CN114702622A - Thixotropic self-healing gel plugging agent and preparation method and application thereof - Google Patents
Thixotropic self-healing gel plugging agent and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
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- 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
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- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
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Abstract
The invention relates to the technical field of leakage prevention and leakage stoppage of drilling fluid, in particular to a thixotropic self-healing gel leakage stoppage agent and a preparation method thereof, wherein the thixotropic self-healing gel leakage stoppage agent is prepared from the following raw materials: 20-30 parts of acrylamide, 0.05-0.1 part of hydroxyethyl methacrylate, 10-15 parts of zwitterionic monomer, 1.5-2 parts of first hydrophobic monomer, 0.5-1 part of second hydrophobic monomer, 0.05-0.5 part of initiator and 1-3 parts of dispersant. The invention also provides a preparation method of the thixotropic self-healing gel plugging agent. The thixotropic self-healing gel plugging agent formed by the invention is a reversible supermolecular dynamic cross-linked network, has excellent thixotropic self-healing capability and plugging bearing capability, and can realize effective plugging of a target leakage layer.
Description
Technical Field
The invention belongs to the technical field of leakage prevention and leakage stoppage of drilling fluid, and particularly relates to a thixotropic self-healing gel leakage stoppage agent and a preparation method and application thereof.
Background
Lost circulation is the most common and difficult to manage downhole complex accident in the drilling process, mainly occurring in fractured, karst cave and fractured formations. Aiming at the difficult problem of lost circulation, the prior art mainly injects a plugging material into a lost stratum to plug the stratum. The viscoelastic material formed by interaction of a plurality of polymer materials of polymer gel has strong deformability, can break through the limitation of a leakage passage, is one of the most common plugging materials, but is difficult to control the gelling time, cannot enter a leakage layer accurately, and is easy to cause the waste of a large amount of materials and accidents such as drilling jamming and well collapse.
The intelligent polymer gel plugging material can respond to the external stimulus to adapt to the environmental change, improve the strain capacity and realize the controllability of the polymer gel material. The thixotropic self-healing polymer gel system has a reversible supermolecule dynamic physical cross-linking network, has fluidity under the action of high shear stress, enters a leakage channel under a static condition and expands to form gel with certain strength, effectively prevents the gel from being cemented before entering the leakage channel, and realizes controllability of a leakage stopping process.
Thixotropic self-healing polymer special gel ZND is developed and developed by Rotoneia academicians according to the structural fluid theory and the supermolecule chemical principle [ ZND, Yonghai, Yongping, etc.. the application of the special gel in well drilling and plugging [ J ]. drilling fluid and completion fluid, 2007, 24 (5): 83-84.]. Research [ J ] on DNG of a novel plugging gel DNG [ J ] drilling fluid and completion fluid, 2010, 27 (3): 33-35.]. A special functional monomer is introduced into a macromolecular chain of the thixotropic self-healing gel plugging material to form a hydrophilic-hydrophobic micro-area structure, a reversible supermolecule dynamic network structure is formed through intermolecular action, and the degree of network crosslinking is controlled by utilizing a shearing action, so that the controllability of the gel material is realized.
Patent document CN113501910A discloses a multiple non-covalent synergistic self-healing gel plugging agent and its preparation and application, the gel plugging agent is prepared from a first copolymerization reaction monomer, a second copolymerization reaction monomer, a surfactant, an initiator, a first cross-linking agent, a second cross-linking agent, an accelerator, and a sodium chloride aqueous solution, the gel plugging agent forms a weak network at a target layer by means of ionic bonds to rapidly realize primary healing, a strong network based on hydrophobic association reaction is formed on the basis of the weak network, an energy dissipation mechanism based on the strong/weak network is formed, the mechanical strength is good, and the effect is stronger than that of the gel plugging agent healed by covalent bonds.
Patent document CN105504158A discloses an intelligent gel particle that can be re-crosslinked under formation conditions, wherein the gel particle is prepared from acrylamide, an anionic monomer, a cationic monomer, N-vinyl pyrrolidone, a pH regulator, an initiator, a crosslinking agent i, a crosslinking agent ii, a stabilizer, a nanoparticle and water, and after entering the formation, the intelligent gel particle is re-crosslinked under formation conditions to form a high-strength gel, thereby realizing effective plugging.
Patent document CN112250787A discloses a gel particle plugging agent with self-healing property, which comprises comonomer, surfactant a, initiator, cross-linking agent and cationic latex particle raw material, wherein the gel particle material can be recovered after being damaged, injected into formation cracks in a particle form, and can form an integral gel after healing, so as to achieve the purpose of effectively plugging the cracks and pores.
