Spraying sealing material for compressed air energy and gas storage and application method of spraying sealing material

Abstract

The invention belongs to the technical field of compressed air energy storage, and particularly relates to a spraying sealing material for a compressed air energy and gas storage and an application method of the spraying sealing material. The modified montmorillonite modified by quaternary ammonium salt and silane coupling agent is introduced, and the components of the spraying sealing material are reasonably compounded, so that the prepared spraying sealing material has excellent air tightness, pressure resistance, corrosion resistance, aging resistance and fatigue resistance; the material can effectively deal with high-pressure, low-temperature, humid and other extreme environments in the compressed air energy and gas storage, provides long-acting airtightness, aging resistance and long-term stability, and has high construction convenience and material performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of compressed air energy storage (CAES), and in particular relates to a spray sealing material for a compressed air energy storage reservoir and an application method thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] With the rapid development of renewable energy, compressed air energy storage technology (CAES) has received widespread attention as an emerging energy storage method. Compressed air energy storage systems are usually composed of underground gas storage, compressors, expanders and generators. Its core working principle is to convert excess electrical energy into compressed air for storage, and release compressed air to drive the generator to generate electricity when electricity is needed. However, the sealing of the gas storage directly affects the gas storage efficiency and the safety of the system.

[0004] At present, the sealing technology of compressed air energy storage mainly relies on mechanical seals, rubber gaskets or liquid sealing materials. These traditional materials usually need to be combined in multiple layers to achieve the sealing effect, but under long-term high-pressure environment and temperature changes, they are prone to problems such as airtightness decline, aging, and insufficient pressure resistance. These problems not only affect the long-term operation of the gas storage, but also increase the maintenance frequency and cost.

[0005] Existing sealing technologies still have many limitations when dealing with the special environment of compressed air energy storage reservoirs. First, mechanical seals and rubber gaskets have poor high-pressure resistance and are prone to deformation or aging due to long-term pressure. Secondly, although liquid sealing materials have a certain degree of airtightness, they are prone to flow or overflow under the action of high-pressure gas and cannot form a long-term stable sealing layer. Therefore, it is necessary to develop a new type of sealing material that can maintain a long-term stable sealing effect and effectively prevent compressed air leakage under harsh environments such as high pressure, temperature changes, and humidity.

[0006] In order to meet these challenges, spray sealing materials, as a new solution, have become an ideal choice due to their excellent gas barrier properties, good adhesion and adjustable flexibility. The sealing material is evenly covered on the inner wall of the gas storage reservoir through the spraying process, which can effectively avoid the defects of traditional sealing materials under high pressure and temperature difference changes. Therefore, the development of a spray sealing material suitable for compressed air energy storage reservoirs has important technical significance and broad application prospects. Summary of the invention

[0007] In view of the above-mentioned problems, the purpose of the present invention is to provide a spray sealing material for compressed air energy storage and its application method. The spray sealing material prepared by the present invention has excellent air tightness, pressure resistance, corrosion resistance, aging resistance and fatigue resistance, can effectively cope with the extreme environment of high pressure, low temperature, humidity and so on in compressed air energy storage, provides long-term air tightness, aging resistance and long-term stability, and has high construction convenience and material performance.

[0008] Specifically, the present invention provides the following technical solutions:

[0009] The first aspect of the present invention provides a spray sealing material for a compressed air energy storage reservoir, which includes a component A and a component B; the component A includes 0.5 to 15 parts of modified montmorillonite, 80 to 100 parts of epoxy resin, 0.5 to 5 parts of nano-silicon dioxide, 0.5 to 5 parts of nano-zinc oxide, 0 to 0.5 parts of a dispersant, and 0 to 50 parts of a first solvent; the component B includes 80 to 100 parts of a curing agent, 0 to 0.5 parts of a leveling agent, 0 to 0.5 parts of a defoaming agent, and 15 to 25 parts of a second solvent; the modified montmorillonite is a double-modified montmorillonite of a quaternary ammonium salt and a silane coupling agent; the mass ratio of the A and B components is 100:30 to 50.

[0010] Preferably, the epoxy resin is selected from one or more of bisphenol A epoxy resins E54, E51, E44, and E20.

[0011] Preferably, the dispersant is selected from one or more of fatty alcohol polyoxyethylene ether, polyurethane dispersants, polyester phosphate salt solutions, and polyacrylate dispersants.

[0012] More preferably, the fatty alcohol polyoxyethylene ether includes Lutensol A8, the polyurethane dispersant includes BYK-103 and BYK-220S, the polyester phosphate salt solution includes TEGO ViscoPlus 3000, and the polyacrylate dispersant includes EFKA 4010 and EFKA4310.

[0013] Preferably, the leveling agent is selected from one or more of polyether-modified polydimethylsiloxane, polysiloxane polyether copolymer, and fluorine-containing surfactant polymer, including BYK-088, BYK-1790, TEGO Airex 902W, TEGO Airex900, and DF-695.

[0014] Preferably, the defoaming agent is selected from one or more of organic phosphonic acid, polysiloxane, fatty alcohol, fatty acid ester, and hydrophobic silica, including BYK-333, BYK-377, TEGO Glide 450, TEGO Flow 370, and EFKA-3232.

