CN114163202A - Controllable curing plugging agent for natural gas hydrate reservoir and preparation method thereof - Google Patents

Controllable curing plugging agent for natural gas hydrate reservoir and preparation method thereof Download PDF

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Publication number
CN114163202A
CN114163202A CN202111269040.2A CN202111269040A CN114163202A CN 114163202 A CN114163202 A CN 114163202A CN 202111269040 A CN202111269040 A CN 202111269040A CN 114163202 A CN114163202 A CN 114163202A
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parts
agent
controllable
curing
plugging
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CN114163202B (en
Inventor
李龙
王韧
王成
张蝶
龙一夫
屈沅治
程荣超
李爽
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China National Petroleum Corp
CNPC Engineering Technology R&D Co Ltd
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China National Petroleum Corp
CNPC Engineering Technology R&D Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Sealing Material Composition (AREA)

Abstract

The invention relates to the technical field of natural gas hydrate reservoir protection, in particular to a controllable curing plugging agent for a natural gas hydrate reservoir and a preparation method thereof. The controllable curing plugging agent comprises 20-30 parts of acrylamide, 15-20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12-20 parts of tert-butyl styrene, 0.1-0.3 part of azodiisobutyronitrile, 180 parts of curing agent 120-containing liquid, 45-80 parts of filter aid, 6-12 parts of reinforcing agent, 3-8 parts of retarder, 2-6 parts of dispersing agent and 2-12 parts of activating agent. The controllable curing plugging agent has the advantages of wide temperature application range, fast strength development, high plugging strength, high acid solubility, no pollution to a reservoir stratum and the like, and meanwhile, in use, the controllable curing plugging agent is slightly influenced by a construction process, high in plugging success rate and strong in controllability.

Description

Controllable curing plugging agent for natural gas hydrate reservoir and preparation method thereof
Technical Field
The invention relates to the technical field of natural gas hydrate reservoir protection, in particular to a controllable curing plugging agent for a natural gas hydrate reservoir and a preparation method thereof.
Background
The natural gas hydrate exists in a high-pressure low-temperature environment, due to the physicochemical characteristics of the natural gas hydrate, when the natural gas hydrate is exploited, the problems of well wall collapse and slurry leakage are more prominent and complex than those of a conventional oil-gas layer, and the phenomena of well wall collapse, hole shrinkage, slurry leakage and the like frequently occur in drilling, so that the drilling time is lost, a large amount of drilling fluid and plugging materials are consumed, the oil-gas layer is damaged, logging is influenced, accidents such as drilling sticking, blowout and the like can be caused, even engineering scrapping is caused, the geological target realization is influenced, and the smooth operation of natural gas hydrate drilling is seriously influenced.
Taking the group of the applicant as an example, the lost time of complicated accidents in 2017 drilling is accumulated to 4122.52 days, wherein the lost circulation accounts for 71.01%, the lost period is 2927.5 days, the lost drilling fluid is 29.4 ten thousand, about 10 ten thousand tons of plugging agent is consumed, and about 23 million yuan is directly lost economically. Therefore, research work for performing wall protection and plugging on natural gas hydrate reservoirs is urgent.
In recent years, the plugging material has been developed to a certain extent, however, the existing plugging agent generally has the technical defects of low success rate, long time consumption, low pressure bearing capacity after plugging, difficult replication of plugging construction effect and the like. For other plugging technologies, such as special gel, downhole crosslinking, expandable plugging materials and technologies, the use is mainly empirical construction, the success rate needs to be improved, and the novel plugging materials and plugging processes are less explored.
The existing plugging materials mostly have the problems of insufficient adaptability to fractured leaking layers, low pressure bearing capacity, low plugging success rate and poor reproducibility in field use.
Disclosure of Invention
The invention aims to solve the technical problem of providing a controllable curing plugging agent for a natural gas hydrate reservoir and a preparation method thereof.
The technical scheme for solving the technical problems is as follows:
the invention provides a controllable curing plugging agent for a natural gas hydrate reservoir, which comprises the following components in parts by mass: 20-30 parts of acrylamide, 15-20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12-20 parts of tert-butyl styrene, 0.1-0.3 part of azobisisobutyronitrile, 180 parts of curing agent, 45-80 parts of filter aid, 6-12 parts of reinforcing agent, 3-8 parts of retarder, 2-6 parts of dispersant and 2-12 parts of activator.
Further, the paint comprises the following components in parts by weight: 24 parts of acrylamide, 20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 15 parts of tert-butyl styrene, 0.15 part of azobisisobutyronitrile, 120 parts of a curing agent, 60 parts of a filter aid, 9 parts of a reinforcing agent, 5 parts of a retarder, 3 parts of a dispersant and 9 parts of an activator.
