Resin type leakage control agent for CO2 geological sequestration leakage as well as preparation method and application of resin type leakage control agent

Abstract

The invention discloses a CO2 geological sequestration leakage resin type leakage control agent and a preparation method and application thereof, and relates to the technical field of carbon dioxide capture, utilization and sequestration. The composite material comprises the following raw materials in parts by weight: 85-105 parts of thermosetting organic silicon resin, 30-45 parts of an anhydride curing agent, 7-10 parts of a catalytic heat stabilizer, 0.5-3 parts of a silane coupling agent and 0.2-2 parts of an inorganic nano material. The preparation method comprises the following steps: primary dispersion: mixing and dispersing the thermosetting organic silicon resin, the silane coupling agent and the inorganic nano-material in an ultrasonic reactor at room temperature to obtain a premixed system; catalytic modification: heating the premixed system to 80-110 DEG C, reducing the viscosity, adding a thermocatalytic stabilizer, and performing ultrasonic stirring until the mixture is completely homogenized; and finally mixing and curing: after the system is cooled to 25-30 DEG C, adding an anhydride curing agent, stirring and mixing, so that the plugging agent is used for plugging the microcracks of the cover layer in the CO2 geological sequestration, is rapidly cured under the formation temperature condition, and has good formation adaptability and long-term stability.

Description

Technical Field

[0001] This invention relates to the field of carbon dioxide capture, utilization and storage technology, and in particular to a CO2 geological storage leakage control resin-type leak control agent, its preparation method and application. Background Technology

[0002] With the rapid development of global carbon capture, utilization, and storage (CCUS) technologies, CO2 geological storage has become a key means to achieve carbon neutrality. However, during the storage process, caprock (such as shale, mudstone, or salt rock layers) may leak CO2 due to changes in geological stress, chemical corrosion, or the expansion of existing fractures, leading to storage failure and environmental risks. Therefore, developing efficient, stable, and adaptable leak-sealing materials is of significant engineering importance.

[0003] Currently, the sealing technologies for CO2 leaks mainly include the following categories: (1) Cement-based materials: Traditional cement slurry or modified cement is widely used for well plugging, but it is prone to carbonization reaction in acidic CO2 environment, resulting in decreased strength, increased permeability, and insufficient long-term stability; (2) Gel system: Polymer gels (such as polyacrylamide) can be injected and expanded to plug pores, but its temperature resistance is poor (usually below 80℃), and it is prone to dehydration shrinkage or chemical degradation in high-pressure CO2 environment; (3) Resin materials: Epoxy resin or polyurethane resin is tried to be used for crack plugging due to its strong adhesion, but its curing conditions are harsh (temperature and humidity need to be precisely controlled), its compatibility with rock interface is poor, and some materials are prone to swelling failure in CO2 saturated water environment.

[0004] Organosilicon resins have potential advantages in high-temperature and high-pressure sealing scenarios due to their excellent high-temperature resistance (withstanding temperatures above 200°C), chemical inertness (stable against CO2 and acidic media), and high bonding strength. However, the direct use of conventional organosilicon resins for CO2 leak sealing still has the following problems: (1) contradiction between speed and permeability: although low-viscosity resins can be injected into microcracks, the curing time is too long, making it difficult to quickly form an effective seal; high-viscosity resins cannot penetrate deep into small pores; (2) brittleness: the resin is brittle after curing and is prone to secondary cracks under stress fluctuations in the caprock; (3) insufficient environmental adaptability: the performance has not been optimized for high CO2 partial pressure, formation water salinity, and multiphase flow conditions in geological storage environments; (4) therefore, it is urgent to develop an organosilicon resin-based CO2 leak control agent that combines rapid curing, high permeability, strong interfacial bonding, and long-term stability to improve sealing efficiency and ensure the safety of the storage system. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art or related art.

[0006] Therefore, in a first aspect, the present invention provides a CO2 geological storage leakage control resin-type leak control agent, the raw material composition of which, by weight, includes: 85-105 parts of thermosetting organosilicon resin, 30-45 parts of acid anhydride curing agent, 7-10 parts of catalytic heat stabilizer, 0.5-3 parts of silane coupling agent, and 0.2-2 parts of inorganic nanomaterials.