[0015] Preferably, the curing agent is selected from polyamide curing agent 651, triethylenetetramine (TETA), diethylenetriamine (DETA), polyetheramine ( D-230), 4,4'-diaminodiphenyl sulfone (DDS), 4,4'-diaminodiphenylmethane (MDA), isophorone diamine (IPDA), hydrogenated diphenylmethane diamine (PACM), polyamide resin ( 140), methyltetrahydrophthalic anhydride (MTHPA) or one or more thereof.

[0016] Preferably, the first solvent is selected from one or more of acetone, methyl ethyl ketone, xylene, n-butanol, ethyl acetate, and cyclohexanone, and the second solvent is selected from one or more of acetone, methyl ethyl ketone, xylene, n-butanol, ethyl acetate, and cyclohexanone. The first solvent and the second solvent may be the same or different.

[0017] Preferably, the modified montmorillonite is prepared by two steps of quaternary ammonium salt modification and silane coupling agent modification, and the specific preparation method is as follows:

[0018] (1) adding a quaternary ammonium salt to a montmorillonite dispersion to perform intercalation modification through an ion exchange reaction, and obtaining a quaternary ammonium salt intercalation-modified montmorillonite after washing, drying, and grinding;

[0019] (2) The quaternary ammonium salt intercalated modified montmorillonite is dispersed in a mixed solution of deionized water and ethanol, the pH value of the obtained suspension is adjusted, a silane coupling agent solution is added, and then a heating reaction is performed. After washing, drying and grinding, the modified montmorillonite powder is obtained.

[0020] Further preferably, in step (1), the mass ratio of the montmorillonite to the quaternary ammonium salt is 1.5-2.5:1; in step (2), the mass ratio of the quaternary ammonium salt intercalated modified montmorillonite to the silane coupling agent is 100:5-20.

[0021] Further preferably, in step (1), the montmorillonite is an inorganic montmorillonite, preferably a sodium montmorillonite. The quaternary ammonium salt is selected from one of hexadecyltrimethylammonium chloride (CTAB), octadecyldimethylbenzylammonium chloride and dodecyltrimethylammonium bromide.

[0022] Further preferably, in step (2), the silane coupling agent is selected from one of γ-aminopropyltriethoxysilane (APTES), methacryloxypropyltrimethoxysilane (KH-570), epoxytrimethoxysilane (KH-560), and epoxytrimethoxysilane (KH-560).

[0023] Further preferably, in step (1) and step (2), the drying process is drying in an oven at 80-100° C. for 24 h or drying in a vacuum drying oven at 60-100° C. for 12 h until the product is completely dry.

[0024] A second aspect of the present invention provides a method for preparing a spray sealing material for a compressed air energy storage reservoir, comprising the following steps:

[0025] S1, adding the modified montmorillonite into the first solvent for premixing, and ultrasonically treating to obtain a modified montmorillonite dispersion;

[0026] S2, adding epoxy resin to the modified montmorillonite dispersion, heating, stirring and ultrasonically dispersing to obtain a uniform liquid mixture;

[0027] S3, adding dispersant, nano silicon dioxide, and nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0028] S4, adding the curing agent, defoaming agent and leveling agent to the second solvent and mixing evenly to obtain component B;

[0029] S5, mixing component A and component B, and subjecting the mixed slurry to vacuum treatment to obtain.

[0030] Preferably, in step S2, the temperature of the heating and stirring is 35-45° C., and the time is 30-50 min.

[0031] The third aspect of the present invention provides the use of the spray sealing material for compressed air energy storage reservoir described in the first aspect in a compressed air energy storage device.

[0032] A fourth aspect of the present invention provides a sealing coating, comprising the spray sealing material for a compressed air energy storage reservoir as described in the first aspect.

[0033] Preferably, the specific preparation method of the sealing coating is: determine the spraying area, clean the spraying surface, spray the spray sealing material described in the first aspect onto the target surface, and perform a curing reaction to obtain the sealing coating.

[0034] Further preferably, the spraying surface is cleaned to ensure that the surface is free of impurities such as oil, dust, etc.; the equipment used for spraying is an air spray gun or high-pressure spraying equipment to ensure uniform coverage of the material without leakage; the coating thickness of the spray sealing material is 0.5 to 2 mm, which is adjusted according to actual needs; after spraying, curing treatment is carried out, and the curing time is adjusted according to specific temperature and humidity conditions to ensure that the spray sealing material forms a strong and durable sealing layer.

[0035] Further preferably, whether a second spraying is required is examined according to performance requirements. If required, the above preparation method is repeated; if not required, the spraying process is completed.

[0036] One or more embodiments of the present invention have at least the following beneficial effects:

[0037] (1) The present invention is the first to use double-modified montmorillonite for epoxy-based spray sealing coatings for compressed air storage tanks. The core goal is high-pressure gas barrier properties (extremely low permeability). The prepared spray sealing material is mainly based on epoxy resin, supplemented with modified montmorillonite and other ingredients. Among them, epoxy resin has excellent mechanical strength, corrosion resistance and good adhesion, and can effectively provide stability for the sealing layer.