At present, the research on the self-healing intelligent gel plugging material is less, and the research on the thixotropic self-healing gel plugging material is in a primary stage. The existing thixotropic self-healing gel plugging material is difficult to meet the continuous well leakage problem, and a new supermolecule gel plugging agent with thixotropic self-healing type needs to be developed, so that the aim of plugging cracks more efficiently is fulfilled.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a thixotropic self-healing gel plugging agent and a preparation method and application thereof. The gel plugging agent has high fluidity under high shear stress after entering a stratum while drilling, and gradually forms integral gel with good mechanical strength and expansibility under the static action after reaching a target layer, thereby realizing efficient plugging of fracture pores.
The invention aims to provide a thixotropic self-healing gel plugging agent.
The invention also aims to provide a preparation method of the thixotropic self-healing gel plugging agent.
The invention further aims to provide application of the thixotropic self-healing gel plugging agent.
The thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight:
20-30 parts of acrylamide, 0.05-0.1 part of hydroxyethyl methacrylate, 10-15 parts of zwitterionic monomer, 1.5-2 parts of first hydrophobic monomer, 0.5-1 part of second hydrophobic monomer, 0.05-0.5 part of initiator and 1-3 parts of dispersant.
According to the thixotropic self-healing gel plugging agent of the embodiment of the invention, the zwitterionic monomer is sulfobetaine acrylamide;
the first hydrophobic monomer is one or the combination of more than two of lauryl acrylate, lauryl methacrylate, dodecafluoro heptyl acrylate and tridecafluorooctyl acrylate;
the second hydrophobic monomer is one or the combination of more than two of styrene, 1-vinyl imidazole and 1- (4-vinyl benzyl) -1H-imidazole;
the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobiscyclohexyl carbonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide and methyl ethyl ketone peroxide;
further, the dispersant is a mixture of an inorganic dispersant and an organic dispersant, the inorganic dispersant is one of calcium carbonate, nano-silica and talcum powder, the organic dispersant is one or two of polyvinyl alcohol and hydroxypropyl methyl cellulose, and the addition ratio of the inorganic dispersant to the organic dispersant is (5-10): 1.
according to the thixotropic self-healing gel plugging agent of the embodiment of the invention, the sulfobetaine acrylamide is one or two of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt.
According to the thixotropic self-healing gel plugging agent provided by the specific embodiment of the invention, the raw materials further comprise deionized water and a pH regulator, wherein the addition amount of the deionized water is 100 parts by weight; the pH regulator is sodium hydroxide solution with the concentration of 10-20%.
The preparation method of the thixotropic self-healing gel plugging agent according to the embodiment of the invention comprises the following steps:
(1) adding acrylamide, hydroxyethyl methacrylate and a zwitterionic monomer into deionized water according to the proportion, uniformly stirring and adjusting the pH value of the solution; adding a dispersing agent, and uniformly stirring to form an aqueous phase solution A;
(2) adding a second hydrophobic monomer and an initiator into the first hydrophobic monomer, and uniformly stirring to form an organic phase solution B;
(3) placing the phase solution A obtained in the step (1) in a water bath kettle, controlling the temperature to be 60-75 ℃, introducing nitrogen for 15-30min, dropwise adding the organic phase solution B obtained in the step (2) into the aqueous phase solution A at the stirring speed of 800r/min, and continuously stirring for 2-3h after the addition is finished to form a solution C;
(4) keeping the temperature of the solution C obtained in the step (3) and standing to obtain a thixotropic self-healing gel base material;
(5) and (4) drying and crushing the thixotropic self-healing gel base material obtained in the step (4) to obtain the thixotropic self-healing gel plugging agent.
According to the preparation method of the thixotropic self-healing gel plugging agent, the heat preservation time is 10-12 hours and the heat preservation temperature is 75-80 ℃ in the step (5).
According to the preparation method of the thixotropic self-healing gel plugging agent, in the step (5), the drying is specifically drying for 20-24 hours at 55-70 ℃ under vacuum condition.
In the step (5), the particle size of the crushed particles is adjusted according to the field requirements.
According to the application of the thixotropic self-healing gel plugging agent disclosed by the embodiment of the invention, the thixotropic self-healing gel plugging agent is dispersed in drilling fluid in a particle form and enters a target stratum while drilling.
Furthermore, the addition amount of the plugging agent particles is 1-3.5% of the mass of the drilling fluid.
The thixotropic self-healing gel plugging agent has fluidity and low viscosity under the action of high shear, enters a leakage channel under the static condition, and is crosslinked and expanded to form high-strength integral gel. The preparation mechanism is as follows: (1) the introduction of the first hydrophobic monomer enables macromolecular chains to spontaneously aggregate through intermolecular hydrophobic association to form a reversible supermolecular dynamic network which can be reversibly opened under the action of shear force so as to facilitate the migration of the gel plugging agent in a stratum, and the hydrophobic monomers are helpful for maintaining the elasticity of the network; (2) the zwitterion component is introduced in the preparation of the gel, so that the hydration capability is strong, the ion effect between molecular chains and in the molecular chains is generated, the cross-linking points of the network structure are increased, and the formation of the network structure is promoted; the hydroxyethyl methacrylate can form hydrogen bond acting force in a network per se and among networks, and the acting force and intermolecular ion action are beneficial to maintaining a supramolecular system and enhancing the gel strength; (3) the benzene ring and imidazole structures introduced into the molecular structure greatly improve the mechanical toughness of the gel and further enhance the gel strength.