[0007] Furthermore, the thermosetting silicone resin includes solid silicone resin and / or high-temperature silicone resin.

[0008] Furthermore, the anhydride curing agent is at least one of trimellitic anhydride, pyromellitic anhydride, and dichloromaleic anhydride.

[0009] Furthermore, the catalytic heat stabilizer is at least one of stearoylbenzoylmethane, zinc acetylacetonate, and stannous octoate.

[0010] Furthermore, the silane coupling agent is at least one of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0011] Furthermore, the inorganic nanomaterial is at least one of alumina powder, iron oxide powder, nano silica powder, and copper oxide powder, and the average particle size of the inorganic nanomaterial powder is between 10 nm and 250 nm.

[0012] A second aspect of the present invention provides a method for preparing a resin-type leak control agent for CO2 geological storage, the method comprising:

[0013] Raw material ratio: Take the raw materials according to the above-mentioned parts by weight of CO2 geological storage leakage resin-type leakage control agent;

[0014] Primary dispersion: The thermosetting organosilicon resin, the silane coupling agent, and the inorganic nanomaterials are mixed and dispersed in an ultrasonic reactor at room temperature until a uniform premixed system is formed.

[0015] Catalytic modification: After heating the premixed system to 80℃-110℃ to reduce the viscosity, the thermal catalytic stabilizer is added and ultrasonically stirred until completely homogenized;

[0016] Final mixing and curing: After the system cools to 25℃-30℃, add the acid anhydride curing agent and stir to mix, finally obtaining the resin-type leakage control agent.

[0017] A third aspect of the present invention provides an application of a resin-type leakage control agent for CO2 geological storage, wherein the aforementioned resin-type leakage control agent is used for sealing microcracks in the caprock during CO2 geological storage.

[0018] Furthermore, the sealing method includes: injecting the resin-based leak control agent into the formation fissure and allowing it to cool and solidify naturally.

[0019] Furthermore, the width of the formation microfractures is 0.1 μm-150 μm.

[0020] Compared with the prior art, the present invention has at least the following beneficial effects:

[0021] This invention provides a CO2 geological storage leakage control agent, a silicone resin-based composite sealing material designed for efficient sealing of micro-fractures in formations during CO2 geological storage. The material uses high-temperature resistant and corrosion-resistant organosilicon resin as the matrix, incorporating inorganic nanomaterials as an inorganic reinforcing phase. These nanomaterials have small particle sizes and large specific surface areas, effectively filling the micropores in the resin, improving its viscosity and sealing performance, and enhancing the hardness and wear resistance of the cured resin. Simultaneously, a silane coupling agent is introduced as an interface modifier, effectively improving the dispersibility and interfacial adhesion of the composite system by constructing a stable chemical bond interface between the nanoparticles and the silicone resin. This CO2 geological storage leakage control agent exhibits good fluidity at room temperature, penetrating fractures less than 150 μm wide. It rapidly cures under formation temperature conditions (80℃-120℃), forming a dense, flexible, and somewhat elastic three-dimensional network structure. Attached Figure Description

[0022] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of this application.

[0023] Figure 1 The graph shows the thermal conductivity of the samples prepared in the embodiments and comparative examples of this invention.

[0024] Figure 2 The diagram shows the compressive strength of the samples prepared in the embodiments and comparative examples of this invention.

[0025] Figure 3 An evaluation device for the sealing and cross-contamination effect of resin-type leakage control agents provided in an embodiment of the present invention; wherein, 1, beaker; 2, pressure gauge; 3, hand pump; 4, core holder; 5, gas flow meter; 6, gas drying device; 7, valve; 8, gas cylinder.

[0026] Figure 4 The compressive strength curve of the resin-type leakage control agent after coagulation provided in Example 1 of the present invention.

[0027] Figure 5The compressive strength curve of the resin-type leakage control agent after coagulation provided in Example 1 of the present invention. Detailed Implementation

[0028] To better understand the above technical solutions, the technical solutions of the embodiments of this application will be described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the embodiments of this application and the specific features in the embodiments are detailed descriptions of the technical solutions of the embodiments of this application, rather than limitations on the technical solutions of this application. In the absence of conflict, the embodiments of this application and the technical features in the embodiments can be combined with each other.