[0038] (2) The modified montmorillonite in the present invention is first treated with quaternary ammonium salt for intercalation, and then grafted with silane coupling agent through hydroxyl covalent bond to form a chemical anchoring network. Specifically, the layered structure formed by intercalation and silane coupling of the modified montmorillonite can extend the gas diffusion path, while the epoxy resin matrix provides a continuous and dense film layer, and nano-silicon dioxide / zinc oxide further fills microporous defects. The three work together to achieve ultra-low permeability;

[0039] Therefore, the addition of modified montmorillonite not only improves the hydrophobicity of the material, but also enhances its compatibility with epoxy resin and gas barrier properties. The optimized ratio of these components not only reduces the cost, but also improves the overall performance of the material, especially in a humid environment, and can achieve stable sealing for a long time.

[0040] (3) The spray sealing material prepared by the present invention has good fluidity and adaptability, and can evenly cover surfaces of different shapes and sizes to ensure the integrity of the sealing effect. It is particularly suitable for occasions with extremely high requirements for sealing, such as compressed air energy storage systems and underground projects.

[0041] (4) The preparation method of the present invention is simple and does not rely on high-end equipment. It can flexibly adjust the material ratio and curing process under on-site conditions to adapt to construction requirements under different environmental conditions. The good construction performance and operability of the material enable it to be efficiently applied in complex environments, improve construction efficiency and reduce material waste, and has strong market application prospects and promotion value.

[0042] (5) The spray sealing material prepared by the present invention has excellent gas barrier properties, water resistance and UV resistance, and has high adhesion and flexibility. It can maintain good performance stability during long-term use. Therefore, it has broad application potential and is particularly suitable for compressed air energy storage, underground gas storage facilities, offshore platforms and other fields with high requirements for air tightness. It has important application value and market competitiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0044] Figure 1 This is a diagram showing the change in interlayer spacing of montmorillonite before and after modification in Example 1 of the present invention;

[0045] Figure 2 The mixed state of component A in the spray sealing material prepared in Example 1 of the present invention;

[0046] Figure 3 The mixed state of component B in the spray sealing material prepared in Example 1 of the present invention;

[0047] Figure 4 The state of the component A and the component B in the spray sealing material prepared in Example 1 of the present invention after mixing;

[0048] Figure 5 This is a diagram showing the effect of applying the spray sealing material prepared in Example 1 of the present invention to a sandstone sample. DETAILED DESCRIPTION

[0049] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0050] The present invention will be further described in detail below in conjunction with specific embodiments. It should be noted that the specific embodiments are intended to explain the present invention rather than to limit it.

[0051] In the following examples, 1 g represents 1 part of a component.

[0052] Example 1 :This embodiment provides a spray sealing material for compressed air energy storage gas storage, and the preparation method is as follows:

[0053] (1) Preparation of modified montmorillonite:

[0054] S1. Disperse 20g of sodium montmorillonite in 1000mL of deionized water, heat to 85°C, and stir at 800rpm for 4h to obtain a montmorillonite suspension. Weigh 10g of octadecyl dimethyl benzyl ammonium chloride and dissolve it in 200mL of deionized water, add it into the system to continue the reaction, keep the heating temperature and stirring speed unchanged, and continue the reaction for 3h. After the system is cooled, filter, wash, dry, and grind the product to obtain a preliminarily modified montmorillonite.

[0055] S2. Take 10 g of the preliminary modified montmorillonite obtained in step S1, disperse it in 200 g of a mixture of deionized water and anhydrous ethanol, the mass ratio of deionized water to anhydrous ethanol is 15:85, stir at 60-70°C and 850 rpm for 1 hour to make a uniform suspension. Adjust the pH value of the suspension to 3.5-4.5 by adding dilute hydrochloric acid, and keep stirring at the heating temperature for 30-60 minutes.

[0056] Take 0.5g APTES and add it to 12g ethanol to prepare an APTES ethanol solution, and slowly add it to the suspension obtained in step S2. After continuing to heat and stir at 60-70°C for 2-3h, the product is filtered, washed, dried and ground with anhydrous ethanol to obtain modified montmorillonite powder.

[0057] (2) Preparation of component A

[0058] S1. Take 10 g of the modified montmorillonite in step (1) and add 50 g of a mixed solution of xylene and n-butanol (V 二甲苯 / V 正丁醇 =7:3), rapidly stirred and dispersed for 30 min for premixing, and ultrasonically treated for 1 h to obtain a uniform modified montmorillonite dispersion;

[0059] S2, adding 100 g of epoxy resin E51 to the dispersion, stirring for 30 min at 40° C. and 600 rpm using a magnetic stirrer, and then performing ultrasonic dispersion for 40 min to ensure full dispersion and obtain a uniform liquid mixture;

[0060] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0061] (3) Preparation of component B

[0062] Take 100g polyamide curing agent 651, 0.3g BYK-088, 0.4g EFKA-3232 and add them into 20g xylene n-butanol mixed solution (V 二甲苯 / V 正丁醇 =7:3) and mixed evenly to obtain component B;

[0063] (4) Coating preparation

[0064] The A and B components are mixed at a mass ratio of 100:50 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0065] (5) Performance testing

[0066] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this embodiment was coated on a medium-grained sandstone standard test block (diameter 50 mm, height 100 mm) for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was measured by pulse attenuation method to be 3.93×10 -5 mD (full name: millidarcy).

[0067] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 2000h.