Further, the paint comprises the following components in parts by weight: 26 parts of acrylamide, 18 parts of 2-acrylamido-2-methylpropanesulfonic acid, 16 parts of tert-butyl styrene, 0.18 part of azobisisobutyronitrile, 140 parts of a curing agent, 60 parts of a filter aid, 9 parts of a reinforcing agent, 6 parts of a retarder, 3 parts of a dispersant and 8 parts of an activator.
Further, the curing agent comprises one or more of sulphoaluminate cement, micro-manganese mineral powder and superfine calcium carbonate; the filter aid comprises one or more of sepiolite wool, superfine diatomite, perlite and cellulose filter aid; the reinforcing agent comprises one or more of asbestos fiber and mineral fiber; the retarder comprises one or more of boric acid, aluminum sulfate and sodium gluconate; the dispersant comprises one or more of polyacrylamide, sodium hexametaphosphate and lignosulfonate; the activator comprises one or more of calcium oxide, sodium silicate, potassium phosphate and sodium carbonate.
Further, the curing agent comprises sulphoaluminate cement and micro-manganese mineral powder, and the mass ratio of the sulphoaluminate cement to the micro-manganese mineral powder in each part of the curing agent is (3-1) to (1-1).
Further, the filter aid comprises sepiolite wool and superfine diatomite, wherein the mass ratio of the sepiolite wool to the superfine diatomite is (1-1) to (1-3).
Further, the retarder comprises boric acid and aluminum sulfate, and the mass ratio of the boric acid to the aluminum sulfate is (10-1): (2-1).
Further, the activator comprises calcium oxide and sodium silicate in a mass ratio of (1-3) to (1-1).
The invention provides a preparation method of the controllable curing plugging agent for the natural gas hydrate reservoir, which comprises the following steps of mixing acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, tert-butyl styrene and azobisisobutyronitrile according to corresponding parts by weight to obtain a polymer gel expanding agent; adding the curing agent, the filter aid, the reinforcing agent, the retarder and the dispersant into the polymer gel expanding agent solution; adding the activator to obtain the controllable solidified leakage-stopping slurry; and finally, drying the controllable curing plugging slurry to obtain the controllable curing plugging agent.
Further, the method comprises the following steps:
s1), dissolving acrylamide and 2-acrylamido-2-methylpropanesulfonic acid in water according to the corresponding mass parts, and adjusting the pH value of the solution to 8-9;
adding tert-butyl styrene into the solution according to the mass part, uniformly mixing, and controlling the temperature of the solution at 60-70 ℃;
introducing nitrogen into the solution, and adding azodiisobutyronitrile according to parts by mass to obtain the polymer gel expanding agent;
s2), adding the curing agent, the filter aid, the reinforcing agent, the retarder and the dispersant into the polymer gel expanding agent obtained in the step S1) according to the mass parts, and uniformly mixing to obtain a mixture;
s3), adding an activator into the mixture obtained in the step S2) according to the mass part of the activator, and uniformly stirring to obtain the controllable solidified leakage-stopping slurry;
s4), drying the controllable solidified plugging slurry and preparing the slurry into powder to obtain the controllable solidified plugging agent.
The technical scheme of the invention has the beneficial effects that:
1) the multi-field coupling response type controllable curing plugging agent is very sensitive to environmental pressure, temperature and chemical components of the environment: when the environmental pressure is more than 1MPa, the concentration of the chemical activator is more than 0.1 percent, and the temperature is 0-100 ℃, the components of the controllable curing plugging agent of the invention generate rapid response, the plugging pressure-bearing capacity is more than 20MPa, and the controllable curing cementation is realized.
2) According to the controllable curing plugging agent, after a formed plugging layer meets formation water, a gel expanding agent obtained by mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, tert-butyl styrene and azodiisobutyronitrile polymers can be further expanded, so that the plugging agent has better rigidity and flexibility, can simultaneously play a role in deformation and filling, and can effectively fill and block cracks and microcracks.
3) The controllable curing plugging agent can solve the problems of low one-time plugging success rate, serious repeated leakage loss and the like caused by multi-leakage-point well leakage of a natural gas hydrate reservoir stratum, can adapt to fracture-cave natural gas hydrate reservoir stratums with different leakage rates, and can obviously reduce the drilling cost.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The controllable curing plugging agent for the natural gas hydrate reservoir is particularly suitable for quick leakage control of a complex natural gas hydrate reservoir, and is a multi-field coupling response type controllable curing plugging agent.
The controllable curing plugging agent comprises the following components in parts by weight: 20-30 parts of acrylamide, 15-20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 10-20 parts of tert-butyl styrene, 0.1-0.3 part of azobisisobutyronitrile, 120-180 parts of curing agent, 40-80 parts of filter aid, 6-12 parts of reinforcing agent, 3-8 parts of retarder, 1-6 parts of dispersant and 2-12 parts of activator.
