A sealed material for underground space energy storage and preparation method thereof

Abstract

This application proposes a sealing material for underground space energy storage and its preparation method, comprising the following components by weight: 30-40 parts in situ polymerization monomer, 1-2 parts initiator, 1-2 parts crystallization nucleating agent, 1-3 parts crystallization accelerator, 1-2 parts dispersant, 1-2 parts emulsifier, and 90-100 parts gelling material. The sealing material provided in this application is a high-crystallinity sealing material with an outstanding sealing effect. This application also proposes a preparation method for the sealing material with the characteristics of simple process, low cost, and easy promotion and application.

Description

Technical Field

[0001] The present application relates to the field of green, low-carbon, and new energy technologies such as underground space energy storage and gas storage, and in particular to a sealed material for underground space energy storage and a preparation method thereof. Background Art

[0002] Deep underground energy storage is an important direction for the future development of energy reserves. It is the only way to solve the problems of traditional oil strategic reserves, natural gas peak-shaving security, sustainable supply of renewable energy, and large-scale and efficient utilization of hydrogen energy in the future. At present, there are many abandoned coal mines, large spaces, and low utilization rates. The maximum utilization of closed coal mines has not been achieved, resulting in a huge waste of underground space resources. The sealing problem of the gas seepage pathways formed in abandoned mines makes the key to gas storage in abandoned coal mine spaces. In abandoned coal mine spaces with continuous rheological and large deformation, the sealing material has insufficient sealing and insufficient deformation resistance, which has limited the sealing effect on the stored gas, seriously affecting the gas storage effect of the underground space and is the most important constraint on underground space energy storage.

[0003] Therefore, there is an urgent need to develop new high-crystallinity sealed materials with high airtightness and excellent mechanical properties for underground space energy storage and their preparation methods and promote their application. Summary of the Invention

[0004] This application aims to solve, at least to some extent, one of the technical problems in the related art. This application proposes a sealing material for underground space energy storage and a preparation method thereof. The preparation method has the characteristics of simple process, low cost and easy promotion and application. The sealing material provided in this application is a high-crystallinity sealing material with outstanding sealing effect.

[0005] According to an embodiment of the first aspect of the present application, a sealing material for underground space energy storage is proposed, comprising the following components in parts by mass: 30-40 parts of in-situ polymerization monomer, 1-2 parts of initiator, 1-2 parts of crystallization nucleating agent, 1-3 parts of crystallization promoter, 1-2 parts of dispersant, 1-2 parts of emulsifier and 90-100 parts of gelling material.

[0006] In some embodiments, the in situ polymerized monomers include 4,4'-diphenylenediamine, pentachloroaniline, 2-chloroaniline, and 3-fluoroaniline in a mass ratio of 2:1:4:1.

[0007] In some embodiments, the initiator includes ammonium pyrosulfate and ammonium pyrosulfite in a mass ratio of 4:1.

[0008] In some embodiments, the crystal nucleating agent includes nano nickel ferrite and nano silicon nitride powder in a mass ratio of 1:1.

[0009] In some embodiments, the crystallization accelerator comprises cellulose triacetate and nitrocellulose in a mass ratio of 3:1.

[0010] In some embodiments, the emulsifier includes triethanolamine dodecylbenzenesulfonate and sodium dodecyldimethylbenzenesulfonate in a mass ratio of 1:1.

[0011] In some embodiments, the dispersant is monomethyl sebacate.

[0012] In some embodiments, the cementitious material is a sulphoaluminate cementitious material.

[0013] According to an embodiment of the second aspect of the present application, a method for preparing an underground space energy storage sealing material is proposed, comprising the following steps:

[0014] Sulphoaluminate gelling material, crystallization nucleating agent, dispersant and crystallization accelerator are mixed uniformly according to stoichiometric amount to obtain a closed base material;

[0015] The in-situ polymerization monomer, initiator and emulsifier are mixed according to stoichiometric amount to obtain an active mixed solution;

[0016] The sealing base material is mixed with water at a water-cement ratio of 0.6 to obtain slurry A; the slurry A and the active mixed solution are sprayed at a volume ratio of 1:1 to obtain the sealing material described in any of the above embodiments.

[0017] According to an embodiment of the third aspect of the present application, a closed underground energy storage space is proposed, and the surface of the underground closed space is sprayed with the closed material described in any of the above embodiments to obtain the underground energy storage space.

[0018] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0020] Figure 1 This is a flow chart of a method for preparing a sealed material according to one embodiment of the present application. DETAILED DESCRIPTION

[0021] The embodiments of the present application are described in detail below. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended only to explain the present application and are not to be construed as limiting the present application. On the contrary, this application includes all variations, modifications, and equivalents that fall within the spirit and scope of the appended claims.

[0022] The technical solution of the embodiment of the present application provides a sealed material for underground space energy storage and a preparation method thereof. The present application provides a high-crystallinity sealed material that can be used for underground space energy storage. The preparation method has the characteristics of simple process, low cost and easy promotion and application.