[0068] like Figure 1 As shown in the figure, the interlayer spacing of montmorillonite increases after modification, indicating that the modification is successful. The modifier enters the interlayer of montmorillonite. The large interlayer spacing makes it easier for the montmorillonite sheets to be peeled off and evenly dispersed in the epoxy resin matrix, forming a parallel nanosheet structure, while enhancing the interfacial bonding force between montmorillonite and the epoxy resin matrix.

[0069] like Figures 2 to 4 As shown, a uniform system is formed after mixing, indicating that the surface functional groups of the modified montmorillonite (such as the epoxy groups introduced by the silane coupling agent) form strong chemical bonds with the active sites of the epoxy resin; after dispersion, each component exists stably in the resin matrix without phase separation or sedimentation. This verifies the rationality of the formula design and ensures that each component works synergistically at the molecular / nanoscale.

[0070] like Figure 5 As shown, when the coating is applied to the sandstone standard specimen, it has good leveling and fluidity, indicating that the coating can be spread evenly before curing and has good wettability, which can not only improve the coating quality, but also reduce micro defects. When the smooth coating is subjected to pressure cycling, the stress distribution is more uniform, delaying the initiation of cracks, thereby improving air tightness and pressure resistance.

[0071] Example 2: This example provides a spray sealing material for a compressed air energy storage reservoir, and the preparation method is as follows:

[0072] (1) Preparation of modified montmorillonite:

[0073] S1. Disperse 20g of sodium montmorillonite in 1000mL of deionized water, heat to 85°C, and stir at 800rpm for 4h to obtain a montmorillonite suspension. Weigh 10g of octadecyl dimethyl benzyl ammonium chloride and dissolve it in 200mL of deionized water, add it into the system to continue the reaction, keep the heating temperature and stirring speed unchanged, and continue the reaction for 3h. After the system is cooled, filter, wash, dry, and grind the product to obtain a preliminarily modified montmorillonite.

[0074] S2. Take 10 g of the preliminary modified montmorillonite obtained in step S1, disperse it in 200 g of a mixture of deionized water and anhydrous ethanol, the mass ratio of deionized water to anhydrous ethanol is 15:85, stir at 60-70°C and 850 rpm for 1 hour to make a uniform suspension. Adjust the pH value of the suspension to 3.5-4.5 by adding dilute hydrochloric acid, and keep stirring at the heating temperature for 30-60 minutes.

[0075] Take 0.5g APTES and add it to 12g ethanol to prepare an APTES ethanol solution, and slowly add it to the suspension obtained in step S2. After continuing to heat and stir at 60-70°C for 2-3h, the product is filtered, washed, dried and ground with anhydrous ethanol to obtain modified montmorillonite powder.

[0076] (2) Preparation of component A

[0077] S1, take 0.5g of the modified montmorillonite in step (1) and add 50g of a mixed solution of xylene and n-butanol (V 二甲苯 / V 正丁醇 =7:3), rapidly stirred and dispersed for 30 min for premixing, and ultrasonically treated for 1 h to obtain a uniform modified montmorillonite dispersion;

[0078] S2, adding 100 g of epoxy resin E51 to the dispersion, stirring for 30 min at 40° C. and 600 rpm using a magnetic stirrer, and then performing ultrasonic dispersion for 40 min to ensure full dispersion and obtain a uniform liquid mixture;

[0079] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0080] (3) Preparation of component B

[0081] Take 100g of isophorone diamine IPDA, 0.3g BYK-1790, and 0.4g TEGO Flow 370 and add them to 20g of xylene n-butanol mixed solution (V 二甲苯 / V 正丁醇 =7:3) and mixed evenly to obtain component B;

[0082] (4) Coating preparation

[0083] The A and B components are mixed at a mass ratio of 100:40 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0084] (5) Performance testing

[0085] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this embodiment was coated on a medium-grained sandstone standard test block (diameter 50 mm, height 100 mm) for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was determined by the pulse attenuation method to be 7.12×10 -5 mD.

[0086] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 1700h.

[0087] Example 3: This example provides a spray sealing material for a compressed air energy storage reservoir, and the preparation method is as follows:

[0088] (1) Preparation of modified montmorillonite:

[0089] S1. Disperse 20g of sodium montmorillonite in 1000mL of deionized water, heat to 85°C, and stir at 800rpm for 4h to obtain a montmorillonite suspension. Weigh 10g of octadecyl dimethyl benzyl ammonium chloride and dissolve it in 200mL of deionized water, add it into the system to continue the reaction, keep the heating temperature and stirring speed unchanged, and continue the reaction for 3h. After the system is cooled, filter, wash, dry, and grind the product to obtain a preliminarily modified montmorillonite.

[0090] S2. Take 10 g of the preliminary modified montmorillonite obtained in step S1, disperse it in 200 g of a mixture of deionized water and anhydrous ethanol, the mass ratio of deionized water to anhydrous ethanol is 15:85, stir at 60-70°C and 850 rpm for 1 hour to make a uniform suspension. Adjust the pH value of the suspension to 3.5-4.5 by adding dilute hydrochloric acid, and keep stirring at the heating temperature for 30-60 minutes.