The finished product of the controllable curing plugging agent prepared by the invention is solid powder particles. When in use, the plugging agent can be directly added into clear water for use, or various base liquids can be adopted as solvents to prepare plugging slurry. The components of the plugging slurry also comprise water or other base fluid, and the amount of the plugging agent is 50-150% of the amount of the water or other base fluid.
According to the controllable curing plugging agent, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, tert-butyl styrene and azodiisobutyronitrile polymer are added, so that when the controllable curing plugging agent is used, a gel expanding agent obtained by mixing the components can be further expanded after a plugging layer formed by the plugging agent meets formation water, the controllable curing plugging agent has better rigidity and flexibility, and can play a role in deformation and filling at the same time, so that cracks and microcracks are effectively filled and blocked.
The controllable curing plugging agent has the advantages of wide temperature application range, fast strength development, high plugging strength, high acid solubility, no pollution to a reservoir stratum and the like, and is less influenced by the construction process, high in plugging success rate and strong in controllability in use.
Specifically, the controllable curing plugging agent disclosed by the invention is suitable for an environment temperature range of 0-100 ℃.
The controllable curing plugging agent has a pressure response range of 1.0-25MPa, and when the environmental pressure is greater than or equal to 1MPa, the response effect is achieved, and the highest pressure-bearing plugging capacity reaches more than 20 MPa; the controllable curing plugging agent has high sensitivity to environmental pressure, can generate consolidation reaction under the pressure condition and has pressure response capability. When the pressure reaches the lowest critical pressure (the lowest critical pressure is about 1MPa generally), the components of the controllable curing plugging agent can quickly generate dehydration phase change and generate aggregates in water, so that the local concentration of the controllable curing plugging agent is improved, and a consolidation reaction is performed under the action of a water-soluble activator to form a compact consolidation slug plugging layer.
The solidification process of the controllable solidification plugging agent meets the following equation:
Figure BDA0003328000560000051
wherein S is a curing rate; c is the concentration of the activator, and the unit is mol/L; r is a proportionality constant, specifically 8.314J/mol/K; p is the pressure born by the plugging agent and has the unit of Pa; p0Is atmospheric pressure in Pa; t is the indoor temperature in K; t isaThe temperature tolerated by the plugging agent is given in K; t is time; when P is less than 10P0(1MPa), S is 0.
According to the consolidation process equation, in order to improve the solidification rate S, the concentration of the activating agent can be properly increased, or the pressure bearing capacity and the temperature tolerance of the plugging agent can be increased; however, the concentration of the activator cannot be simply increased in consideration of the compounding with other components, because the concentration of the activator is too high, which leads to a decrease in pressure-bearing capacity.
The controllable curing plugging agent has the curing rate of 10-100% in the pressure response range, and the plugging adaptation crack width is 1.0-10 mm.
The hydrochloric acid dissolution rate of the controllable curing plugging agent is more than 96 percent, so that the controllable curing plugging agent is suitable for the leakage occurring in a reservoir section; in the implementation process of plugging construction, the controllable curing plugging agent can not only realize quick leak control, but also effectively protect a reservoir stratum, and achieve the purposes of increasing production, improving quality and improving efficiency.
Preferably, the curing agent comprises one or more of sulphoaluminate cement, micro-manganese mineral powder and superfine calcium carbonate.
Further preferably, the curing agent comprises sulphoaluminate cement and micro-manganese mineral powder in a mass ratio of (3-1) to (1-1). In a specific embodiment, the curing agent comprises sulphoaluminate cement and micro-manganese ore powder in a mass ratio of 2: 1.
Preferably, the filter aid comprises one or more of sepiolite wool, ultra-fine diatomaceous earth, perlite and cellulose filter aids.
Further preferably, the filter aid comprises sepiolite wool and superfine diatomite in a mass ratio of (1-1) to (1-3); the particle size of the superfine diatomite is larger than 1500 meshes. In a particular embodiment, the filter aid comprises sepiolite wool and ultra-fine diatomaceous earth in a mass ratio of 1: 2.
Preferably, the reinforcing agent is one or more of asbestos fiber and mineral fiber; among them, the mineral fiber is preferably brucite fiber.
Further preferred, the reinforcing agent comprises asbestos fibers and mineral fibers; in a particular embodiment, the reinforcing agent comprises asbestos fibers.
Preferably, the retarder comprises one or more of boric acid, aluminium sulphate and sodium gluconate.
Further preferably, the retarder comprises boric acid and aluminum sulfate in a mass ratio of (10-1) to (2-1); in a particular embodiment, the set retarder comprises boric acid and aluminum sulfate in a 6:1 mass ratio.