Compared with the prior art, the invention has the following beneficial effects:
1. the thixotropic self-healing gel plugging agent disclosed by the invention forms gel particles on the ground, enters a stratum while drilling, has high fluidity under the action of shearing force, forms an integral gel with excellent mechanical strength under a static condition after reaching a target leaking layer, plugs the stratum, and has good viscoelasticity and expansibility and good plugging performance.
2. The thixotropic self-healing gel plugging agent has good water dilution resistance.
3. The thixotropic self-healing gel plugging agent disclosed by the invention forms a dynamic network with a supermolecular structure by virtue of non-covalent actions such as an electrostatic action, a hydrogen bond action, a hydrophobic action and the like, can be reversibly opened under a shearing action, realizes self-healing on a target leaking layer, and plugs a leaking stratum in time, so that the plugging time is effectively saved, and the effect is good.
4. The thixotropic self-healing gel plugging agent has excellent compatibility with drilling fluid, is simple to prepare and is suitable for mass production.
5. The thixotropic self-healing gel plugging agent can adjust the particle size according to the characteristics of a leakage layer, and has wide applicability.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
In some more specific embodiments, the thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight:
20-30 parts of acrylamide, 0.05-0.1 part of hydroxyethyl methacrylate, 10-15 parts of zwitterionic monomer, 1.5-2 parts of first hydrophobic monomer, 0.5-1 part of second hydrophobic monomer, 0.05-0.5 part of initiator and 1-3 parts of dispersant.
Wherein the zwitterionic monomer is sulfobetaine acrylamide;
the first hydrophobic monomer is one or the combination of more than two of lauryl acrylate, lauryl fluoroheptyl methacrylate, lauryl fluoroheptyl acrylate and tridecyl octyl acrylate;
the second hydrophobic monomer is one or the combination of more than two of styrene, 1-vinyl imidazole and 1- (4-vinyl benzyl) -1H-imidazole;
the initiator is one of azodiisobutyronitrile, azodiisoheptonitrile, azodiisovaleronitrile, azodiisocyclohexylcarbonitrile, dimethyl azodiisobutyrate, benzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide and methyl ethyl ketone peroxide;
the dispersing agent is a combination of one of calcium carbonate, nano-silica and talcum powder and one or two of polyvinyl alcohol and hydroxypropyl methyl cellulose, and the mass ratio of the dispersing agent is (5-10): 1.
wherein, the sulfobetaine acrylamide is one or the combination of two of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt.
The raw materials also comprise deionized water and a pH regulator, wherein the addition amount of the deionized water is 100 parts by weight; the pH regulator is sodium hydroxide solution with the concentration of 10-20%, and the pH value of the solution after regulation is 5.0-8.0.
The preparation method of the thixotropic self-healing gel plugging agent comprises the following steps:
(1) adding acrylamide, hydroxyethyl methacrylate and a zwitterionic monomer into deionized water according to the proportion, and uniformly stirring; adding a pH regulator to regulate the pH value of the solution; adding a dispersing agent, and uniformly stirring to form an aqueous phase solution A;
(2) adding a second hydrophobic monomer and an initiator into the first hydrophobic monomer, and uniformly stirring to form an organic phase solution B;
(3) placing the phase solution A obtained in the step (1) in a water bath kettle, controlling the temperature to be 60-75 ℃, introducing nitrogen for 15-30min, dropwise adding the organic phase solution B obtained in the step (2) into the aqueous phase solution A at the stirring speed of 800r/min, and continuously stirring for 2-3h after the addition is finished to form a solution C;
(4) preserving the heat of the solution C obtained in the step (3), and standing to obtain a thixotropic self-healing gel base material;
(5) and (5) drying and crushing the thixotropic self-healing gel base material obtained in the step (4) to obtain the thixotropic self-healing gel plugging agent.
Wherein, in a more specific embodiment, in the step (5), the heat preservation time is 10-12h, and the heat preservation temperature is 75-80 ℃.
In the step (5), the drying is specifically drying for 20-24h at 55-70 ℃ under vacuum condition.
The technical solution of the present invention will be described in further detail below with reference to examples. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
The raw materials used in the examples are conventional commercially available materials, and the particle size of the nanosilica raw material is 1-100 nm.
In the following examples 1 part by weight represents 1 kg.
Example 1
A thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight: 100 parts of deionized water, 20 parts of acrylamide, 0.05 part of hydroxyethyl methacrylate, 15 parts of a zwitterionic monomer, 1.5 parts of a first hydrophobic monomer, 1 part of a second hydrophobic monomer, 0.1 part of an initiator, 1.2 parts of a dispersant and a proper amount of a 10% sodium hydroxide aqueous solution.