[0091] Take 0.5g APTES and add it to 12g ethanol to prepare an APTES ethanol solution, and slowly add it to the suspension obtained in step S2. After continuing to heat and stir at 60-70°C for 2-3h, the product is filtered, washed, dried and ground with anhydrous ethanol to obtain modified montmorillonite powder.

[0092] (2) Preparation of component A

[0093] S1, take 15g of the modified montmorillonite in step (1) and add 50g of a mixed solution of xylene and n-butanol (V 二甲苯 / V 正丁醇 =7:3), rapidly stirred and dispersed for 30 min for premixing, and ultrasonically treated for 1 h to obtain a uniform modified montmorillonite dispersion;

[0094] S2, add 80g of epoxy resin E51 to the dispersion, stir for 30min at 40°C and 600rpm using a magnetic stirrer, and then perform ultrasonic dispersion for 40min to ensure full dispersion and obtain a uniform liquid mixture;

[0095] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0096] (3) Preparation of component B

[0097] 100 g of polyamide curing agent 651, 0.3 g of TEGO Airex 900, and 0.4 g of BYK-333 were added to 25 g of acetone and mixed evenly to obtain component B;

[0098] (4) Coating preparation

[0099] The A and B components are mixed at a mass ratio of 100:30 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0100] (5) Performance testing

[0101] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this embodiment was coated on a medium-grained sandstone standard test block (diameter 50 mm, height 100 mm) for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was determined by the pulse attenuation method to be 5.85×10 -5 mD.

[0102] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 1900h.

[0103] Example 4: This example provides a spray sealing material for a compressed air energy storage reservoir, and the preparation method is as follows:

[0104] (1) Preparation of modified montmorillonite:

[0105] S1. Disperse 20g of sodium montmorillonite in 1000mL of deionized water, heat to 85°C, and stir at 800rpm for 4h to obtain a montmorillonite suspension. Weigh 10g of octadecyl dimethyl benzyl ammonium chloride and dissolve it in 200mL of deionized water, add it into the system to continue the reaction, keep the heating temperature and stirring speed unchanged, and continue the reaction for 3h. After the system is cooled, filter, wash, dry, and grind the product to obtain a preliminarily modified montmorillonite.

[0106] S2. Take 10 g of the preliminary modified montmorillonite obtained in step S1, disperse it in 200 g of a mixture of deionized water and anhydrous ethanol, the mass ratio of deionized water to anhydrous ethanol is 15:85, stir at 60-70°C and 850 rpm for 1 hour to make a uniform suspension. Adjust the pH value of the suspension to 3.5-4.5 by adding dilute hydrochloric acid, and keep stirring at the heating temperature for 30-60 minutes.

[0107] Take 0.5g KH-570 and add it to 16g ethanol to prepare KH-670 ethanol solution, and slowly add it to the suspension obtained in step S2. After continuing to heat and stir at 60-70°C for 2-3h, filter, wash, dry and grind the product with anhydrous ethanol to obtain modified montmorillonite powder.

[0108] (2) Preparation of component A

[0109] S1, take 15g of the modified montmorillonite in step (1) and add 50g of a mixed solution of xylene and n-butanol (V 二甲苯 / V 正丁醇 =7:3), rapidly stirred and dispersed for 30 min for premixing, and ultrasonically treated for 1 h to obtain a uniform modified montmorillonite dispersion;

[0110] S2, add 80g of epoxy resin E51 to the dispersion, stir for 30min at 40°C and 600rpm using a magnetic stirrer, and then perform ultrasonic dispersion for 40min to ensure full dispersion and obtain a uniform liquid mixture;

[0111] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0112] (3) Preparation of component B

[0113] 100 g of polyamide curing agent 651, 0.3 g of TEGO Airex 900, and 0.4 g of BYK-333 were added to 25 g of acetone and mixed evenly to obtain component B;

[0114] (4) Coating preparation

[0115] The A and B components are mixed at a mass ratio of 100:30 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0116] (5) Performance testing

[0117] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this embodiment was coated on a medium-grained sandstone standard test block (diameter 50 mm, height 100 mm) for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was measured by pulse attenuation method to be 4.21×10 -5 mD.

[0118] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 1950h.

[0119] Comparative Example 1 :This comparative example provides a spray sealing material and preparation method for compressed air energy storage gas storage. Different from Example 1, this comparative example is a quaternary ammonium salt single modified montmorillonite, and the specific preparation method is as follows:

[0120] (1) Preparation of modified montmorillonite:

[0121] Take 20g of sodium montmorillonite and disperse it in 1000mL of deionized water, heat it to 85℃, and stir it at 800rpm for 4h to obtain a montmorillonite suspension. Weigh 10g of octadecyl dimethyl benzyl ammonium chloride and dissolve it in 200mL of deionized water, add it into the system and continue the reaction, keep the heating temperature and stirring speed unchanged, and continue the reaction for 3h. After the system is cooled, filter, wash, dry and grind the product to obtain a modified montmorillonite powder.