Preferably, the dispersant is one or more of polyacrylamide, sodium hexametaphosphate and lignosulfonate.
Further preferably, the dispersant comprises sodium polyacrylamide and sodium hexametaphosphate, wherein the average molecular weight of the polyacrylamide is 6000000; in a particular embodiment, the dispersant is polyacrylamide.
Preferably, the activator is one or more of calcium oxide, sodium silicate, potassium phosphate and sodium carbonate.
Further preferably, the activator comprises calcium oxide, sodium silicate and potassium phosphate; more preferably, the activator comprises calcium oxide and sodium silicate in a mass ratio of (1-3) to (1-1); in a specific embodiment, the activator comprises calcium oxide and sodium silicate in a mass ratio of 6: 10.
The preparation method of the controllable curing plugging agent for the natural gas hydrate reservoir comprises the following steps of mixing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, tert-butyl styrene and azobisisobutyronitrile according to corresponding parts by weight to obtain a polymer gel expanding agent; then adding a curing agent, a filter aid, a reinforcing agent, a retarder, a dispersant and the activator into the polymer gel expanding agent to obtain a controllable curing plugging agent; the method comprises the following specific steps:
s1), dissolving acrylamide and 2-acrylamido-2-methylpropanesulfonic acid in deionized water, adding sodium hydroxide to adjust the pH value to 8-9, adding tert-butyl styrene, stirring at a high speed for 20-30 minutes, mixing uniformly, controlling the reaction temperature to be 60-70 ℃, introducing nitrogen, slowly adding azobisisobutyronitrile, stirring at a constant temperature to react for 3-4 hours, and obtaining the polymer gel expanding agent.
S2), adding components such as curing agent, filter aid, reinforcing agent, retarder, dispersant and the like into the reaction product obtained in the step S1, and stirring for 20-30 minutes until the components are uniformly mixed to obtain a mixture.
S3), adding an activating agent into the mixture obtained in the step S2, and stirring at medium speed for 10-30 minutes to obtain the multi-field coupling response type controllable solidified leakage-stopping slurry.
S4), drying the controllable curing plugging slurry and preparing the slurry into powder to obtain the controllable curing plugging agent.
The effect of the controllably curable plugging agent of the present invention will be described below with reference to examples.
Example 1
The controllable curing plugging agent comprises the following components in parts by weight: 20 parts of acrylamide, 15 parts of 2-acrylamido-2-methylpropanesulfonic acid, 20 parts of tert-butyl styrene, 0.1 part of azobisisobutyronitrile, 120 parts of a curing agent, 80 parts of a filter aid, 6 parts of a reinforcing agent, 3 parts of a retarder, 6 parts of a dispersant and 3 parts of an activator.
The preparation process of the controllable curing plugging agent of the embodiment is as follows:
s1), dissolving 20 parts by mass of acrylamide and 15 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid in deionized water, and adding sodium hydroxide to adjust the pH value of the solution to 8; adding 20 parts of tert-butyl styrene, stirring at a high speed for 20 minutes, and uniformly mixing; controlling the reaction temperature of the solution to be 60 ℃; and introducing nitrogen, slowly adding 0.1 part of azodiisobutyronitrile, and stirring at constant temperature for reaction for 3 hours to obtain the polymer gel expanding agent.
S2), adding 120 parts of curing agent, 80 parts of filter aid, 6 parts of reinforcing agent, 3 parts of retarder and 6 parts of dispersant into the polymer gel expanding agent obtained in the step S1, and stirring for 20 minutes until the mixture is uniformly mixed to obtain a mixture.
S3), adding 3 parts of activating agent into the mixture obtained in the step S2, and stirring at medium speed for 10 minutes to obtain multi-field coupling response type controllable solidified leakage-stopping slurry which is in the form of an aqueous solution of a leakage-stopping agent.
S4), drying the controllable curing plugging slurry and preparing the slurry into powder to obtain the controllable curing plugging agent.
Example 2
The controllable curing plugging agent comprises the following components in parts by weight: 24 parts of acrylamide, 20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 15 parts of tert-butyl styrene, 0.15 part of azobisisobutyronitrile, 120 parts of a curing agent, 60 parts of a filter aid, 9 parts of a reinforcing agent, 5 parts of a retarder, 3 parts of a dispersant and 9 parts of an activator.
The preparation process of the controllable curing plugging agent of the embodiment is as follows:
s1), dissolving 24 parts by mass of acrylamide and 20 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid in deionized water, adding sodium hydroxide to adjust the pH value of the solution to 9, adding 15 parts by mass of tert-butyl styrene, stirring at high speed for 25 minutes, and uniformly mixing; controlling the reaction temperature to be 65 ℃; and introducing nitrogen, slowly adding 0.15 part of azodiisobutyronitrile, and stirring at constant temperature for reaction for 3 hours to obtain the polymer gel expanding agent.