The zwitterionic monomer is [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide; the first hydrophobic monomer is dodecafluoroheptyl methacrylate; the second hydrophobic monomer is 1-vinyl imidazole; the initiator is azobisisobutyronitrile; the dispersing agent is a combination of two raw materials of calcium carbonate and polyvinyl alcohol, and the mass ratio of the two raw materials of calcium carbonate to polyvinyl alcohol is 5: 1; the polyvinyl alcohol is a polyvinyl alcohol 1788 type.
The preparation method of the thixotropic self-healing gel plugging agent comprises the following steps: weighing the raw materials according to the weight ratio, adding acrylamide, hydroxyethyl methacrylate and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide into deionized water, uniformly stirring, adding 10% sodium hydroxide aqueous solution to adjust the pH value to 5.0-8.0, adding 17880.2 parts of calcium carbonate and polyvinyl alcohol, and uniformly stirring to obtain an aqueous phase solution A; adding 1-vinyl imidazole and azobisisobutyronitrile into the methacrylic acid dodecafluoroheptyl ester, and uniformly stirring to obtain an organic phase solution B; thirdly, placing the aqueous phase solution A in a water bath, controlling the temperature to 60 ℃, introducing nitrogen for 15min, dropwise adding the organic phase solution B into the aqueous phase solution A at the stirring speed of 500r/min, and continuously stirring for 3h after the addition is finished to obtain a solution C; fourthly, keeping the temperature of the solution C at 75 ℃ for 10 hours to obtain a thixotropic self-healing gel base material; fifthly, drying the thixotropic self-healing gel base material for 20 hours at 55 ℃ under vacuum condition, crushing and sieving to obtain the thixotropic self-healing gel plugging agent with the particle size of 20 meshes.
Example 2
A thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight: 100 parts of deionized water, 30 parts of acrylamide, 0.1 part of hydroxyethyl methacrylate, 12 parts of a zwitterionic monomer, 2 parts of a first hydrophobic monomer, 0.5 part of a second hydrophobic monomer, 0.3 part of an initiator, 3 parts of a dispersant and a proper amount of a 10% sodium hydroxide aqueous solution;
the zwitterionic monomer is [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt; the first hydrophobic monomer is a combination of two raw materials of dodecafluoroheptyl acrylate and tridecafluorooctyl acrylate, and the mass ratio of the dodecafluoroheptyl acrylate to the tridecafluorooctyl acrylate is 1: 1; the second hydrophobic monomer is 1- (4-vinyl benzyl) -1H-imidazole; the initiator is benzoyl peroxide; the dispersing agent is a combination of two raw materials of nano silicon dioxide and hydroxypropyl methyl cellulose, and the mass ratio of the two raw materials of nano silicon dioxide to hydroxypropyl methyl cellulose is 10: 1; the particle size of the nano silicon dioxide is 30 nm;
the preparation method of the thixotropic self-healing gel plugging agent is as described in example 1.
Example 3
A thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight: 100 parts of deionized water, 25 parts of acrylamide, 0.06 part of hydroxyethyl methacrylate, 10 parts of a zwitterionic monomer, 1.8 parts of a first hydrophobic monomer, 0.7 part of a second hydrophobic monomer, 0.1 part of an initiator, 2 parts of a dispersant and a proper amount of a 20% sodium hydroxide aqueous solution;
the zwitterionic monomer is a combination of two raw materials of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt, wherein the mass ratio of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide to the [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt is 1: 1; the first hydrophobic monomer is a combination of two raw materials, namely lauryl acrylate and dodecafluoroheptyl methacrylate, wherein the mass ratio of the lauryl acrylate to the dodecafluoroheptyl methacrylate is 2: 1; the second hydrophobic monomer is a combination of two raw materials of styrene and 1- (4-vinyl benzyl) -1H-imidazole, and the mass ratio of the styrene to the 1- (4-vinyl benzyl) -1H-imidazole is 1: 1; the initiator is hydrogen peroxide diisopropylbenzene; the dispersing agent is a combination of two raw materials of talcum powder and polyvinyl alcohol, and the mass ratio of the two raw materials of calcium carbonate and polyvinyl alcohol is 8: 1; the polyvinyl alcohol is a polyvinyl alcohol 1788 type.
The preparation method of the thixotropic self-healing gel plugging agent is described in example 1.
Example 4
A thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight: 100 parts of deionized water, 28 parts of acrylamide, 0.1 part of hydroxyethyl methacrylate, 12 parts of a zwitterionic monomer, 2 parts of a first hydrophobic monomer, 1 part of a second hydrophobic monomer, 0.3 part of an initiator, 1.5 parts of a dispersant and a proper amount of 15% sodium hydroxide aqueous solution.