[0029] In a first aspect, the present invention provides a CO2 geological storage leakage control resin-type leak control agent, the raw material composition of which includes, by weight: 85-105 parts of thermosetting organosilicon resin, 30-45 parts of acid anhydride curing agent, 7-10 parts of catalytic heat stabilizer, 0.5-3 parts of silane coupling agent, and 0.2-2 parts of inorganic nanomaterials.

[0030] It is understandable that existing CO2 sealing materials generally suffer from key defects such as insufficient acid resistance, poor environmental adaptability, and low long-term stability. In high-pressure acidic CO2 environments, they are prone to carbonization, degradation, or swelling, leading to deterioration of mechanical properties. Furthermore, they are limited by harsh curing conditions, poor interfacial bonding, and a narrow temperature and pressure application range, making it difficult to meet the dual requirements of material durability and construction feasibility for geological sealing, severely restricting the safety and reliability of CO2 sealing technology. The CO2 geological sealing leakage control resin provided in this invention uses high-temperature resistant and corrosion-resistant organosilicon resin as the matrix, and adds inorganic nanomaterials as the inorganic reinforcing phase. These nanomaterials have small particle size and large specific surface area, effectively filling the micropores in the resin, improving the resin's viscosity and sealing performance, and also enhancing the hardness and wear resistance of the cured resin. Simultaneously, a silane coupling agent is introduced as an interfacial modifier, effectively improving the dispersibility and interfacial adhesion of the composite system by constructing a stable chemical bond interface between the inorganic nanoparticles and the silicone resin.

[0031] The CO2 geological storage leakage control agent provided in this invention is a thermosetting organosilicon resin repair composite material. After the composite material cures, even if microcracks reappear in the caprock, the inorganic nanoparticles in the composite material significantly enhance its thermal conductivity due to their high thermal conductivity, allowing the material to be rapidly heated within 1.5 hours. Under heating conditions, the dynamic ester bonds within the material can break and reshape according to the crack shape to form new ester bonds, thereby achieving self-healing function under high-temperature environments. Furthermore, this composite material also possesses advantages such as low viscosity, high toughness, high strength, and automatic formation curing. Its excellent comprehensive performance makes it promising for applications in CO2 geological storage crack repair and other fields.

[0032] In some embodiments, thermosetting silicone resins include solid silicone resins and / or high-temperature silicone resins.

[0033] Specifically, thermosetting silicone resins undergo irreversible cross-linking and curing through heating or catalysis. Compared to conventional phenolic resins, solid silicone resins and high-temperature silicone resins can cure rapidly at lower temperatures and withstand long-term thermal shock; moreover, this resin material has higher strength and better sealing performance.

[0034] In some embodiments, the anhydride curing agent is at least one of trimellitic anhydride, pyromellitic anhydride, and dichloromaleic anhydride.

[0035] Specifically, acid anhydride curing agents can transform linear polymer compounds into insoluble and infusible three-dimensional structures. These three acid anhydride curing agents achieve medium- and low-temperature, low-stress curing of resins through ring-opening esterification reactions, forming a three-dimensional network dominated by ester bonds, and giving it ultra-low shrinkage and temperature resistance after cooling.

[0036] In some embodiments, the catalytic heat stabilizer is at least one of stearoylbenzoylmethane, zinc acetylacetonate, and stannous octoate.

[0037] Specifically, catalytic heat stabilizers reduce the curing activation energy, enabling the resin to form a dense three-dimensional network at a lower temperature or in a shorter time, thereby reducing oxidative cracking caused by prolonged exposure to high temperatures.

[0038] In some embodiments, the silane coupling agent is at least one of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane.

[0039] Specifically, the aforementioned silane coupling agent, through its amphiphilic structure (the inorganic end hydrolyzes to form silanol groups that bond to the filler surface, while the organic end active groups react with the resin), constructs a stable chemical bridge between the phenolic resin and the inorganic filler / reinforcement, significantly improving the interfacial bonding strength and water resistance. At the same time, it improves the filler dispersion and regulates the curing process, ultimately enhancing the mechanical properties and environmental stability of the composite material.