S2), adding 120 parts of curing agent, 60 parts of filter aid, 9 parts of reinforcing agent, 5 parts of retarder and 3 parts of dispersant into the polymer gel expanding agent obtained in the step S1, and stirring for 30 minutes until the mixture is uniformly mixed to obtain a mixture.
S3), adding 9 parts of activating agent into the mixture obtained in the step S2, and stirring at medium speed for 25 minutes to obtain the multi-field coupling response type controllable solidified leakage-stopping slurry which is in the form of an aqueous solution of a leakage-stopping agent.
S4), drying the controllable curing plugging slurry and preparing the slurry into powder to obtain the controllable curing plugging agent.
Example 3
The controllable curing plugging agent comprises the following components in parts by weight: 28 parts of acrylamide, 15 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12 parts of tert-butyl styrene, 0.15 part of azobisisobutyronitrile, 128 parts of a curing agent, 60 parts of a filter aid, 10 parts of a reinforcing agent, 5 parts of a retarder, 5 parts of a dispersant and 12 parts of an activator.
The preparation process of the controllable curing plugging agent of the embodiment is as follows:
s1), dissolving 28 parts by mass of acrylamide and 15 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid in deionized water, adding sodium hydroxide to adjust the pH value of the solution to 8, adding 12 parts by mass of tert-butyl styrene, stirring at high speed for 30 minutes, and uniformly mixing; controlling the reaction temperature to be 70 ℃; and introducing nitrogen, slowly adding 0.2 part of azodiisobutyronitrile, and stirring at constant temperature for reaction for 3 hours to obtain the polymer gel expanding agent.
S2), adding 128 parts of curing agent, 60 parts of filter aid, 10 parts of reinforcing agent, 5 parts of retarder and 5 parts of dispersant into the polymer gel expanding agent of the step S1, and stirring for 20 minutes until the mixture is uniformly mixed to obtain a mixture.
S3), adding 12 parts of activating agent into the mixture obtained in the step S2, and stirring at medium speed for 30 minutes to obtain multi-field coupling response type controllable solidified leakage-stopping slurry which is in the form of an aqueous solution of a leakage-stopping agent.
S4), drying the controllable curing plugging slurry and preparing the slurry into powder to obtain the controllable curing plugging agent.
Example 4
The controllable curing plugging agent comprises the following components in parts by weight: 30 parts of acrylamide, 15 parts of 2-acrylamido-2-methylpropanesulfonic acid, 20 parts of tert-butyl styrene, 0.3 part of azobisisobutyronitrile, 180 parts of a curing agent, 45 parts of a filter aid, 8 parts of a reinforcing agent, 8 parts of a retarder, 4 parts of a dispersant and 4 parts of an activator.
The preparation process of the controllable curing plugging agent of the embodiment is as follows:
s1), dissolving 30 parts by mass of acrylamide and 15 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid in deionized water, adding sodium hydroxide to adjust the pH value of the solution to 8, adding 20 parts by mass of tert-butyl styrene, stirring at high speed for 25 minutes, and uniformly mixing; controlling the reaction temperature to be 60 ℃; and introducing nitrogen, slowly adding 0.3 part of azodiisobutyronitrile, and stirring at constant temperature for reaction for 3 hours to obtain the polymer gel expanding agent.
S2), adding 180 parts of curing agent, 45 parts of filter aid, 8 parts of reinforcing agent, 8 parts of retarder and 4 parts of dispersant into the polymer gel expanding agent obtained in the step S1, and stirring for 20 minutes until the mixture is uniformly mixed to obtain a mixture.
S3), adding 4 parts of activating agent into the mixture obtained in the step S2, and stirring at medium speed for 25 minutes to obtain the multi-field coupling response type controllable solidified leakage-stopping slurry which is in the form of an aqueous solution of the leakage-stopping agent.
S4), drying the controllable curing plugging slurry and preparing the slurry into powder to obtain the controllable curing plugging agent.
Example 5
The controllable curing plugging agent comprises the following components in parts by weight: 28 parts of acrylamide, 20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 14 parts of tert-butyl styrene, 0.28 part of azobisisobutyronitrile, 180 parts of a curing agent, 70 parts of a filter aid, 12 parts of a reinforcing agent, 3 parts of a retarder, 2 parts of a dispersant and 2 parts of an activator.
The preparation process of the controllable curing plugging agent of the embodiment is as follows:
s1), dissolving 28 parts by mass of acrylamide and 20 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid in deionized water, adding sodium hydroxide to adjust the pH value of the solution to 9, adding 14 parts by mass of tert-butyl styrene, stirring at high speed for 25 minutes, and uniformly mixing; controlling the reaction temperature to be 60 ℃; and introducing nitrogen, slowly adding 0.28 part of azodiisobutyronitrile, and stirring at constant temperature for reaction for 3 hours to obtain the polymer gel expanding agent.
