CN115925341A - Tough self-healing cement slurry for well cementation of salt cavern gas storage and preparation method thereof - Google Patents
Tough self-healing cement slurry for well cementation of salt cavern gas storage and preparation method thereof Download PDFInfo
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
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- 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 2
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Abstract
The application discloses a tough self-healing cement slurry for well cementation of a salt cavern gas storage and a preparation method thereof, wherein the tough self-healing cement slurry for well cementation of the salt cavern gas storage comprises the following components: 100 portions of cement, 4 to 6 portions of toughener, 8 to 12 portions of self-healing agent, 3 to 5 portions of fluid loss additive, 0.05 to 0.2 portion of retarder, 1 to 2 portions of drag reducer, 0.1 to 0.2 portion of defoaming agent and 30 to 50 portions of saline water with the concentration of 15 percent. Wherein the fluid loss agent is an AMPS polymer with salt-resistant low-temperature early-strength characteristics. The tough self-healing cement slurry for cementing the salt cavern gas storage has the characteristics of good salt resistance, early strength at low temperature, water loss control, excellent rheological and mechanical properties, 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 well cementation cement, in particular to a tough self-healing cement slurry for well cementation of a salt cavern gas storage and a preparation method thereof.
Background
The key of the long-term and high-efficiency operation of the salt cavern gas storage depends on the sealing performance of a salt cavern cavity and a 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 buried depth, low in stratum temperature, 60 ℃ at the highest temperature, about 50 ℃ at the highest temperature in a well during normal well cementation operation and lower in winter. For a saline cement slurry system, the cement slurry has poor stability at low temperature, difficult control of water loss, slow development of compressive strength, strong thixotropy and poor rheological property, so that 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 the alternating stress must be considered in the operation period of the salt cavern gas storage so as to ensure the aim of safe operation of the gas storage for at least 30 years. Therefore, in order to ensure the long-term safe operation of the gas storage, the strength stability and the long-term sealing performance of the cement sheath must be ensured. Therefore, the development of a salt-resistant, low-temperature and early-strength tough self-healing cement slurry is needed to ensure long-term efficient and stable operation of the salt cavern type gas storage.
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 following technical scheme is adopted in the application:
the application provides a toughness self-healing cement slurry for cementing a salt cavern gas storage, which comprises the following components: 100 portions of cement, 4 to 6 portions of toughener, 8 to 12 portions of self-healing agent, 3 to 5 portions of fluid loss additive, 0.05 to 0.2 portion of retarder, 1 to 2 portions of drag reducer, 0.1 to 0.2 portion of defoaming agent and 30 to 50 portions of saline water with the concentration of 15 percent. Wherein the fluid loss agent is an AMPS polymer with salt-resistant low-temperature early-strength characteristics.
Further, the fluid loss agent is obtained by polymerizing the following components: 100 weight portions of 2-acrylamide-2-methylpropanesulfonic acid, 0.1 to 0.5 weight portion of crosslinking monomer, 1 to 3 weight portions of molecular weight regulator, 1 to 3 weight portions of alcohol monomer, 8 to 10 weight portions of amide monomer, 0.5 to 1.0 weight portion of carboxylic acid monomer and 300 to 400 weight portions of water. The crosslinking monomer and the molecular weight regulator are used for controlling the crosslinking structure and the molecular weight distribution of the fluid loss agent, and comprehensively improving the fluid loss control capability of the fluid loss agent in the saline cement slurry prepared from the fluid loss agent. Alcohol monomers are used to promote strength development of brine-containing muds under cryogenic conditions.
Further, the cement includes class G oil well cement.
Further, the set retarder includes a phosphonate.
Further, the drag reducer comprises polynaphthalenesulfonate.
Further, the defoaming agent includes tributyl phosphate and/or dimethyl silicone oil.
Further, the toughening agent is prepared from the following components: 20-60 parts of whisker material, 5-10 parts of surfactant, 5-10 parts of silane coupling agent, 1-5 parts of defoaming agent, 10-25 parts of stabilizer, 100 parts of water and 250-1000 parts of absolute ethyl alcohol.