[0023] " range " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of special range. The scope limited in this way can be to include end value or not include end value, and can be arbitrarily combined, that is, any lower limit can form a range with any upper limit combination. For example, if the scope of 60-120 and 80-110 is listed for specific parameters, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range value 1 and 2 are listed, and if the maximum range value 3,4 and 5 are listed, then the following range can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise specified, the numerical range " ab " represents the abbreviation of any real number combination between a and b, wherein a and b are all real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, when a parameter is expressed as an integer ≥ 2, this is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0024] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0025] To achieve the above-mentioned purpose, according to an embodiment of the first aspect of the present application, a sealing material for underground space energy storage is proposed, comprising the following components in parts by mass: 30-40 parts of in-situ polymerization monomer, 1-2 parts of initiator, 1-2 parts of crystallization nucleating agent, 1-3 parts of crystallization promoter, 1-2 parts of dispersant, 1-2 parts of emulsifier and 90-100 parts of gelling material.

[0026] In this embodiment, the sealing material includes 30-40 parts of in-situ polymerized monomers, for example, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, or 40 parts, wherein the in-situ polymerized monomers include 4,4'-diphenylenediamine (CAS: 92-87-5), pentachloroaniline (CAS: 527-20-8), 2-chloroaniline (CAS: 95-51-2), and 3-fluoroaniline (CAS: 372-19-0) in a mass ratio of 2:1:4:1. If the number of in-situ polymerized monomers is small, such as less than 30 parts, the molecular weight of the in-situ cross-linked product is low, and the strength and airtightness of the sealing material are insufficient. If the number of in-situ polymerized monomers is large, such as greater than 40 parts, a large amount of unreacted residual monomers will remain, affecting the strength of the sealing material.

[0027] In some embodiments, the initiator is present in 1 part or 2 parts, and includes ammonium pyrosulfate (CAS: 10031-68-2) and ammonium pyrosulfite (CAS: 32736-64-4) in a mass ratio of 4:1. If the initiator is present in a smaller amount, such as less than 1 part, the reaction may be incomplete, resulting in a large amount of unreacted residual monomers, which may affect the strength of the sealing material. If the initiator is present in a larger amount, such as greater than 2 parts, the molecular weight of the in-situ cross-linked product may be low, resulting in insufficient strength and airtightness of the sealing material.

[0028] In some embodiments, the crystal nucleating agent may be 1 part or 2 parts, etc., which includes nano nickel ferrite (CAS: 12168-54-6) and nano silicon nitride powder (CAS: 12033-89-5) in a mass ratio of 1:1. If the crystal nucleating agent is present in a small amount, such as less than 1 part, the crystal nucleation effect is poor, the crystal nucleation and growth are poor, and the sealing material is not strong. If the crystal nucleating agent is present in a large amount, such as greater than 2 parts, the crystal nucleation density is high, the crystal size is small, and there are many crystal defects, which affects the sealing material.

[0029] In some embodiments, the crystallization accelerator may be present in 1 part, 2 parts, or 3 parts, and the crystallization accelerator includes cellulose triacetate (CAS: 9012-09-3) and cellulose nitrocellulose (CAS: 132980-16-6) in a mass ratio of 3:1. If the crystallization accelerator is present in a relatively small amount, such as less than 1 part, the nucleation effect of the crystals may be poor, crystal nucleation and growth may be poor, and the strength and sealing properties of the sealed material may be weak. If the crystallization accelerator is present in a relatively large amount, such as greater than 3 parts, the crystal nucleation and growth rates may be slow, and the crystals may contain many defects.

[0030] In some embodiments, the emulsifier may be present in an amount of 1 part or 2 parts, wherein the emulsifier comprises triethanolamine dodecylbenzenesulfonate (CAS: 27323-41-7) and sodium dodecyldimethylbenzenesulfonate (CAS: 63428-97-7) in a mass ratio of 1:1. If the emulsifier is present in a smaller amount, such as less than 1 part, the emulsification effect may be poor and phase separation may occur. If the emulsifier is present in a larger amount, such as greater than 2 parts, the mechanical strength and durability of the sealing material may be affected.

[0031] In some embodiments, the powder may be 1 part or 2 parts, wherein the powder includes monomethyl sebacate. If the powder is in a smaller amount, such as less than 1 part, the dispersion effect is poor and agglomeration is likely to occur. If the powder is in a larger amount, such as greater than 2 parts, the mechanical strength and durability of the sealing material are affected.

[0032] In some embodiments, the cementitious material is a sulfoaluminate cementitious material, which includes 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, or 100 parts. If the cementitious material has a small proportion, such as less than 90 parts, the compressive strength and durability of the sealing material may be insufficient. If the cementitious material has a large proportion, such as greater than 100 parts, the sealing performance of the sealing material may be affected.

[0033] When the sealed base material and active mixed solution in this embodiment are used on site, the sealed base material is mixed with water at a water-cement ratio of 0.6 to obtain slurry A; the slurry A and the active mixed solution are sprayed at a volume ratio of 1:1 to obtain the sealed material in any of the above embodiments.