S2), adding 180 parts of curing agent, 70 parts of filter aid, 12 parts of reinforcing agent, 3 parts of retarder and 2 parts of dispersant into the polymer gel expanding agent obtained in the step S1, and stirring for 20 minutes until the mixture is uniformly mixed to obtain a mixture.
S3), adding 2 parts of activating agent into the mixture obtained in the step S2, and stirring at medium speed for 30 minutes to obtain multi-field coupling response type controllable solidified leakage-stopping slurry which is in the form of an aqueous solution of a leakage-stopping agent.
S4), drying the controllable curing plugging slurry and preparing the slurry into powder to obtain the controllable curing plugging agent.
Example 6
The controllable curing plugging agent comprises the following components in parts by weight: 26 parts of acrylamide, 18 parts of 2-acrylamido-2-methylpropanesulfonic acid, 16 parts of tert-butyl styrene, 0.18 part of azobisisobutyronitrile, 140 parts of a curing agent, 60 parts of a filter aid, 9 parts of a reinforcing agent, 6 parts of a retarder, 3 parts of a dispersant and 8 parts of an activator.
The preparation process of the controllable curing plugging agent of the embodiment is as follows:
s1), dissolving 26 parts by mass of acrylamide and 18 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid in deionized water, adding sodium hydroxide to adjust the pH value of the solution to 9, adding 16 parts by mass of tert-butyl styrene, stirring at a high speed for 30 minutes, uniformly mixing, controlling the reaction temperature to be 70 ℃, introducing nitrogen, slowly adding 0.18 part by mass of azobisisobutyronitrile, and stirring at a constant temperature for reacting for 4 hours to obtain the polymer gel expanding agent.
S2), adding 140 parts of curing agent, 60 parts of filter aid, 9 parts of reinforcing agent, 6 parts of retarder and 3 parts of dispersant into the polymer gel expanding agent obtained in the step S1, and stirring for 20 minutes until the mixture is uniformly mixed to obtain a mixture.
S3), adding 8 parts of activating agent into the mixture obtained in the step S2, and stirring at medium speed for 30 minutes to obtain multi-field coupling response type controllable solidified leakage-stopping slurry which is in the form of an aqueous solution of a leakage-stopping agent.
S4), drying the controllable curing plugging slurry and preparing the slurry into powder to obtain the controllable curing plugging agent.
The components of the controllable curing plugging agent of the embodiments 1-6 are shown in the following table 1:
TABLE 1 Components of the controlled curing plugging agents of examples 1 to 6 (in parts by mass)
Figure BDA0003328000560000131
The concrete components of the curing agent, the filter aid, the reinforcing agent, the retarder, the dispersant and the activator in the embodiments 1-6 are as follows: the curing agent is sulphoaluminate cement and micro-manganese mineral powder in a mass ratio of 2:1, the filter aid is sepiolite wool and superfine diatomite in a mass ratio of 1:2, the reinforcing agent is asbestos wool fiber, the retarder is boric acid and aluminum sulfate in a mass ratio of 6:1, and the dispersant is polyacrylamide activator which is calcium oxide and sodium silicate in a mass ratio of 6: 10.
The controllable curing plugging agent of the embodiment 1-6 is added into clear water or water-based drilling fluid for the following performance tests.
Test 1 acid solubility test
The test results are shown in Table 2, according to the test method specified in the trade standard SY/T5559 1992 Universal test method for treating agents for drilling fluids.
TABLE 2 acid solubility of each of the curable plugging agents of examples 1 to 6
Figure BDA0003328000560000141
The acid solubility test results in table 2 show that the acid solubility of the controllable curing plugging agents of examples 1 to 6 is 96% or more, the average acid solubility is 96.64%, and particularly, the acid solubility of the samples 2 and 6 is the most preferable.
Test 2 pressure bearing plugging capability test
Multi-field coupling response type controllable solidified leakage-stopping slurry: adding a multi-field coupling response type controllable curing plugging agent into clear water and uniformly stirring, wherein the effective content of the controllable curing plugging agent is 60-200% of the mass of the clear water.
The pressure-bearing plugging capacity is determined according to a method specified in an industry standard SY/T5840-2007 indoor test method for bridging plugging materials for drilling fluid. The plugging agent of the multi-field coupling response type controllable curing plugging agent of the embodiment containing 100% of clear water volume is used for carrying out high-temperature and high-pressure dynamic plugging simulation experiments, forward plugging experiments are carried out on test modules with the seam widths of 1-3mm, 3-5mm and 8-10mm, and the displayed final pressure is pressure-bearing plugging capacity. The test results of the highest pressure-bearing plugging capacity corresponding to each embodiment are shown in table 3.