Further, the self-healing agent has a core-shell structure. The proportion of the components of the core structure in the self-healing agent is as follows: the mass ratio of the styrene-based monomer to the vinyl polymer cross-linking agent to the initiator is 100:20 to 40:2 to 6. The proportion of the components of the shell structure in the self-healing agent is as follows: the mass ratio of the styrene-based monomer to the acrylate to the vinyl polymer cross-linking agent to the initiator is 100:30 to 70:5 to 10:2 to 8.
The application also provides a preparation method of the tough self-healing cement slurry for cementing the salt cavern gas storage, which comprises the following steps: uniformly mixing cement, a toughening agent, a self-healing agent, a fluid loss additive, a retarder, a drag reducer, a defoaming agent and 15% saline water to obtain the tough self-healing cement slurry for cementing the salt cavern gas storage.
Further, cement, a toughening agent, a self healing agent, a fluid loss additive, a retarder, a drag reducer, a defoaming agent and 15% saline water are uniformly mixed, and the method comprises the following steps: under the condition of stirring, adding cement, a toughening agent, a self-healing agent meeting air, a fluid loss reducer, a retarder, a drag reducer and a defoaming agent into saline water with the concentration of 15%, and continuously stirring until the mixture is uniform.
Compared with the prior art, the method has the following beneficial effects:
1. the tough self-healing cement slurry for cementing the salt cavern gas storage has the characteristic of good salt resistance, and can be prepared by adopting 15% saline water.
2. The tough self-healing cement slurry for cementing the salt cavern gas storage has the characteristics of low temperature and early strength, the strength is 6h, and the strength is more than 30MPa in 24 h.
3. The tough self-healing cement slurry for well cementation of the salt cavern gas storage has the characteristic of excellent mechanical property, all the mechanical properties meet the requirements in the industrial standard SY-T7648-2021 technical requirements for well cementation of the gas storage, and the cement slurry is not damaged after being operated for 50 times under the conditions of the confining pressure of 28MPa, the alternating internal pressure of 4-24 MPa and the alternating temperature of 50-65 ℃, so that the long-term sealing integrity of the salt cavern gas storage can be guaranteed.
4. The application provides a salt cavern gas storage is toughness self-healing grout for well cementation has the characteristic of self-healing, can form effectual secondary protection to the cement sheath.
In conclusion, the tough self-healing cement slurry for 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 of the static gelation of cement paste at 52 ℃ in example 1 of the cement paste of the present application;
FIG. 2 is a three-axis plot of the cement slurry of example 2 of the present application.
FIG. 3 is a graph of integrity check of cement sheath obtained from cement slurry of example 3 of the present application under alternating load conditions.
Detailed Description
The technical method in the embodiments of the present application will be clearly and completely described below. It should be apparent that the described embodiments are only a few embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a toughness self-healing cement slurry for cementing a salt cavern gas storage, which comprises the following components: 100 portions of cement, 4 to 6 portions of toughener, 8 to 12 portions of self-healing agent, 3 to 5 portions of fluid loss additive, 0.05 to 0.2 portion of retarder, 1 to 2 portions of drag reducer, 0.1 to 0.2 portion of defoaming agent and 30 to 50 portions of saline water with the concentration of 15 percent. Preferably, 100 parts by weight of cement, 5 parts by weight of toughening agent, 8 parts by weight of self-healing agent, 4 parts by weight of fluid loss additive, 0.2 part by weight of retarder, 1 part by weight of drag reducer, 0.2 part by weight of defoaming agent and 50 parts by weight of saline with the concentration of 15%.
Wherein, the cement can be G-grade oil well cement.
The retarder may be a phosphonate. The retarder can be used in an amount of 0.05, 0.1, 0.15, 0.2 parts by weight.
The drag reducer may be a polynaphthalene sulfonate. Drag reducers may be used in amounts of 1, 1.5, 2 parts by weight.
The defoaming agent can be tributyl phosphate and/or dimethyl silicone oil, for example, the defoaming agent can be tributyl phosphate, and can also be a mixture of tributyl phosphate and dimethyl silicone oil. The defoaming agent can be used in an amount of 0.1, 0.15, 0.2 parts by weight.