The zwitterionic monomer is a combination of two raw materials of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt, wherein the mass ratio of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide to the [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt is 2: 1; the first hydrophobic monomer is tridecafluorooctyl acrylate; the second hydrophobic monomer is a combination of two raw materials of styrene and 1-vinyl imidazole, and the mass ratio of the styrene to the 1-vinyl imidazole is 1.5: 1; the initiator is hydrogen peroxide diisopropylbenzene; the dispersing agent is a combination of calcium carbonate, polyvinyl alcohol and hydroxypropyl methyl cellulose, and the mass ratio of the calcium carbonate to the polyvinyl alcohol to the hydroxypropyl methyl cellulose is 8: 0.5: 0.5; the polyvinyl alcohol is polyvinyl alcohol 1788 type.
The preparation method of the thixotropic self-healing gel plugging agent is as described in example 1.
Example 5
A thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight: 100 parts of deionized water, 25 parts of acrylamide, 0.1 part of hydroxyethyl methacrylate, 15 parts of a zwitterionic monomer, 1.8 parts of a first hydrophobic monomer, 0.8 part of a second hydrophobic monomer, 0.2 part of an initiator, 2.5 parts of a dispersant and a proper amount of a 10% sodium hydroxide aqueous solution;
the zwitterionic monomer is [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt; the first hydrophobic monomer is a combination of two raw materials of dodecafluoroheptyl methacrylate and tridecafluorooctyl acrylate, and the mass ratio of the dodecafluoroheptyl methacrylate to the tridecafluorooctyl acrylate is 2: 1; the second hydrophobic monomer is 1- (4-vinyl benzyl) -1H-imidazole; the initiator is methyl ethyl ketone peroxide; the dispersing agent is a combination of two raw materials of calcium carbonate and hydroxypropyl methyl cellulose, and the mass ratio of the two raw materials of calcium carbonate and hydroxypropyl methyl cellulose is 8: 1;
the preparation method of the thixotropic self-healing gel plugging agent is as described in example 1.
Example 6
A thixotropic self-healing gel plugging agent is prepared from the following raw materials in parts by weight: 100 parts of deionized water, 30 parts of acrylamide, 0.1 part of hydroxyethyl methacrylate, 12 parts of a zwitterionic monomer, 2 parts of a first hydrophobic monomer, 1 part of a second hydrophobic monomer, 0.5 part of an initiator, 3 parts of a dispersant and a proper amount of a 20% sodium hydroxide aqueous solution;
the zwitterionic monomer is a combination of two raw materials of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt, wherein the mass ratio of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide to the [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt is 1: 3; the first hydrophobic monomer is lauryl acrylate; the second hydrophobic monomer is a combination of two raw materials, namely 1-vinyl imidazole and 1- (4-vinyl benzyl) -1H-imidazole, and the mass ratio of the 1-vinyl imidazole to the 1- (4-vinyl benzyl) -1H-imidazole is 1: 2; the initiator is azobisisobutyronitrile; the dispersing agent is a combination of two raw materials of nano silicon dioxide and polyvinyl alcohol, and the mass ratio of the two raw materials of nano silicon dioxide to polyvinyl alcohol is 10: 1; the particle size of the nano silicon dioxide is 50 nm; the polyvinyl alcohol is a polyvinyl alcohol 1788 type.
The preparation method of the thixotropic self-healing gel plugging agent is as described in example 1.
Comparative example 1
A plugging agent was obtained by using the same raw materials and preparation method as in example 1, except that hydroxyethyl methacrylate was not added.
Comparative example 2
A plugging agent was obtained by using the same raw materials and preparation methods as in example 1, except that a zwitterionic monomer was not added.
Comparative example 3
A plugging agent was obtained using the same raw materials and preparation method as in example 1, except that the first hydrophobic monomer was not added.
Comparative example 4
A plugging agent was obtained using the same raw materials and preparation method as in example 1, except that the second hydrophobic monomer was not added.
Comparative example 5
A plugging agent was obtained by using the same raw materials and preparation methods as those of example 1, except that no dispersant was added.
The following are the experimental part of the invention:
test 1 thixotropic property test of thixotropic self-healing gel plugging agent
The test method comprises the following steps:
(1) adding 10 parts by weight of the prepared thixotropic self-healing gel plugging agent into 100 parts by weight of water, standing for 4 hours at 100 ℃ to self-heal into an integral gel system;
(2) taking 10 parts by weight of the gel system in the step (1), and shearing at a rotating speed of 600r/min by using a high-speed stirrer (the shearing speed is more suitable for a drilling rod in an actual stratum), wherein the shearing time is 30 min;
(3) placing the gel stirred in the step (2) in a thermostat at 100 ℃ and standing;
(3) the gel viscosities at 0h, 1h, 2h, 3h and 4h at rest were measured using a DNJ-5S rotary viscometer in an automatic measurement mode.
The gel viscosity at different times of standing is shown in table 1.