[0040] In some embodiments, the inorganic nanomaterial is at least one of alumina powder, iron oxide powder, nano silica powder, and copper oxide powder, and the average particle size of the inorganic nanomaterial powder is between 10 nm and 250 nm.

[0041] Specifically, the introduction of inorganic nanomaterials not only enhances the material's compressive and impermeability properties but also effectively improves its heat resistance and resistance to CO2 / saltwater corrosion. These nanomaterials possess high thermal conductivity; when dispersed in phenolic resin, they can rapidly conduct heat from the material to the formation, allowing for rapid cooling and solidification. Furthermore, nanoparticles can act as a polymer skeleton to support the resin, increasing its strength. However, excessively large particle sizes of nanomaterials will reduce their specific surface area, hindering the efficient conduction of heat from the resin.

[0042] A second aspect of the present invention provides a method for preparing the above-mentioned CO2 geological sequestration leakage control resin-type leak control agent, comprising:

[0043] Raw material ratio: Take the raw materials according to the weight parts of the CO2 geological storage leakage resin-type leakage control agent;

[0044] Primary dispersion: The thermosetting organosilicon resin, the silane coupling agent, and the inorganic nanomaterials are mixed and dispersed in an ultrasonic reactor at room temperature until a uniform premixed system is formed.

[0045] Catalytic modification: After heating the premixed system to 80℃-110℃ to reduce the viscosity, the thermal catalytic stabilizer is added and ultrasonically stirred until completely homogenized;

[0046] Final mixing and curing: After the system cools to 25℃-30℃, add the acid anhydride curing agent and stir to mix, finally obtaining the resin-type leakage control agent.

[0047] The preparation method of the resin-based leakage control agent provided in this embodiment of the invention is simple and easy to scale up.

[0048] A third aspect of the present invention provides the application of the above-mentioned CO2 geological storage leakage resin-type leakage control agent for sealing microcracks in the caprock during CO2 geological storage.

[0049] Optionally, the method for repairing formation microfractures includes injecting a resin-based leakage control agent into the formation fracture, allowing it to cure naturally without heating due to the formation's own temperature. Preferably, the width of the formation microfracture is 0.1 μm-150 μm.

[0050] The resin-based leakage control agent of this invention exhibits good fluidity at room temperature and is used for sealing micro-fractures in caprock during CO2 geological storage. It can penetrate fractures less than 150 μm wide and rapidly solidifies under formation temperature conditions (80℃-120℃), forming a dense, flexible, and somewhat elastic three-dimensional network structure. Experimental results show that this resin-based leakage control agent effectively seals core fractures after sealing, with a maximum CO2 breakthrough pressure of 4.64 MPa. It demonstrates good formation adaptability and long-term stability, making it suitable for fine sealing of micro-fractures in deep geological storage projects.

[0051] Example 1 - Sample 1

[0052] (I) Resin-type leak control agent for CO2 geological storage leaks

[0053] By weight, 100 parts solid organosilicon resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 0.2 parts iron oxide powder.

[0054] (II) Preparation Method

[0055] Includes the following steps:

[0056] (1) Primary dispersion: 100 parts of solid organosilicon resin, 1.5 parts of KH-560 and 0.2 parts of iron oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0057] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0058] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0059] (III) Performance Evaluation

[0060] See details Figure 1 , Figure 2 , Figure 4 , Figure 5 And Table 1.

[0061] Example 2 - Sample Two

[0062] (I) Resin-type leak control agent for CO2 geological storage leaks

[0063] By weight, 100 parts solid organosilicon resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 0.6 parts iron oxide powder.

[0064] (II) Preparation Method

[0065] Includes the following steps:

[0066] (1) Primary dispersion: 100 parts of solid organosilicon resin, 1.5 parts of KH-560 and 0.6 parts of iron oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0067] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0068] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0069] (III) Performance Evaluation

[0070] See details Figure 1 , Figure 2 , and Table 1.