The saline with the concentration of 15% can be saline prepared by 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 of whisker material, 5-10 parts of surfactant, 5-10 parts of silane coupling agent, 1-5 parts of defoaming agent, 10-25 parts of stabilizer, 100 parts of water and 250-1000 parts of absolute ethyl alcohol, for example, the toughening agent can be prepared according to example 1 in the patent application No. 201611089451.2, namely, the fiber toughening agent for well-cementing cement slurry and the preparation method thereof, and the type of the fiber toughening agent can be BCE-310S.
The self-healing agent (or called self-healing agent in case of gas) 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 cross-linking agent to the initiator is 100:20 to 40: 2-6, the self-healing agent mesochite structure can be prepared by the following components in percentage by weight: the mass ratio of the styrene-based monomer to the acrylate to the vinyl polymer cross-linking agent to the initiator is 100:30 to 70:5 to 10:2 to 8, for example, the self-healing agent can be prepared according to example 1 in the patent application with the application number of 201310426597.1, namely core-shell polymer microsphere and preparation and application thereof, and the type can be BCY-201S.
In addition, the fluid loss agent is an AMPS polymer with salt-resistant, low-temperature and early-strength characteristics. The fluid loss agent can be obtained by polymerizing the following components: 100 weight portions of 2-acrylamide-2-methylpropanesulfonic acid, 0.1 to 0.5 weight portion of crosslinking monomer, 1 to 3 weight portions of molecular weight regulator, 1 to 3 weight portions of alcohol monomer, 8 to 10 weight portions of amide monomer, 0.5 to 1.0 weight portion of carboxylic acid monomer and 300 to 400 weight portions of water.
Wherein, the 2-acrylamide-2-methylpropanesulfonic acid has good water solubility, and hydrophilic sulfonic group and polymerizable vinyl in the molecule can generate copolymerization reaction with other components under certain conditions.
The crosslinking monomer can be at least one of ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate, for example, the crosslinking monomer can be ethylene glycol dimethacrylate, and also can be a mixture of the ethylene glycol dimethacrylate and the polyethylene glycol dimethacrylate.
By adding the crosslinking monomer, when the water loss agent is used for preparing the brine cement slurry, the water loss agent is crosslinked to form a space net structure in the brine cement slurry, so that the water loss control capability of the brine cement slurry can be still controlled even under the condition of reducing the carboxylic acid strong adsorption monomer, and the strength development of the brine cement slurry at low temperature is promoted.
When the amount of the crosslinking monomer exceeds 0.5 part by weight, the brine cement slurry prepared by the fluid loss additive of the present application has high consistency and poor rheological properties, and therefore, the amount of the crosslinking monomer does not exceed 0.5 part 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 can be at least one of isopropanol and dodecyl mercaptan, for example, the molecular weight regulator can be isopropanol, and can also be 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.
By adding the molecular weight regulator, when the brine cement slurry is prepared from the water loss reducing agent, the molecular weight of the water loss reducing agent can be reduced, and the dosage of the crosslinking monomer is controlled to ensure that the water loss reducing agent forms a micro-crosslinking state, so that the water loss of the brine cement slurry can be controlled, the rheological property of the brine cement slurry is not excessively influenced, and a certain suspension stabilizing effect can be achieved on the brine cement slurry.
In conclusion, the crosslinking structure and the molecular weight distribution of the water loss reducing agent are controlled by the crosslinking monomer and the molecular weight regulator, and the water loss control capability of the water loss reducing agent in the brine cement slurry prepared by using the water loss reducing agent is comprehensively improved on the basis of basically not influencing the rheological property of the brine cement slurry.
The alcohol monomer can be at least one of methallyl alcohol and vinyl alcohol, for example, the alcohol monomer can be methallyl alcohol, and can also be a mixture of methallyl alcohol and vinyl alcohol. The alcohol monomer may be used in an amount of 1, 1.2, 1.5, 2, 2.3, 2.5, 3, etc. parts by weight.