[0122] (2) Preparation of component A

[0123] S1. Take 10 g of the modified montmorillonite in step (1) and add 50 g of a mixed solution of xylene and n-butanol (V 二甲苯 / V 正丁醇 =7:3), rapidly stirred and dispersed for 30 min for premixing, and ultrasonically treated for 1 h to obtain a uniform modified montmorillonite dispersion;

[0124] S2, adding 100 g of epoxy resin E51 to the dispersion, stirring for 30 min at 40° C. and 600 rpm using a magnetic stirrer, and then performing ultrasonic dispersion for 40 min to ensure full dispersion and obtain a uniform liquid mixture;

[0125] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0126] (3) Preparation of component B

[0127] Take 100g polyamide curing agent 651, 0.3g BYK-088, 0.4g EFKA-3232 and add them into 20g xylene n-butanol mixed solution (V 二甲苯 / V 正丁醇 =7:3) and mixed evenly to obtain component B;

[0128] (4) Coating preparation

[0129] The A and B components are mixed at a mass ratio of 100:50 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0130] (5) Performance testing

[0131] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this comparative example was coated on the medium-grained sandstone standard test block for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was determined by the pulse attenuation method to be 1.22×10 -4 mD.

[0132] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 1500h.

[0133] Comparative Example 2 :This comparative example provides a spray sealing material and preparation method for compressed air energy storage gas storage. Different from Example 1, this comparative example is a silane-modified montmorillonite. The specific preparation method is as follows:

[0134] (1) Preparation of modified montmorillonite:

[0135] S1. Take 10g of sodium montmorillonite and disperse it in 200g of a mixture of deionized water and anhydrous ethanol, with a mass ratio of deionized water to anhydrous ethanol of 15:85. Stir at 60-70℃ and 850rpm for 1h to make a uniform suspension. Adjust the pH value of the suspension to 3.5-4.5 by adding dilute hydrochloric acid, and keep stirring at the heating temperature for 30-60min.

[0136] S2. Take 0.5 g of APTES and add it to 12 g of ethanol to prepare an APTES ethanol solution, and slowly add it to the suspension obtained in step S1. Continue to heat and stir at 60-70° C. for 2-3 hours, then filter, wash, dry and grind the product with anhydrous ethanol to obtain modified montmorillonite powder.

[0137] (2) Preparation of component A

[0138] S1. Take 10 g of the modified montmorillonite in step (1) and add it to 50 g of a mixed solution of xylene and n-butanol, stir rapidly and continue to disperse for 30 min for premixing, and perform ultrasonic treatment for 1 h to obtain a uniform modified montmorillonite dispersion;

[0139] S2, adding 100 g of epoxy resin E51 to the dispersion, stirring for 30 min at 40° C. and 600 rpm using a magnetic stirrer, and then performing ultrasonic dispersion for 40 min to ensure full dispersion and obtain a uniform liquid mixture;

[0140] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0141] (3) Preparation of component B

[0142] Take 100g polyamide curing agent 651, 0.3g BYK-088, 0.4g EFKA-3232 and add them into 20g xylene n-butanol mixed solution (V 二甲苯 / V 正丁醇 =7:3) and mixed evenly to obtain component B;

[0143] (4) Coating preparation

[0144] The A and B components are mixed at a mass ratio of 100:50 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0145] (5) Performance testing

[0146] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this comparative example was coated on the medium-grained sandstone standard test block for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was measured by the pulse attenuation method to be 8.56×10 -5 mD.

[0147] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 1800h.

[0148] Comparative Example 3 :This comparative example provides a spray sealing material and preparation method for compressed air energy storage gas storage. Different from Example 1, in the preparation of component A, the amount of modified montmorillonite in this comparative example is halved. The specific preparation method is as follows:

[0149] (1) Preparation of modified montmorillonite:

[0150] S1. Disperse 20g of sodium montmorillonite in 1000mL of deionized water, heat to 85°C, and stir at 800rpm for 4h to obtain a montmorillonite suspension. Weigh 10g of octadecyl dimethyl benzyl ammonium chloride and dissolve it in 200mL of deionized water, add it into the system to continue the reaction, keep the heating temperature and stirring speed unchanged, and continue the reaction for 3h. After the system is cooled, filter, wash, dry, and grind the product to obtain a preliminarily modified montmorillonite.

[0151] S2. Take 10g of the preliminary modified montmorillonite obtained in step S1, disperse it in 200g of a mixture of deionized water and anhydrous ethanol, the mass ratio of deionized water to anhydrous ethanol is 15:85, stir at 60-70°C and 850rpm for 1h to make a uniform suspension. Adjust the pH value of the suspension to 3.5-4.5 by adding dilute hydrochloric acid, and keep stirring at the heating temperature for 30-60min.

[0152] Take 0.5g APTES and add it to 12g ethanol to prepare an APTES ethanol solution, and slowly add it to the suspension obtained in step S2. After continuing to heat and stir at 60-70°C for 2-3h, the product is filtered, washed, dried and ground with anhydrous ethanol to obtain modified montmorillonite powder.