[0071] Example 3 - Sample Three

[0072] (I) Resin-type leak control agent for CO2 geological storage leaks

[0073] By weight, 100 parts solid organosilicon resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 1 part iron oxide powder.

[0074] (II) Preparation Method

[0075] Includes the following steps:

[0076] (1) Primary dispersion: 100 parts of solid organosilicon resin, 1.5 parts of KH-560 and 1 part of iron oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0077] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0078] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0079] (III) Performance Evaluation

[0080] See details Figure 1 , Figure 2 , and Table 1.

[0081] Example 4 - Sample Four

[0082] (I) Resin-type leak control agent for CO2 geological storage leaks

[0083] By weight, 100 parts solid organosilicon resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 2 parts iron oxide powder.

[0084] (II) Preparation Method

[0085] Includes the following steps:

[0086] (1) Primary dispersion: 100 parts of solid organosilicon resin, 1.5 parts of KH-560 and 2 parts of iron oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0087] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0088] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0089] (III) Performance Evaluation

[0090] See details Figure 1 , Figure 2 , and Table 1.

[0091] Example 5 - Sample 5

[0092] (I) Resin-type leak control agent for CO2 geological storage leaks

[0093] By weight, 100 parts solid silicone resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 0.6 parts alumina powder.

[0094] (II) Preparation Method

[0095] Includes the following steps:

[0096] (1) Primary dispersion: 100 parts of solid silicone resin, 1.5 parts of KH-560 and 0.6 parts of alumina powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0097] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0098] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0099] (III) Performance Evaluation

[0100] See details Figure 1 , Figure 2 , and Table 1.

[0101] Example 6 - Sample Six

[0102] (I) Resin-type leak control agent for CO2 geological storage leaks

[0103] By weight, 100 parts solid organosilicon resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 0.6 parts nano silica powder.

[0104] (II) Preparation Method

[0105] Includes the following steps:

[0106] (1) Primary dispersion: 100 parts of solid organosilicon resin, 1.5 parts of KH-560 and 0.6 parts of nano silica powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0107] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0108] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0109] (III) Performance Evaluation

[0110] See details Figure 1 , Figure 2 , and Table 1.

[0111] Example 7 - Sample Seven

[0112] (I) Resin-type leak control agent for CO2 geological storage leaks

[0113] By weight, 100 parts solid silicone resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 0.6 parts copper oxide powder.

[0114] (II) Preparation Method

[0115] Includes the following steps:

[0116] (1) Primary dispersion: 100 parts of solid silicone resin, 1.5 parts of KH-560 and 0.6 parts of copper oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0117] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0118] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0119] (III) Performance Evaluation

[0120] See details Figure 1 , Figure 2 , and Table 1.

[0121] Example 8 - Sample 8

[0122] (I) Resin-type leak control agent for CO2 geological storage leaks

[0123] By weight, 100 parts solid organosilicon resin, 35 parts trimellitic anhydride, 10 parts stearoylbenzoylmethane, 1.5 parts KH-560, and 0.6 parts iron oxide powder.

[0124] (II) Preparation Method

[0125] Includes the following steps:

[0126] (1) Primary dispersion: 100 parts of solid organosilicon resin, 1.5 parts of KH-560 and 0.6 parts of iron oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0127] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 10 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0128] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0129] (III) Performance Evaluation

[0130] See details Figure 1 , Figure 2 , and Table 1.

[0131] Example 9 - Sample Nine

[0132] (I) Resin-type leak control agent for CO2 geological storage leaks

[0133] By weight, 100 parts solid silicone resin, 35 parts trimellitic anhydride, 8 parts zinc acetylacetonate, 1.5 parts KH-560, and 0.6 parts iron oxide powder.

[0134] (II) Preparation Method

[0135] Includes the following steps:

[0136] (1) Primary dispersion: 100 parts of solid organosilicon resin, 1.5 parts of KH-560 and 0.6 parts of iron oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0137] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of zinc acetylacetone and ultrasonically stir until completely homogenized;

[0138] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0139] (III) Performance Evaluation

[0140] See details Figure 1 , Figure 2 , and Table 1.