By adding the alcohol monomer, when the salt water cement paste is prepared by the fluid loss agent, the molecular chain of the fluid loss agent contains hydroxyl, so that the concentration of liquid-phase calcium hydroxide in the salt water cement paste can be improved, and the C is accelerated 3 The hydration speed of S promotes the strength development of the saline cement slurry at low temperature. It is known that the alcohol monomer is used to promote the strength development of brine cement 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, so that the fluid loss amount of the saline cement paste can be reduced when the saline cement paste is prepared, the sedimentation stability and the rheological property of the saline cement paste are improved, and the phenomenon of thickening of the saline cement paste is avoided. Meanwhile, the hydration of the saline cement slurry under the low-temperature condition can be effectively promoted, and the effect of early strength at low temperature 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, good rheological property, high well cementation quality and high operation efficiency.
The amide monomer may be at least one of N, N-dimethylacrylamide and acrylamide, for example, the amide monomer may be N, N-dimethylacrylamide, or a mixture of N, N-dimethylacrylamide and acrylamide. Wherein, N, N-dimethylacrylamide and acrylamide are easy to generate polymers with high polymerization degree, and the water loss of the brine cement slurry can be reduced.
The amide monomers may be used in amounts of 8, 8.2, 8.5, 9, 9.3, 9.5, 10, etc. parts by weight.
The carboxylic acid monomer may be at least one of itaconic acid and acrylic acid, for example, the carboxylic acid monomer may be itaconic acid, and may also 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 is prolonged and the strength development of the brine cement paste at low temperature is delayed due to the excessive addition of the itaconic acid and the acrylic acid.
When the using amount of the carboxylic acid monomer exceeds 1.5 parts by weight, the thickening time of the brine cement slurry prepared by the fluid loss agent is prolonged, and the strength development at low temperature is slow. Therefore, in the examples of the present application, the amount of the carboxylic acid-based monomer is not more than 1.0 part by weight. Preferably, the carboxylic acid monomer is used in an amount of 0.5 to 1.0 part 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. by weight.
The amount of water may be 300, 320, 340, 350, 370, 380, 400, etc. parts by weight.
The salt cavern type gas storage is generally shallow in salt layer buried depth, low in stratum temperature and 60 ℃ of the highest temperature, the highest temperature in a well is generally about 50 ℃ during normal well cementation operation, and the highest temperature is lower in winter. For a salt water cement slurry system, the cement slurry has poor stability at low temperature, water loss is difficult 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 water loss reducing agent added for cementing 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. Particularly, the fluid loss agent has good low-temperature early strength performance, the cement paste prepared from the fluid loss agent has the strength of 6 hours at 52 ℃, the compressive strength of 24 hours is more than 30MPa, and the comprehensive performance is good.
The fluid loss agent can be obtained by polymerization under the action of 0.5-0.7 weight part of initiator.
The initiator is used for initiating the polymerization reaction of all components of the fluid loss agent to obtain the fluid loss agent. The initiator may be at least one of ammonium persulfate, potassium persulfate, azobisisobutyramidine hydrochloride, and azobisisobutyrimidazoline hydrochloride, and for example, the initiator may be ammonium persulfate, or a mixture of potassium persulfate and azobisisobutyramidine hydrochloride, or a mixture of azobisisobutyramidine hydrochloride and azobisisobutyrimidazoline hydrochloride, which is not specifically limited in this embodiment of the 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 can be a four-mouth flask with a thermometer, a stirrer and a reflux condenser.
Step 2: stirring the reaction solution, adjusting the hydrogen ion concentration index (pH value) of the reaction solution to 6-7, raising the temperature of the reaction solution to 50-60 ℃, adding an initiator into the reaction solution after all components in the reaction solution 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 faint yellow liquid with certain viscosity.