TABLE 1 comparison of viscosity with standing time for each example and comparative example
As can be seen from Table 1, the gel of the present invention has the advantages of destroyed formed supermolecule network under the shearing action, small viscosity and good fluidity, and when the gel is kept still, the system forms the supermolecule network again by the ion action, the hydrophobic action, the hydrogen bond action, etc., and the viscosity is gradually increased. The tests show that the thixotropic self-healing gel particles have good thixotropy, have small viscosity and high fluidity under the action of shearing force after entering the stratum while drilling, are convenient for the gel plugging agent to migrate in the stratum, form integral gel under the static condition of a target leaking layer, have high viscosity and plug the stratum. The method comprises the following steps of (1) not adding hydroxyethyl methacrylate in comparative example 1, influencing the formation of partial hydrogen bonds and limiting the increase of gel viscosity, adding a zwitterionic monomer and a first hydrophobic monomer in comparative example 2 and comparative example 3, so that gel particles cannot form a supermolecular network structure, and limiting the performance of gel, which shows that the zwitterionic monomer and the first hydrophobic monomer are important in the formation of supermolecular gel, adding a second hydrophobic monomer in comparative example 4, so that the viscosity of a gel system is lower than that in the examples (the effect of the second hydrophobic monomer is mainly shown in the aspect of improving gel strength), adding no dispersant in comparative example 5, influencing the uniform dispersion of the hydrophobic monomer, so that the performance is poor, and showing that the dispersion of the monomer is important for the formation of the hydrophobic network structure.
Test 2 thixotropic self-healing gel plugging agent water dilution resistance test
The test method comprises the following steps:
(1) adding 30 parts by weight of the prepared thixotropic self-healing gel plugging agent into 300 parts by weight of water, standing at 100 ℃ for 4 hours, and self-healing into an integral gel system;
(2) taking 3 parts of 10 parts by weight of the gel system in the step (1), adding 30 parts by weight of water into one part of the gel system for dilution, and adding 20 parts by weight of water into the other part of the gel system for dilution; the last portion was taken as a control without water;
(3) placing the three parts of the diluent in the step (2) in a constant temperature box at 100 ℃ for standing for 4 hours;
(4) then, using a DNJ-5S rotary viscometer to dilute the viscosity of the sample before and after the sample is diluted in an automatic measurement mode;
the gel viscosities before and after dilution of each example and comparative example are shown in table 2.
TABLE 2 comparison of viscosity before and after dilution for each example and comparative example
As can be seen from Table 2, the viscosity of the thixotropic self-healing gel of the invention is always kept above 78000mPa · s under the dilution effect of water and is almost kept unchanged, which shows that the gel of the invention has strong water-resistant dilution capability, and the strength and the gelling effect are still good under the dilution effect of water. In comparative example 1, hydroxyethyl methacrylate was not added, resulting in poor resistance of the gel particles to water dilution; in comparative examples 2 and 3, the zwitterionic monomer and the first hydrophobic monomer are not added, the lack of ionic action and hydrophobic association action causes the initial viscosity of a gel network structure to be very high and the gel network structure to be easily diluted by water, comparative examples 2 and 3 illustrate that the zwitterionic monomer and the first hydrophobic monomer are very important for the viscosity and the water dilution resistance of the gel, comparative example 4 does not add the second hydrophobic monomer, the water dilution resistance of the gel is influenced (the action of the second hydrophobic monomer is mainly shown in the aspect of improving the gel strength), and comparative example 5 does not add the dispersing agent, the hydrophobic monomer cannot be uniformly dispersed, the reaction process with the hydrophilic monomer is influenced, and the gel material has the water dilution resistance but has the lower gel viscosity.
Experiment 3 thixotropic self-healing gel plugging agent thixotropic self-healing effect test
The test method comprises the following steps:
(1) adding 100 parts by weight of water into 10 parts by weight of the prepared thixotropic self-healing gel plugging agent, standing at 100 ℃ for 4 hours, and self-healing into an integral gel system;
(2) cutting the gel system prepared in the step (1) into two cuboid block-shaped samples with the length of 2cm, the width of 1cm and the height of 3 cm;
(3) a rectangular block in the step (2) with the length of 2cm, the width of 1cm and the height of 3cmThe length l of the bulk sample stretched to fracture at room temperature was measured using a WDW-20 electronic universal tester1；
(4) Adding another cuboid block sample with the length of 2cm, the width of 1cm and the height of 3cm in the step (2) into a stirring cup, stirring for 30min at 15000r/min, stopping stirring, standing for 4h at 100 ℃, and self-healing again to form an integral gel system;
(5) cutting the gel system prepared in the step (4) into cuboid block-shaped samples with the length of 2cm, the width of 1cm and the height of 3cm, and measuring the length l of the samples stretched to be broken at room temperature by using a WDW-20 electronic universal tester again2；
Calculating the thixotropic self-healing rate theta of the thixotropic self-healing gel plugging agent by using the following formula:
thixotropic self-healing rate: theta ═ l2/l1*100％
The thixotropic self-healing plugging agent prepared in each example had the thixotropic self-healing rate test results shown in table 3.