[0141] Comparative Example 1 - Sample 10

[0142] (I) Resin-type leak control agent for CO2 geological storage leaks

[0143] By weight, 100 parts solid silicone resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, and 1.5 parts KH-560.

[0144] (II) Preparation Method

[0145] Includes the following steps:

[0146] (1) Primary dispersion: 100 parts of solid silicone resin and 1.5 parts of KH-560 were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0147] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0148] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0149] (III) Performance Evaluation

[0150] See details Figure 1 , Figure 2 , and Table 1.

[0151] Comparative Example 2 - Sample Eleven

[0152] (I) Resin-type leak control agent for CO2 geological storage leaks

[0153] By weight, 100 parts solid organosilicon resin, 35 parts trimellitic anhydride, 8 parts stearoylbenzoylmethane, and 0.6 parts iron oxide powder.

[0154] (II) Preparation Method

[0155] Includes the following steps:

[0156] (1) Primary dispersion: 100 parts of solid organosilicon resin and 0.6 parts of iron oxide powder were placed in an ultrasonic reactor and mixed and dispersed at room temperature until a uniform premixed system was formed.

[0157] (2) Catalytic modification: After heating the premixed system to 95°C to reduce the viscosity, add 8 parts of stearoylbenzoylmethane and ultrasonically stir until completely homogenized;

[0158] (3) Final mixing and curing: After the system is cooled to 25-30℃, 35 parts of trimellitic anhydride are added at a uniform rate and stirred and mixed to finally obtain an organosilicon resin composite material with dynamic ester bond recombination characteristics; wherein, the material can achieve reversible breakage and recombination of dynamic ester bonds under heating conditions, giving it self-healing properties.

[0159] (III) Performance Evaluation

[0160] See details Figure 1 , Figure 2 , and Table 1.

[0161] Table 1. Performance of the resin-based leak control agents prepared in Examples 1-9 and Comparative Examples 1-2

[0162]

[0163]

[0164] Results Analysis

[0165] The thermal conductivity of different samples was determined according to GB / T 29313-2012 Test Method for Thermal Conductivity of Electrical Insulation Materials. The results of the thermal conductivity of different samples are as follows: Figure 1 As shown. By Figure 1 It can be seen that inorganic nanomaterials can significantly improve the thermal conductivity of thermosetting silicone resins. When the cracks are large, the excellent thermal conductivity of inorganic nanomaterials can enable the resin to solidify quickly and achieve the effect of sealing the cracks.

[0166] Different samples were evaluated for their compressive strength according to GB / T 1041-92 "Test Method for Compression Properties of Plastics". The samples were cured at 95℃ for 48 days. The results are as follows: Figure 2 As shown. By Figure 2 It is known that adding silane coupling agents to resin can improve the compatibility and binding force between the filler and the resin, and increase the dispersibility of the filler in the resin, thereby greatly improving the compressive strength of the resin. However, the addition of inorganic nanomaterials reduces the compressive strength of the resin. The change in compressive strength is related to the concentration and particle size of the inorganic nanomaterials. Inorganic nanomaterials should be added appropriately according to the material.

[0167] The sealing effect of thermosetting silicone resin materials was evaluated using the following steps: First, cement grout was used to create a crack. The prepared cement grout was poured into a mold with a diameter of 25 mm and a height of 50 mm. After 4 hours of setting, a 1 mm thin iron wire was inserted from the top when the cement grout had initially solidified. The setting time was continued for another 72 hours. Once the cement had completely solidified into a columnar shape, the iron wire was removed, forming a vertically continuous crack. Then, the resin-based leakage control agent (resin sealing agent) from Example 1 was squeezed into the crack and placed in a 100°C water bath for 48 hours to ensure complete curing. After curing, the sample was demolded to obtain the final sample. The resin sealing agent sealing effect evaluation device is as follows: Figure 3 As shown, the sample was placed in the core holder 4, and CO2 was injected after applying a confining pressure of 6.0 MPa. The changes in injection pressure were recorded. When the first bubble appeared in the outlet flowmeter, the injection pressure at this time was recorded as the CO2 breakthrough pressure. The higher the breakthrough pressure, the better the sealing effect of the resin sealing agent. Figure 4 As can be seen, the sealing ability of the resin sealant in Example 1 is of great significance for solving the CO2 leakage problem in the capping layer. Figure 4 The changes in CO2 injection pressure during the displacement of cement stone samples are shown. Figure 4 It is evident that in the unsealed cement stone sample, bubbles appeared at the outlet when the CO2 injection pressure reached 0.13 MPa, indicating that the presence of cracks caused gas leakage. However, in the cement stone sample sealed with resin sealant, bubbles only appeared at the outlet when the CO2 injection pressure reached 4.64 MPa. This result demonstrates that the resin sealant has a significant sealing effect on cement stone cracks and can effectively prevent CO2 leakage.