[0153] (2) Preparation of component A

[0154] S1, take 5g of the modified montmorillonite in step (1) and add 50g of a mixed solution of xylene and n-butanol (V 二甲苯 / V 正丁醇 =7:3), rapidly stirred and dispersed for 30 min for premixing, and ultrasonically treated for 1 h to obtain a uniform modified montmorillonite dispersion;

[0155] S2, adding 100 g of epoxy resin E51 to the dispersion, stirring for 30 min at 40° C. and 600 rpm using a magnetic stirrer, and then performing ultrasonic dispersion for 40 min to ensure full dispersion and obtain a uniform liquid mixture;

[0156] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0157] (3) Preparation of component B

[0158] Take 100g polyamide curing agent 651, 0.3g BYK-088, 0.4g EFKA-3232 and add them into 20g xylene n-butanol mixed solution (V 二甲苯 / V 正丁醇 =7:3) and mixed evenly to obtain component B;

[0159] (4) Coating preparation

[0160] The A and B components are mixed at a mass ratio of 100:50 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0161] (5) Performance testing

[0162] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this comparative example was coated on the medium-grained sandstone standard test block for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was determined by the pulse attenuation method to be 5.93×10 -4 mD.

[0163] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 1200h.

[0164] Comparative Example 4 :This comparative example provides a spray sealing material and preparation method for compressed air energy storage gas storage. Different from Example 1, in the preparation of modified montmorillonite, the amount of montmorillonite modified by silane in this comparative example is reduced. The specific preparation method is as follows:

[0165] (1) Preparation of modified montmorillonite:

[0166] S1. Disperse 20g of sodium montmorillonite in 1000mL of deionized water, heat to 85°C, and stir at 800rpm for 4h to obtain a montmorillonite suspension. Weigh 10g of octadecyl dimethyl benzyl ammonium chloride and dissolve it in 200mL of deionized water, add it into the system to continue the reaction, keep the heating temperature and stirring speed unchanged, and continue the reaction for 3h. After the system is cooled, filter, wash, dry, and grind the product to obtain a preliminarily modified montmorillonite.

[0167] S2. Take 1 g of the preliminary modified montmorillonite obtained in step S1, disperse it in 200 g of a mixture of deionized water and anhydrous ethanol, the mass ratio of deionized water to anhydrous ethanol is 15:85, stir at 60-70°C and 850 rpm for 1 hour to make a uniform suspension. Adjust the pH value of the suspension to 3.5-4.5 by adding dilute hydrochloric acid, and keep stirring at the heating temperature for 30-60 minutes.

[0168] Take 0.5g APTES and add it to 12g ethanol to prepare an APTES ethanol solution, and slowly add it to the suspension obtained in step S2. After continuing to heat and stir at 60-70°C for 2-3h, the product is filtered, washed, dried and ground with anhydrous ethanol to obtain modified montmorillonite powder.

[0169] (2) Preparation of component A

[0170] S1. Take 10 g of the modified montmorillonite in step (1) and add it to 50 g of a mixed solution of xylene and n-butanol, stir rapidly and continue to disperse for 30 min for premixing, and perform ultrasonic treatment for 1 h to obtain a uniform modified montmorillonite dispersion;

[0171] S2, adding 100 g of epoxy resin E51 to the dispersion, stirring for 30 min at 40° C. and 600 rpm using a magnetic stirrer, and then performing ultrasonic dispersion for 40 min to ensure full dispersion and obtain a uniform liquid mixture;

[0172] S3, adding 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0173] (3) Preparation of component B

[0174] Take 100g polyamide curing agent 651, 0.3g BYK-088, 0.4g EFKA-3232 and add them into 20g xylene n-butanol mixed solution (V 二甲苯 / V 正丁醇 =7:3) and mixed evenly to obtain component B;

[0175] (4) Coating preparation

[0176] The A and B components are mixed at a mass ratio of 100:50 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0177] (5) Performance testing

[0178] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this comparative example was coated on the medium-grained sandstone standard test block for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was measured by the pulse attenuation method to be 9.23×10 -4 mD.

[0179] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 900h.

[0180] Comparative Example 5 :This comparative example provides a spray sealing material and a preparation method for a compressed air energy storage reservoir. Different from Example 1, this comparative example does not add any modified montmorillonite. The preparation method is as follows:

[0181] (1) Preparation of component A

[0182] S1. Take 100 g of epoxy resin E51 and add it to 50 g of a mixed solution of xylene and n-butanol, stir it with a magnetic stirrer at 40° C. and 600 rpm for 30 min, and then perform ultrasonic dispersion for 40 min to ensure full dispersion and obtain a uniform liquid mixture;

[0183] S2, add 0.5g dispersant, 3g nano silicon dioxide, and 2g nano zinc oxide, and continue to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material;

[0184] (3) Preparation of component B

[0185] Take 100g polyamide curing agent 651, 0.3g BYK-088, 0.4g EFKA-3232 and add them into 20g xylene n-butanol mixed solution (V 二甲苯 / V 正丁醇 =7:3) and mixed evenly to obtain component B;

[0186] (4) Coating preparation

[0187] The A and B components are mixed at a mass ratio of 100:50 to obtain the spray material, and the mixed slurry is vacuum treated to remove bubbles therein.

[0188] (5) Performance testing

[0189] According to the general construction environment of the compressed air energy storage artificial chamber reservoir, the spraying material prepared in this comparative example was coated on the medium-grained sandstone standard test block for gas permeability test. According to GB / T 34533-2023 "Determination of shale porosity, permeability and saturation", the permeability of the standard test block after coating was determined by the pulse attenuation method to be 1.05×10 -3 mD.

[0190] The coating salt spray corrosion resistance test is carried out according to GB / T10125-2012 "Artificial atmosphere corrosion test salt spray test", and the effective protection time of the coating can reach 400h.