Experiment 4 test of sealing pressure-bearing strength of thixotropic self-healing gel plugging agent while drilling
(1) Preparing a drilling fluid base slurry containing thixotropic self-healing gel plugging agent particles: slowly adding 4 parts of bentonite into 100 parts of distilled water stirred at 2000r/min, continuously stirring for 2 hours, stopping stirring, and sealing and maintaining for 24 hours to obtain drilling fluid base slurry; dispersing 10 parts by weight of thixotropic self-healing gel particles into 100 parts by weight of drilling fluid base slurry to obtain drilling fluid base slurry containing the thixotropic self-healing gel particles;
(2) maximum bearing strength test a: stirring the drilling fluid base slurry containing the thixotropic self-healing gel particles for 30min at a stirring speed of 2000r/min, pouring the drilling fluid base slurry into a slurry tank of a DLY-4 type high-temperature high-pressure static dynamic leak stoppage instrument, heating to 100 ℃ at a rotating speed of 300r/min, stopping stirring, wherein the fixed pressure is 0.4Mpa, the drilling fluid base slurry containing the thixotropic self-healing gel particles passes through a crack model with the crack width of 0.1mm, the outlet leakage is large when the gel is not healed, and the gel particles can be considered to block the crack when the outlet leakage slowly decreases to be unchanged; after healing for 4 hours at 100 ℃, slowly increasing the pressure of the leak stoppage instrument until leakage loss occurs, wherein the corresponding pressure is the mostLarge plugging bearing strength tauaThe test results are shown in Table 1.
(3) Maximum bearing strength test b: stirring the drilling fluid base slurry containing the thixotropic self-healing gel particles for 30min at a stirring speed of 2000r/min, pouring the drilling fluid base slurry into a slurry tank of a DLY-4 type high-temperature high-pressure static dynamic leak stoppage instrument, heating to 100 ℃ at a rotating speed of 300r/min, stopping stirring, wherein the fixed pressure is 0.4Mpa, the drilling fluid base slurry containing the thixotropic self-healing gel particles passes through a crack model with the crack width of 3mm, the outlet leakage is large when the gel is not healed, and the gel particles can be considered to block the crack when the outlet leakage slowly decreases to be unchanged; after healing for 4 hours at 100 ℃, slowly increasing the pressure of the leak stoppage instrument until leakage occurs, wherein the corresponding pressure is the maximum plugging pressure-bearing strength taubThe test results are shown in Table 3.
TABLE 3 test results of the performance of thixotropic self-healing gel plugging agent prepared in each example
As can be seen from Table 3, the thixotropic self-healing gel particles have a thixotropic self-healing rate of more than 88%, a maximum plugging pressure-bearing capacity at 100 ℃ for 0.1mm cracks of more than 5MPa, and a maximum plugging pressure-bearing capacity for 3mm cracks of more than 7MPa, and the tests show that the thixotropic self-healing gel particles have good thixotropic self-healing capacity and plugging pressure-bearing capacity. In the comparative example 1, hydroxyethyl methacrylate is not added, so that the formation of partial hydrogen bond is limited, and the self-healing capability and the pressure-bearing strength of the gel are influenced; compared with the prior art, the gel network structure has the advantages that a first hydrophobic monomer is not added in the comparative example 3, so that the self-healing capacity of the formed gel is very weak, and the pressure-bearing strength is very poor; comparative examples 2 and 3 illustrate that the zwitterionic monomer and the first hydrophobic monomer are critical to the self-healing capability of the gel, comparative example 4 does not add the second hydrophobic monomer, which results in lack of a rigid support structure in the gel and limits the bearing strength of the gel, and comparative example 5 does not add a dispersing agent, which affects the dispersion of the hydrophobic monomer, which results in weakening the performance of the gel, which illustrates the importance of the dispersion of the hydrophobic monomer to the network structure of the gel.
The tests show that the thixotropic self-healing gel plugging agent prepared by the invention has good thixotropy and water dilution resistance, has good fluidity under the pumping condition, can form integral gel with high viscosity when reaching a leaking stratum, is difficult to dilute by water, has strong thixotropic self-healing capability, large mechanical strength and strong plugging and pressure-bearing capability, and has good plugging capability in different cracks. In the using process, pumping conditions can be fully utilized to enter a target leakage stratum while drilling to effectively plug cracks, and the controllability of the gel plugging process is improved.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. The thixotropic self-healing gel plugging agent is characterized by comprising the following raw materials in parts by weight:
20-30 parts of acrylamide, 0.05-0.1 part of hydroxyethyl methacrylate, 10-15 parts of zwitterionic monomer, 1.5-2 parts of first hydrophobic monomer, 0.5-1 part of second hydrophobic monomer, 0.05-0.5 part of initiator and 1-3 parts of dispersant.
