alcohol, 2 parts by weight of dodecyl mercaptan, 1 part by weight of methallyl alcohol, 2 parts by weight of vinyl alcohol, 6 parts by weight of acrylamide, 4 parts by weight of N, N-dimethylacrylamide, 0.5 part by weight of acrylic acid, and 0.5 part by weight of itaconic acid were sequentially added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, to obtain a reaction solution.
Step 2: stirring the reaction solution at the speed of 200 revolutions per minute, adding a NaOH solution into the reaction solution, adjusting the hydrogen ion concentration index (pH value) of the reaction solution to 7, raising the temperature of the reaction solution to 60 ℃, adding 0.5 part by weight of ammonium persulfate into the reaction solution after all components in the reaction solution are dissolved, reacting at constant temperature for 2 hours, and naturally cooling to room temperature to obtain the fluid loss agent.
Cement paste example 1
The composition is as follows:
preparing:
according to the API10A standard, under the stirring condition, adding cement, a toughening agent, a gas self-healing agent, a fluid loss reducer, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform to obtain the tough self-healing cement slurry for the well cementation of the salt cavern gas storage.
Cement paste example 2
The composition is as follows:
preparing:
according to the API10A standard, under the stirring condition, adding cement, a toughening agent, a gas self-healing agent, a fluid loss reducer, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform to obtain the tough self-healing cement slurry for the well cementation of the salt cavern gas storage.
Cement paste example 3
The composition is as follows:
preparing:
according to the API10A standard, under the stirring condition, adding cement, a toughening agent, a gas self-healing agent, a fluid loss reducer, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform to obtain the tough self-healing cement slurry for the well cementation of the salt cavern gas storage.
Fluid loss agent comparative example 1
Step 1: to a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser were successively added 300 parts by weight of water, 100 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid, 1 part by weight of methallyl alcohol, 8 parts by weight of acrylamide and 1.5 parts by weight of itaconic acid per 1g of the reaction mixture to obtain a reaction solution.
Step 2: stirring the reaction solution at the speed of 200 revolutions per minute, adding a NaOH solution into the reaction solution, adjusting the hydrogen ion concentration index (pH value) of the reaction solution to 6, raising the temperature of the reaction solution to 60 ℃, adding 0.5 part by weight of ammonium persulfate into the reaction solution after all components in the reaction solution are dissolved, reacting at constant temperature for 2 hours, and naturally cooling to room temperature to obtain the fluid loss agent.
Comparative cement slurry example 1
The composition is as follows:
preparing:
according to the API10A specification, under the stirring condition, adding cement, a toughening agent, a fluid loss agent, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform to obtain cement paste.
Cement paste comparative example 2
The composition is as follows:
preparing:
according to the API10A standard, under the stirring condition, adding cement, a gas self-healing agent, a fluid loss agent, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform to obtain cement paste.
Test example 1
The cement slurries provided in cement slurry examples 1-3 and cement slurry comparative examples 1-2 were subjected to performance testing in accordance with the API10A specification, and the results are shown in tables 1, 2 and 3.
TABLE 1 Cement paste workability
As can be seen from table 1 and fig. 1: compared with cement paste comparative example 1 and cement paste comparative example 2, the brine paste prepared by cement paste example 1, cement paste example 2 and cement paste example 3 has stronger advantages in terms of cement paste water loss, 24h compressive strength, strength onset time and other performances, particularly in terms of cement paste strength onset time and 24h compressive strength, the strength development of the brine paste of cement paste example 1, cement paste example 2 and cement paste example 3 is quick, the strength onset time is basically 6h, the 24h strength is more than 30MPa, and the severe requirements of salt cavern type gas storage well cementation construction are met.
Table 2 mechanical Properties of set cement obtained with Cement slurries
The mechanical properties of the cement paste obtained are shown in Table 2 and FIG. 2. Cement paste of cement paste examples 1, 2 and 3 has 7d uniaxial compressive strength of more than 28MPa,7d tensile strength of more than 1.9MPa,7d Young's modulus of less than 6GPa, and 7d gas permeability of less than 0.05X10 -3 μm 2 The linear expansion rate of 7d is between 0 and 0.2 percent, and all performances meet the specification in the industry standard SY-T7648-2021 technical requirement for gas storage well cementation. The Young's moduli of the cement stones obtained by the cement slurries of the cement slurry comparative examples 1 and 2 are both larger than 6GPa, and do not meet the industrial standard SY-T7648-2021 gas storage well consolidationWell technical requirements.
The cement sheath integrity obtained from the cement sheath of cement sheath example 3 was further checked using an autonomously developed cement sheath integrity simulator (model SJF-3.5). SJF-3.5 is based on the principle of equivalent stress, adopts a small-size model to simulate the actual shaft condition, has a plurality of independent temperature and pressure control systems, can simulate the weightlessness effect of a cement sheath maintenance stage on the basis of ensuring the continuous simulation of the whole well cementation process, and tests the sealing integrity of the cement sheath under the conditions of confining pressure, alternating stress and temperature.
Taking Zhang Xing gas storage as an example, the operating pressure of the Zhang Xing gas storage is 11.5-28 MPa, the minimum ground stress is about 32MPa, and according to the stress equivalent principle, the back calculation simulation conditions are as follows: the confining pressure is 28MPa, the internal pressure is 4-24 MPa, and the alternating temperature is 50-65 ℃.