[0168] The resin-based leakage control agent (resin sealant) of Example 1 was evaluated for its compressive strength according to GB / T 1041-92 "Test Method for Compression Properties of Plastics". It was cured at 95℃ for 48 days. Figure 5 As can be seen, the compressive strength of the resin sealant in Example 1 after coagulation is as high as 67.03 MPa.

[0169] In the description of this specification, the terms "one embodiment," "some embodiments," "specific embodiment," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0170] The above are merely preferred embodiments of the present invention and are not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A resin-type leak control agent for CO2 geological storage, characterized in that, Its raw material composition by weight includes: 85-105 parts of thermosetting silicone resin, 30-45 parts of acid anhydride curing agent, 7-10 parts of catalytic heat stabilizer, 0.5-3 parts of silane coupling agent, and 0.2-2 parts of inorganic nanomaterials.

2. The CO2 geological storage leakage control resin-type leakage control agent according to claim 1, characterized in that, The thermosetting silicone resin includes solid silicone resin and / or high-temperature silicone resin.

3. The CO2 geological storage leakage control resin-type leakage control agent according to claim 1, characterized in that, The anhydride curing agent is at least one of trimellitic anhydride, pyromellitic anhydride, and dichloromaleic anhydride.

4. The CO2 geological storage leakage control resin-type leakage control agent according to claim 1, characterized in that, The catalytic heat stabilizer is at least one of stearoylbenzoylmethane, zinc acetylacetonate, and stannous octoate.

5. The CO2 geological storage leakage control resin-type leakage control agent according to claim 1, characterized in that, The silane coupling agent is at least one of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane.

6. The CO2 geological storage leakage control resin-type leakage control agent according to claim 1, characterized in that, The inorganic nanomaterial is at least one of alumina powder, iron oxide powder, nano silica powder, and copper oxide powder, and the average particle size of the inorganic nanomaterial powder is between 10 nm and 250 nm.

7. A method for preparing a resin-type leakage control agent for CO2 geological storage, characterized in that, The method for preparing the CO2 geological sequestration leakage control resin-type leakage control agent according to any one of claims 1-6 comprises: Raw material proportions: Take the raw materials according to the weight proportions described in any one of claims 1-6; Primary dispersion: The thermosetting organosilicon resin, the silane coupling agent, and the inorganic nanomaterials are mixed and dispersed in an ultrasonic reactor at room temperature until a uniform premixed system is formed. Catalytic modification: After heating the premixed system to 80℃-110℃ to reduce the viscosity, the thermal catalytic stabilizer is added and ultrasonically stirred until completely homogenized; Final mixing and curing: After the system cools to 25℃-30℃, add the acid anhydride curing agent and stir to mix, finally obtaining the resin-type leakage control agent.

8. The application of a resin-type leak control agent for CO2 geological storage, characterized in that, The CO2 geological storage leakage control agent according to any one of claims 1-6 is used for sealing microcracks in the caprock during CO2 geological storage.

9. The application of the CO2 geological storage leakage control resin-type leakage control agent according to claim 8, characterized in that, The sealing method includes injecting the resin-based leak control agent into the formation fissure and allowing it to cool and solidify naturally.

10. The application of the CO2 geological storage leakage control resin-type leakage control agent according to claim 8, characterized in that, The width of the formation microfractures ranges from 0.1 μm to 150 μm.

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