The preparation method of the fluid loss agent is simple, 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, and can ensure good stability, excellent water loss, quick development of compressive strength and good rheological property of brine cement slurry at low temperature, thereby ensuring the well cementation quality. The tough self-healing cement paste prepared by the fluid loss agent has excellent water loss, good rheological property and good stability, the strength development is fast under the condition of low temperature and salt content, the strength is increased for 6 hours under the condition of 52 ℃, the 24-hour compressive strength is greater than 30MPa, and the comprehensive performance is good, so that the safety of well cementation construction is effectively guaranteed, and the well cementation quality is improved.
The application also provides a preparation method of the tough self-healing cement slurry for cementing the salt cavern gas storage, which comprises the following steps:
and uniformly mixing the cement, the toughening agent, the self-healing agent, the fluid loss additive, the retarder, the drag reducer, the defoaming agent and 15% saline water to obtain the tough self-healing cement slurry for cementing the salt cavern gas storage.
Wherein, cement, toughening agent, self-healing agent, fluid loss additive, retarder, drag reducer, defoaming agent and 15% saline water are uniformly mixed, and the mixture can be: under the condition of stirring, adding cement, a toughening agent, a self-healing agent meeting air, a fluid loss reducer, a retarder, a drag reducer and a defoaming agent into saline water with the concentration of 15%, and continuously stirring until the mixture is uniform. The specific parameters such as stirring speed and stirring time can be referred to API10A specifications.
The tough self-healing cement slurry for cementing the salt cavern gas storage has the characteristics of good salt resistance, water loss control, excellent rheological property, good stability, quick development of low-temperature compressive strength and the like, and all the properties meet the cementing construction requirements of the salt cavern gas storage; meanwhile, the sealing material has good mechanical properties, and the sealing integrity of the cement sheath under the condition of alternating load is guaranteed; more importantly, the self-healing cement sheath has the self-healing characteristic in case of air, secondary protection is increased, the cement sheath can be repaired by self even if the cement sheath is damaged with small probability, and the effect of long-term complete sealing is achieved.
The technical scheme of the application is described in detail by combining the specific embodiments as follows:
fluid loss additive example 1
Step 1: to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 were sequentially added per 1g by weight to obtain a reaction solution.
Step 2: stirring the reaction solution at the speed of 200 revolutions per minute, adding 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 for 2 hours at constant temperature, and naturally cooling to room temperature to obtain the fluid loss agent.
Fluid loss additive example 2
Step 1: to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 1g by weight of water 300 parts by weight, 2-acrylamide-2-methylpropanesulfonic acid 100 parts by weight, polyethylene glycol dimethacrylate 0.5 parts by weight, dodecanethiol 3 parts by weight, vinyl alcohol 3 parts by weight, N-dimethylacrylamide 10 parts by weight, and acrylic acid 1 part by weight were sequentially added to obtain a reaction solution.
Step 2: stirring the reaction solution at the speed of 200 revolutions per minute, adding 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 additive example 3
Step 1: to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 400 parts by weight of water, 100 parts by weight of 2-acrylamide-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 dodecanethiol, 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 per 1g by weight to obtain a reaction liquid.
And 2, step: stirring the reaction solution at the speed of 200 revolutions per minute, adding 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.
Grout example 1
Comprises the following components:
preparation:
according to API10A specification, 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 saline water with the concentration of 15%, and continuously stirring until the mixture is uniform to obtain the tough self-healing cement slurry for well cementation of the salt cavern gas storage.
Grout example 2
Consists of the following components:
preparation:
according to API10A specification, 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 saline water with the concentration of 15%, and continuously stirring until the mixture is uniform to obtain the tough self-healing cement slurry for well cementation of the salt cavern gas storage.
Grout example 3
Consists of the following components:
preparation:
according to API10A specifications, 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 saline water with the concentration of 15%, and continuously stirring until the mixture is uniform to obtain the tough self-healing cement slurry for cementing the salt cavern gas storage.
Fluid loss additive comparative example 1
Step 1: to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 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 were sequentially added per 1g by weight to obtain a reaction solution.
Step 2: stirring the reaction solution at the speed of 200 revolutions per minute, adding 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 for 2 hours at constant temperature, and naturally cooling to room temperature to obtain the fluid loss agent.