TABLE 3 highest bearing plugging capability of each of the controlled curing plugging agents of examples 1-6
Figure BDA0003328000560000151
The test results of the highest pressure-bearing plugging capability in table 3 show that the controllable curing plugging agents in examples 1 to 6 can form compact plugging layers in simulated leakage layers of 1-3mm, 3-5mm and 8-10mm seam plates, the pressure-bearing plugging pressures of the compact plugging layers are all greater than 18MPa, the highest pressure-bearing plugging capability of example 2 is used, and the highest pressure-bearing capability reaches 21.6 MPa.
Test 3 flexural Strength test
The flexural strength is determined according to the method specified in the national standard GB/T3001-2007 test method for refractory material-normal temperature flexural strength, and a standard prism test piece with the size of 40mm multiplied by 160mm is adopted. After the multi-field coupling response type controllable curing leaking stoppage slurry is filled in a test mold and a cover plate is covered, the mold is firstly taken out after being solidified at room temperature and the like, then the mold is put into a high-temperature curing kettle with the required temperature, the curing condition is 100 ℃ and 20MPa, the mold is taken out after being cured for 24 hours, and the flexural strength of the mold is evaluated by adopting a flexural strength tester. The test results are shown in Table 4.
TABLE 4 flexural Strength of each of the controllably curable lost circulation additives of examples 1-6
Serial number Flexural strength (MPa)
Example 1 10.9
Example 2 11.6
Example 3 10.4
Example 4 9.9
Example 5 10.2
Example 6 12.8
As shown in the flexural strength test results in Table 4, the flexural strength of the controllable curing plugging agents of examples 1-6 is generally greater than 10MPa, and the flexural strength of example 6 is the maximum, which is 12.8 MPa.
In addition, in each test, the controllable curing plugging agent in each embodiment is fully solidified within about 30 minutes, so that the controllable curing plugging agent has the characteristic of high corresponding speed.
In the test of pressure-bearing plugging capacity and breaking strength, the test temperature is 0-100 ℃, and the environmental pressure is more than 1 MPa.
Through the tests, the multi-field coupling response type controllable curing plugging agent provided by the invention has the characteristics of wide temperature application range, fast strength development, no pollution to a reservoir stratum and the like; the response type controllable curing plugging agent has the response effect at the temperature of 0-100 ℃ and the environmental pressure of more than 1MPa, the highest pressure-bearing plugging capacity of more than 20MPa, the breaking strength of more than 10MPa, and the adaptive crack of 10 mm.
The gas hydrate fracture-cavity leakage layer drilling tool can adapt to hole-seam-hole leakage layers with different leakage rates, can solve the problem of gas hydrate fracture-cavity type reservoir leakage of a plurality of pressure systems, realizes quick and high-strength leakage control of a plurality of leakage layers of a complicated gas hydrate reservoir section, ensures safe and quick drilling of a long open hole gas hydrate reservoir section, and meets the requirement of efficient development of a deep gas hydrate reservoir.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A controllable curing plugging agent for a natural gas hydrate reservoir is characterized by comprising the following components in parts by mass:
20-30 parts of acrylamide, 15-20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 12-20 parts of tert-butyl styrene, 0.1-0.3 part of azobisisobutyronitrile, 180 parts of curing agent, 45-80 parts of filter aid, 6-12 parts of reinforcing agent, 3-8 parts of retarder, 2-6 parts of dispersant and 2-12 parts of activator.
2. A controllable curing plugging agent for a natural gas hydrate reservoir as claimed in claim 1, which comprises the following components in parts by weight:
24 parts of acrylamide, 20 parts of 2-acrylamido-2-methylpropanesulfonic acid, 15 parts of tert-butyl styrene, 0.15 part of azobisisobutyronitrile, 120 parts of a curing agent, 60 parts of a filter aid, 9 parts of a reinforcing agent, 5 parts of a retarder, 3 parts of a dispersant and 9 parts of an activator.
3. A controllable curing plugging agent for a natural gas hydrate reservoir as claimed in claim 1, which comprises the following components in parts by weight:
26 parts of acrylamide, 18 parts of 2-acrylamido-2-methylpropanesulfonic acid, 16 parts of tert-butyl styrene, 0.18 part of azobisisobutyronitrile, 140 parts of a curing agent, 60 parts of a filter aid, 9 parts of a reinforcing agent, 6 parts of a retarder, 3 parts of a dispersant and 8 parts of an activator.