[0191] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A spray sealing material for compressed air energy storage reservoir, characterized in that: The invention comprises a component A and a component B; the component A comprises 0.5-15 parts of modified montmorillonite, 80-100 parts of epoxy resin, 0.5-5 parts of nano silicon dioxide, 0.5-5 parts of nano zinc oxide, 0-0.5 parts of dispersant and 0-50 parts of a first solvent; the component B comprises 80-100 parts of a curing agent, 0-0.5 parts of a leveling agent, 0-0.5 parts of a defoaming agent and 15-25 parts of a second solvent; the modified montmorillonite is a double-modified montmorillonite of a quaternary ammonium salt and a silane coupling agent; and the mass ratio of the components A to B is 100:30-50.

2. The spray sealing material for compressed air energy storage reservoir according to claim 1, characterized in that: The epoxy resin is bisphenol A epoxy resin; the dispersant is selected from one or more of fatty alcohol polyoxyethylene ether, polyurethane dispersants, polyester phosphate salt solutions, and polyacrylate dispersants; the leveling agent is selected from one or more of polyether-modified polydimethylsiloxane, polysiloxane polyether copolymer, and fluorine-containing surfactant polymer; the defoamer is selected from one or more of organic phosphonic acid, polysiloxane, fatty alcohol, fatty acid ester, and hydrophobic silica.

3. The spray sealing material for compressed air energy storage reservoir according to claim 1, characterized in that: The curing agent is selected from one or more of polyamide curing agent 651, triethylenetetramine, diethylenetriamine, polyetheramine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, isophoronediamine, hydrogenated diphenylmethanediamine, polyamide resin, and methyltetrahydrophthalic anhydride; Preferably, the first solvent is selected from one or more of acetone, methyl ethyl ketone, xylene, n-butanol, ethyl acetate, and cyclohexanone, and the second solvent is selected from one or more of acetone, methyl ethyl ketone, xylene, n-butanol, ethyl acetate, and cyclohexanone. The first solvent and the second solvent may be the same or different.

4. The spray sealing material for compressed air energy storage reservoir according to claim 1, characterized in that: The modified montmorillonite is prepared by two steps of quaternary ammonium salt modification and silane coupling agent modification. The specific preparation method is as follows: (1) adding a quaternary ammonium salt to a montmorillonite dispersion to perform intercalation modification through an ion exchange reaction, and obtaining a quaternary ammonium salt intercalation-modified montmorillonite after washing, drying, and grinding; (2) The quaternary ammonium salt intercalated modified montmorillonite is dispersed in a mixed solution of deionized water and ethanol, the pH value of the obtained suspension is adjusted, a silane coupling agent solution is added, and then a heating reaction is performed. After washing, drying and grinding, the modified montmorillonite powder is obtained.

5. The spray sealing material for compressed air energy storage reservoir according to claim 4, characterized in that: In step (1), the mass ratio of the montmorillonite to the quaternary ammonium salt is 1.5-2.5:1; in step (2), the mass ratio of the quaternary ammonium salt intercalated modified montmorillonite to the silane coupling agent is 100:5-20; Preferably, in step (1), the montmorillonite is an inorganic montmorillonite, preferably a sodium montmorillonite. The quaternary ammonium salt is selected from one of hexadecyltrimethylammonium chloride, octadecyldimethylbenzylammonium chloride and dodecyltrimethylammonium bromide; Preferably, in step (2), the silane coupling agent is selected from one of γ-aminopropyltriethoxysilane, methacryloxypropyltrimethoxysilane, epoxytrimethoxysilane and epoxytrimethoxysilane; Preferably, in step (1) and step (2), the drying process is drying in an oven at 80-100° C. for 24 h or drying in a vacuum drying oven at 60-100° C. for 12 h until the product is completely dry.

6. The method for preparing a spray sealing material for a compressed air energy storage reservoir according to any one of claims 1 to 5, characterized in that: The steps include: S1, adding the modified montmorillonite into the first solvent for premixing, and ultrasonically treating to obtain a modified montmorillonite dispersion; S2, adding epoxy resin to the modified montmorillonite dispersion, heating, stirring and ultrasonically dispersing to obtain a uniform liquid mixture; S3, adding dispersant, nano silicon dioxide, and nano zinc oxide, and continuing to stir evenly until all ingredients are completely dispersed to obtain component A of the spray sealing material; S4, adding the curing agent, defoaming agent and leveling agent to the second solvent and mixing evenly to obtain component B; S5, mixing component A and component B, and subjecting the mixed slurry to vacuum treatment to obtain.

7. The preparation method according to claim 6, characterized in that: In step S2, the heating and stirring is performed at a temperature of 35 to 45°C and for a time of 30 to 50 minutes.

8. Use of the spray sealing material for compressed air energy storage reservoir according to any one of claims 1 to 5 in a compressed air energy storage device.

9. A sealing coating, characterized in that: The invention comprises the spray sealing material for compressed air energy storage reservoir as described in any one of claims 1 to 5.

10. The sealing coating according to claim 9, characterized in that The specific preparation method of the sealing coating is: determine the spraying area, clean the spraying surface, spray the spray sealing material of any one of claims 1 to 5 onto the target surface, and perform a curing reaction to obtain the sealing coating.

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