Cement paste comparative example 1
Consists of the following components:
preparation:
according to API10A specification, adding cement, a toughening agent, a fluid loss additive, a retarder, a drag reducer and a defoaming agent into 15% saline water under the stirring condition, and continuously stirring until the mixture is uniform to obtain cement paste.
Comparative cement slurry example 2
Consists of the following components:
preparation:
according to API10A specification, under the stirring condition, adding cement, a self-healing agent meeting air, a fluid loss agent, a retarder, a drag reducer and a defoaming agent into saline water with the concentration of 15%, and continuously stirring until the cement slurry is uniform to obtain the cement slurry.
Test example 1
The slurries provided in slurry examples 1-3 and comparative slurries 1-2 were tested for performance according to the API10A specification and the results are shown in tables 1, 2 and 3.
TABLE 1 Cement mortar workability
As can be seen from table 1 and fig. 1: compared with the cement paste comparative example 1 and the cement paste comparative example 2, the brine cement paste prepared by the cement paste examples 1, 2 and 3 has stronger advantages in the aspects of the water loss amount, the 24h compressive strength, the strength rise time and the like of the cement paste, particularly in the aspects of the strength rise time and the 24h compressive strength of the cement paste, the strength development of the brine cement paste of the cement paste examples 1, 2 and 3 is fast, the strength rise time is basically 6h, and the strength of 24h is more than 30MPa, so that the harsh requirements of the cementing construction of the salt cavern type gas storage are met.
TABLE 2 mechanical Properties of the Cement obtained from the Cement slurries
The mechanical properties of the set cement obtained from the cement slurry are shown in table 2 and fig. 2. Cement slurries of examples 1, 2 and 3 resulted in cements having uniaxial 7d compressive strengths of greater than 28MPa, tensile 7d tensile strengths of greater than 1.9MPa, young's modulus of less than 6GPa, and gas permeability of less than 0.05X 10 -3 μm 2 And the 7d linear expansion rate is between 0 and 0.2 percent, and all the performances meet the regulations in the industrial standard SY-T7648-2021 technical requirements for well cementation of gas storage wells. The Young modulus of the set cement obtained by the cement paste of the comparative cement paste examples 1 and 2 is larger than 6GPa, and the set cement does not meet the regulation in the industrial standard SY-T7648-2021 technical requirement for well cementation of gas storage wells.
The integrity of the cement sheath obtained from the cement slurry of example 3 was further checked using a cement sheath integrity simulator (model number SJF-3.5) developed autonomously. The SJF-3.5 is based on an equivalent stress principle, adopts a small-size model to simulate actual shaft conditions, is provided with a plurality of sets of independent temperature and pressure control systems, can simulate the weightlessness effect of a cement ring maintenance stage on the basis of guaranteeing continuous simulation of the whole well cementation process, and tests the sealing integrity of the cement ring under the conditions of confining pressure, alternating stress and temperature.
Taking the 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 inverse 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 from the cement slurry in the embodiment 3 of the cement slurry is circularly loaded for 50 times without channeling under the conditions of alternating temperature and pressure, and the experimental result is shown in figure 3, which shows that the mechanical property of the salt-resistant low-temperature early-strength toughness self-healing cement slurry system meets the operation requirement of Zhang xing gas storage. The cement sheath obtained by the cement paste of the cement paste comparative example 1 is circularly loaded for 40 times, namely blow-by, and the cement sheath obtained by the cement paste of the cement paste comparative example 2 is circularly loaded for 30 times, namely blow-by.
The self-healing agent (the model is BCY-201S) is a gas self-healing agent developed for a high-pressure natural well, and can generate obvious expansion in natural gas (methane) and crude oil by introducing a functional group responding to hydrocarbon molecules above C1 so as to block micro cracks/micro gaps formed on a cement sheath or an interface. The self-healing agent can form secondary protection on the cement sheath, and can perform self-repairing in a natural gas environment even if the cement sheath generates micro cracks under an alternating load condition.