2. The thixotropic self-healing gel lost circulation agent of claim 1, wherein the zwitterionic monomer is sulfobetaine acrylamide;
the first hydrophobic monomer is one or the combination of more than two of lauryl acrylate, lauryl fluoroheptyl methacrylate, lauryl fluoroheptyl acrylate and tridecyl octyl acrylate;
the second hydrophobic monomer is one or the combination of more than two of styrene, 1-vinyl imidazole and 1- (4-vinyl benzyl) -1H-imidazole;
the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobiscyclohexyl carbonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide and methyl ethyl ketone peroxide;
the dispersing agent is a mixture of an inorganic dispersing agent and an organic dispersing agent, the inorganic dispersing agent is one of calcium carbonate, nano silicon dioxide and talcum powder, the organic dispersing agent is one or a mixture of polyvinyl alcohol and hydroxypropyl methyl cellulose, and the adding amount ratio of the inorganic dispersing agent to the organic dispersing agent is (5-10): 1.
3. the thixotropic self-healing gel plugging agent of claim 2, wherein the sulfobetaine acrylamide is one or a combination of two of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt.
4. The thixotropic self-healing gel plugging agent according to claim 1, wherein the raw materials further comprise deionized water and a pH regulator, and the amount of the deionized water is 100 parts by weight; the pH regulator is sodium hydroxide solution with the concentration of 10-20%.
5. A method of preparing the thixotropic self-healing gel lost circulation agent of any one of claims 1 to 4, comprising the steps of:
(1) adding acrylamide, hydroxyethyl methacrylate and a zwitterionic monomer into deionized water according to the proportion, uniformly stirring and adjusting the pH value of the solution; adding a dispersing agent, and uniformly stirring to form an aqueous phase solution A;
(2) adding a second hydrophobic monomer and an initiator into the first hydrophobic monomer, and uniformly stirring to form an organic phase solution B;
(3) placing the phase solution A obtained in the step (1) in a water bath kettle, controlling the temperature to be 60-75 ℃, introducing nitrogen for 15-30min, dropwise adding the organic phase solution B obtained in the step (2) into the aqueous phase solution A at the stirring speed of 800r/min, and continuously stirring for 2-3h after the addition is finished to form a solution C;
(4) keeping the temperature of the solution C obtained in the step (3) and standing to obtain a thixotropic self-healing gel base material;
(5) and (4) drying and crushing the thixotropic self-healing gel base material obtained in the step (4) to obtain the thixotropic self-healing gel plugging agent.
6. The preparation method of the thixotropic self-healing gel plugging agent according to claim 5, wherein a pH regulator is added to adjust the pH value of the solution to 5.0-8.0; in the step (4), the heat preservation time is 10-12h, and the heat preservation temperature is 75-80 ℃.
7. The preparation method of the thixotropic self-healing gel plugging agent according to claim 5, wherein in the step (5), the drying is specifically drying for 20 to 24 hours at a temperature of 55 to 70 ℃ under vacuum.
8. The application of the thixotropic self-healing gel plugging agent is characterized in that the thixotropic self-healing gel plugging agent is dispersed in drilling fluid in a particle form and enters a target stratum while drilling.
9. The application of the thixotropic self-healing gel plugging agent according to claim 5, wherein the addition amount of the plugging agent particles is 1-3.5% of the mass of the drilling fluid.
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| CN117736705A (en) * | 2024-02-20 | 2024-03-22 | 中国石油大学(华东) | Self-healing resin plugging agent while drilling as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10647902B1 (en) * | 2019-01-14 | 2020-05-12 | China University Of Petroleum (East China) | Temporary plugging agent for drilling fluid and preparation method thereof, and water-based drilling fluid and use thereof |
| CN113501910A (en) * | 2021-09-09 | 2021-10-15 | 中国石油大学(华东) | Non-covalent-bond synergistic self-healing gel plugging agent and preparation method and application thereof |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10647902B1 (en) * | 2019-01-14 | 2020-05-12 | China University Of Petroleum (East China) | Temporary plugging agent for drilling fluid and preparation method thereof, and water-based drilling fluid and use thereof |
| CN113501910A (en) * | 2021-09-09 | 2021-10-15 | 中国石油大学(华东) | Non-covalent-bond synergistic self-healing gel plugging agent and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 沙勇等: "含磺基甜菜碱基团聚丙烯酰胺的合成及其溶液性质", 《天津大学学报(自然科学与工程技术版》 * |
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| CN117736705A (en) * | 2024-02-20 | 2024-03-22 | 中国石油大学(华东) | Self-healing resin plugging agent while drilling as well as preparation method and application thereof |
| CN117736705B (en) * | 2024-02-20 | 2024-05-03 | 中国石油大学(华东) | Self-healing resin plugging agent while drilling as well as preparation method and application thereof |
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