The channeling pressure is 4MPa, the cement sheath obtained by the cement paste of the cement paste example 3 is circularly loaded for 50 times under alternating temperature and pressure conditions, and experimental results are shown in figure 3, which show that the mechanical properties of the salt-resistant low-temperature early-strength-toughness self-healing cement paste system meet the operation requirements of Zhang Xing air reservoirs. The cement sheath obtained by the cement sheath of the cement sheath comparative example 1 was cyclically loaded 40 times, namely, blowby gas, and the cement sheath obtained by the cement sheath of the cement sheath comparative example 2 was cyclically loaded 30 times, namely, blowby gas.
The self-healing agent (model is BCY-201S) is developed for a high-pressure natural well, and can obviously expand in natural gas (methane) and crude oil by introducing functional groups responding to hydrocarbon molecules with more than C1, so as to seal microcracks/microcracks formed by cement rings or interfaces. The self-healing agent can be used for forming secondary protection on the cement sheath, and even if the cement sheath generates microcracks under alternating load, the self-healing agent can be used for self-repairing in a natural gas environment.
TABLE 3 self-healing Properties of cement sheath in methane from Cement paste
| Numbering device | Crack type | Permeability decrease% |
| Cement paste example 1 | Manual cleavage | 80.8 |
| Cement paste example 2 | Manual cleavage | 84.4 |
| Cement paste example 3 | Manual cleavage | 89.3 |
| Comparative cement slurry example 1 | Manual cleavage | 0 |
| Cement paste comparative example 2 | Manual cleavage | 83.9 |
As can be seen from table 3: the cement paste of the cement paste comparative example 1 is not added with a self-healing agent, can not expand when meeting natural gas, can not heal micro cracks, and therefore the permeability reduction rate is zero.
The foregoing has outlined and described the basic principles, main features and advantages of the present application. It will be appreciated by persons skilled in the art that the present application is not limited to the embodiments described above, and that the embodiments and descriptions described herein are merely illustrative of the principles of the application, and various changes and modifications may be made therein without departing from the spirit and scope of the application, which is defined in the appended claims, specification and their equivalents.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present application and not for limiting the scope of protection of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.
Claims (9)
1. The tough self-healing cement slurry for the well cementation of the salt cavern gas storage is characterized by comprising the following components:
100 parts of cement, 4-6 parts of toughening agent, 8-12 parts of self-healing agent, 3-5 parts of fluid loss agent, 0.05-0.2 part of retarder, 1-2 parts of drag reducer, 0.1-0.2 part of defoamer and 30-50 parts of 15% saline water;
wherein, the fluid loss agent is AMPS polymer with salt-resistant low-temperature early strength characteristic;
the fluid loss agent is polymerized by the following components:
100 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 0.1-0.5 part by weight of a crosslinking monomer, 1-3 parts by weight of a molecular weight regulator, 1-3 parts by weight of an alcohol monomer, 8-10 parts by weight of an amide monomer, 0.5-1.0 part by weight of a carboxylic acid monomer and 300-400 parts by weight of water;
the crosslinking monomer comprises at least one of ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate;
the alcohol monomer comprises at least one of methallyl alcohol and vinyl alcohol;
the amide monomer comprises at least one of N, N-dimethylacrylamide and acrylamide;
the carboxylic acid monomer comprises at least one of itaconic acid and acrylic acid.
2. A flexible self-healing cement slurry for salt cavern gas storage well cementation as claimed in claim 1, wherein,
the cement comprises a class G oil well cement.
3. A flexible self-healing cement slurry for salt cavern gas storage well cementation as claimed in claim 1, wherein,
the retarder includes a phosphonate.
4. A flexible self-healing cement slurry for salt cavern gas storage well cementation as claimed in claim 1, wherein,
the drag reducing agent comprises polynaphthalenesulfonic acid.
5. A flexible self-healing cement slurry for salt cavern gas storage well cementation as claimed in claim 1, wherein,
the defoamer comprises tributyl phosphate and/or simethicone.
6. The tough self-healing cement slurry for salt cavern gas storage well cementation as claimed in claim 1, wherein the toughening agent is prepared from the following components:
20-60 parts by weight of whisker material, 5-10 parts by weight of surfactant, 5-10 parts by weight of silane coupling agent, 1-5 parts by weight of defoamer, 10-25 parts by weight of stabilizer, 100 parts by weight of water and 250-1000 parts by weight of absolute ethyl alcohol.
7. A flexible self-healing cement slurry for salt cavern gas storage well cementation as claimed in claim 1, wherein,
the self-healing agent has a core-shell structure;
the self-healing agent comprises the following components in percentage by weight: the mass ratio of the styrene-based monomer to the vinyl polymer crosslinking agent to the initiator is 100: 20-40: 2 to 6;
the self-healing agent comprises the following components in percentage by weight: the mass ratio of the styrene-based monomer to the acrylic ester to the vinyl polymer crosslinking agent to the initiator is 100: 30-70: 5-10: 2 to 8.
8. A method for preparing the ductile self-healing cement slurry for salt cavern gas storage well cementation according to any one of claims 1 to 7, which is characterized by comprising the following steps:
and uniformly mixing cement, a toughening agent, a self-healing agent, a fluid loss agent, a retarder, a drag reducer, a defoaming agent and 15% saline water to obtain the tough self-healing cement slurry for the well cementation of the salt cavern gas storage.
9. The method of claim 8, wherein,
cement, a toughening agent, a self-healing agent, a fluid loss agent, a retarder, a drag reducer, a defoaming agent and 15% saline water are uniformly mixed, and the method comprises the following steps:
under the stirring condition, adding cement, a toughening agent, a gas self-healing agent, a fluid loss agent, a retarder, a drag reducer and a defoaming agent into 15% saline water, and continuously stirring until the mixture is uniform.
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