TABLE 3 self-healing Properties of Cement sheath in methane
| Numbering | Type of crack | Reduction in permeability% |
| Grout example 1 | Manually split | 80.8 |
| Grout example 2 | Manually split | 84.4 |
| Grout example 3 | Manually split | 89.3 |
| Cement paste comparative example 1 | Manually split | 0 |
| Comparative cement slurry example 2 | Artificial operationSplitting by means of a wedge | 83.9 |
As can be seen from Table 3: the cement paste of the comparative cement paste example 1 is not added with a self-healing agent, can not expand when meeting natural gas and can not generate healing effect on microcracks, so that the permeability reduction rate is zero.
The foregoing shows and describes the basic principles, essential features, and advantages of the application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, which are presented solely for purposes of illustrating the principles of the application, and that various changes and modifications may be made without departing from the spirit and scope of the application, which is defined by the appended claims, the specification, and equivalents thereof.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present application and not for limiting the protection scope of the present application, and although the present application is 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 on the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.
Claims (10)
1. The tough self-healing cement slurry for cementing 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 additive, 0.05-0.2 part of retarder, 1-2 parts of drag reducer, 0.1-0.2 part of defoaming agent and 30-50 parts of saline water with the concentration of 15%;
wherein the fluid loss agent is an AMPS polymer with salt-resistant low-temperature early-strength characteristics.
2. The tough self-healing cement slurry for cementing a salt cavern gas storage according to claim 1, wherein the fluid loss agent is obtained by polymerizing the following components:
100 parts by weight of 2-acrylamide-2-methylpropanesulfonic acid, 0.1 to 0.5 part by weight of crosslinking monomer, 1 to 3 parts by weight of molecular weight regulator, 1 to 3 parts by weight of alcohol monomer, 8 to 10 parts by weight of amide monomer, 0.5 to 1.0 part by weight of 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 the molecular weight distribution of the fluid loss agent, and comprehensively improving the fluid loss control capability of the fluid loss agent in saline cement slurry prepared by using the fluid loss agent; the alcohol monomer is used to promote strength development of the saline-containing slurry under low temperature conditions.
3. The tough self-healing cement slurry for cementing a salt cavern gas storage according to claim 1,
the cement comprises grade G oil well cement.
4. The tough self-healing cement slurry for cementing a salt cavern gas storage according to claim 1,
the set retarder includes a phosphonate.
5. The tough self-healing cement slurry for cementing a salt cavern gas storage according to claim 1,
the drag reducer comprises polynaphthalene sulfonate.
6. The tough self-healing cement slurry for cementing a salt cavern gas storage according to claim 1,
the defoaming agent comprises tributyl phosphate and/or dimethyl silicone oil.
7. The tough self-healing cement slurry for cementing a salt cavern gas storage according to claim 1, wherein the toughening agent is prepared from the following components:
20-60 parts of whisker material, 5-10 parts of surfactant, 5-10 parts of silane coupling agent, 1-5 parts of defoaming agent, 10-25 parts of stabilizer, 100 parts of water and 250-1000 parts of absolute ethyl alcohol.
8. The tough self-healing cement slurry for cementing a salt cavern gas storage according to claim 1,
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 cross-linking agent to the initiator is 100:20 to 40:2 to 6;
the self-healing agent comprises a shell structure and is prepared from the following components in percentage by weight: the mass ratio of the styrene-based monomer to the acrylate to the vinyl polymer cross-linking agent to the initiator is 100:30 to 70:5 to 10:2 to 8.
9. The preparation method of the tough self-healing cement slurry for cementing in the salt cavern gas storage according to any one of claims 1 to 8, which is characterized by comprising the following steps:
uniformly mixing cement, a toughening agent, a self-healing agent, a fluid loss additive, a retarder, a drag reducer, a defoaming agent and 15% saline water to obtain the tough self-healing cement slurry for cementing the salt cavern gas storage.
10. The method according to claim 9,
uniformly mixing cement, a toughening agent, a self-healing agent, a fluid loss additive, a retarder, a drag reducer, a defoaming agent and 15% saline water, wherein the mixing process comprises the following steps:
under the condition of stirring, adding cement, a toughening agent, a self-healing agent meeting air, 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.
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