4. A controllable curing plugging agent for a natural gas hydrate reservoir according to any one of claims 1 to 3,
the curing agent comprises one or more of sulphoaluminate cement, micro manganese mineral powder and superfine calcium carbonate; the filter aid comprises one or more of sepiolite wool, superfine diatomite, perlite and cellulose filter aid; the reinforcing agent comprises one or more of asbestos fiber and mineral fiber; the retarder comprises one or more of boric acid, aluminum sulfate and sodium gluconate; the dispersant comprises one or more of polyacrylamide, sodium hexametaphosphate and lignosulfonate; the activator comprises one or more of calcium oxide, sodium silicate, potassium phosphate and sodium carbonate.
5. A controllable curing plugging agent for a natural gas hydrate reservoir stratum according to claim 4, wherein the curing agent comprises sulphoaluminate cement and micro-manganese mineral powder, and the mass ratio of the sulphoaluminate cement to the micro-manganese mineral powder in each curing agent is (3-1): 1-1.
6. The controllable solidification plugging agent for the natural gas hydrate reservoir bed according to claim 4, wherein the filter aid comprises sepiolite wool and superfine diatomite, and the mass ratio of the sepiolite wool to the superfine diatomite is (1-1) to (1-3).
7. The controllable solidification plugging agent for the natural gas hydrate reservoir bed of claim 4, wherein the retarder comprises boric acid and aluminum sulfate, and the mass ratio of the boric acid to the aluminum sulfate is (10-1) to (2-1).
8. A controlled solidification plugging agent for a natural gas hydrate reservoir as claimed in claim 4, wherein the activator comprises the calcium oxide and the sodium silicate in a mass ratio of (1-3) to (1-1).
9. A preparation method of the controllable curing plugging agent for the natural gas hydrate reservoir as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
firstly, mixing and dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, tert-butyl styrene and azobisisobutyronitrile in a solvent according to corresponding parts by weight to obtain a polymer gel swelling agent solution;
adding the curing agent, the filter aid, the reinforcing agent, the retarder and the dispersant into the polymer gel expanding agent solution;
adding the activator to obtain the controllable solidified leakage-stopping slurry;
and finally, drying the controllable curing plugging slurry to obtain the controllable curing plugging agent.
10. The preparation method of the controllable curing plugging agent for the natural gas hydrate reservoir as claimed in claim 9, is characterized by comprising the following steps:
s1), dissolving acrylamide and 2-acrylamido-2-methylpropanesulfonic acid in water according to the corresponding mass parts, and adjusting the pH value of the solution to 8-9;
adding tert-butyl styrene into the solution according to the mass part, uniformly mixing, and controlling the temperature of the solution at 60-70 ℃;
introducing nitrogen into the solution, and adding azodiisobutyronitrile according to parts by mass to obtain the polymer gel expanding agent;
s2), adding the curing agent, the filter aid, the reinforcing agent, the retarder and the dispersant into the polymer gel expanding agent obtained in the step S1) according to the mass parts, and uniformly mixing to obtain a mixture;
s3), adding an activator into the mixture obtained in the step S2) according to the mass part of the activator, and uniformly stirring to obtain the controllable solidified leakage-stopping slurry;
s4), drying the controllable solidified plugging slurry and preparing the slurry into powder to obtain the controllable solidified plugging agent.
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Publication number Priority date Publication date Assignee Title
US20060162930A1 (en) * 2005-01-24 2006-07-27 Jan Gronsveld Methods of plugging a permeable zone downhole using a sealant composition comprising a crosslinkable material and a reduced amount of cement
CN105925253A (en) * 2016-05-10 2016-09-07 中国石油集团渤海钻探工程有限公司 Low-density acid-soluble curing plugging agent
CN108706927A (en) * 2018-05-17 2018-10-26 中国石油集团工程技术研究院有限公司 A kind of high-temperature water mud suspension stabilizer and its high temperature resisting cement grout of preparation
CN112342001A (en) * 2020-11-30 2021-02-09 中国石油天然气集团有限公司 Plugging agent and plugging slurry for oil-based drilling fluid and preparation method of plugging agent and plugging slurry
CN112341998A (en) * 2020-11-16 2021-02-09 成都理工大学 Plugging material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060162930A1 (en) * 2005-01-24 2006-07-27 Jan Gronsveld Methods of plugging a permeable zone downhole using a sealant composition comprising a crosslinkable material and a reduced amount of cement
CN105925253A (en) * 2016-05-10 2016-09-07 中国石油集团渤海钻探工程有限公司 Low-density acid-soluble curing plugging agent
CN108706927A (en) * 2018-05-17 2018-10-26 中国石油集团工程技术研究院有限公司 A kind of high-temperature water mud suspension stabilizer and its high temperature resisting cement grout of preparation
CN112341998A (en) * 2020-11-16 2021-02-09 成都理工大学 Plugging material and preparation method thereof
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