[0034] By incorporating reactive aniline monomers such as 4,4'-diphenylenediamine, pentachloroaniline, 2-chloroaniline, and 3-fluoroaniline into the cementitious material, the material undergoes in-situ polymerization at room temperature, using the heat of hydration as the driving force. This creates a dense, highly crystalline aniline polymer network. This highly crystalline aniline polymer network deprives the sealing material of its fluidity, maintaining its fixed shape and fulfilling its sealing function. The aniline polymer network and the hydration products of the cementitious material form an interconductive network structure. This dense, highly crystalline polymer network formed through in-situ polymerization at room temperature further forms a three-dimensional network structure, improving the mechanical properties of the sealing material and enabling it to withstand deformation in more underground spaces.

[0035] In-situ polymerization at room temperature forms a dense aniline polymer network. Due to the presence of a large number of amino groups, the number of hydrogen bonds within the system increases, strengthening the intermolecular forces. The number of hydrogen bonds has a significant impact on the material's strength and wear resistance, forming physical crosslinks that enhance the strength of the sealed material. Furthermore, in-situ polymerization at room temperature forms a dense aniline polymer network. In the presence of a crystallization accelerator, this promotes crystal nucleation and growth in the sealed material, increasing crystallinity. The dense crystal structure results in a dense molecular network, effectively achieving a sealed effect while filling the pores of the gelling material and improving the material's sealing properties.

[0036] In-situ polymerization at room temperature forms a highly crystalline polymer network. As the material's grain size increases, the interfacial area between the grains increases, increasing the interfacial area available to absorb impact energy and improving the material's impact resistance. Furthermore, increased crystallinity affects the material's fracture pattern and crack propagation rate, thereby enhancing its impact resistance and enabling the material to effectively withstand deformation and impact in underground spaces.

[0037] According to the embodiment of the second aspect of the present application, a method for preparing an energy storage sealing material for underground space is proposed. Figure 1 , including the following steps:

[0038] S1: mixing a sulphoaluminate gelling material, a crystallization nucleating agent, a dispersant and a crystallization accelerator according to stoichiometric amounts to obtain a closed base material; S2: mixing an in-situ polymerization monomer, an initiator and an emulsifier according to stoichiometric amounts to obtain an active mixed solution;

[0039] S3: Mix the sealing base material with water at a water-cement ratio of 0.6 to obtain slurry A; spray the slurry A and the active mixed solution at a volume ratio of 1:1 to obtain the sealing material in any of the above embodiments.

[0040] In step S1, 90-100 parts of sulphoaluminate gelling material, 1-2 parts of crystallization nucleating agent, and 1-3 parts of crystallization accelerator are weighed according to their mass parts, and stirred in a dry powder mixer for 15 minutes to obtain a sealed base material.

[0041] In step S2, 30-40 parts of in-situ polymerization monomer, 1-2 parts of initiator, and 1-2 parts of emulsifier are weighed according to their mass fractions, and the mixture is stirred for 20 minutes to obtain an active mixed solution.

[0042] Step S3: During on-site use, the sealed base material is mixed with water at a water-cement ratio of 0.6 to obtain A slurry. The A slurry and the active mixed solution are sprayed on the surface of the closed space at a volume ratio of 1:1 under the action of a double-liquid spraying pump to obtain a high-crystallinity sealed material.

[0043] According to an embodiment of the third aspect of the present application, a closed underground energy storage space is proposed, and the surface of the underground closed space is sprayed with the closed material in any of the above embodiments to obtain the underground energy storage space.

[0044] To facilitate further understanding of the present application, the present invention is further described below in conjunction with the embodiments. Those skilled in the art will understand that the descriptions in the present application are only partial examples, and any other suitable specific examples are within the scope of the present application.

[0045] Example 1

[0046] This embodiment provides a sealing material for underground space energy storage. The preparation method and specific operating parameters are as follows: 100 parts by mass of a sulphoaluminate gelling material, 2 parts by mass of a crystallization nucleating agent, 1 part by mass of a dispersant, and 1 part by mass of a crystallization accelerator are weighed and stirred in a dry powder mixer for 15 minutes to obtain a sealing base material; wherein the crystallization nucleating agent comprises nano-nickel ferrite and nano-silicon nitride powder in a mass ratio of 1:1; and the crystallization accelerator comprises cellulose triacetate and cellulose nitroate in a mass ratio of 3:1.

[0047] 30 parts by weight of in-situ polymerization monomer, 1 part by weight of initiator, and 1 part by weight of emulsifier were weighed and stirred for 20 minutes to mix uniformly to obtain an active mixed solution. The in-situ polymerization monomers included 4,4'-diphenylenediamine, pentachloroaniline, 2-chloroaniline, and 3-fluoroaniline in a mass ratio of 2:1:4:1; the initiator included ammonium pyrosulfate and ammonium metabisulfite in a mass ratio of 4:1; and the emulsifier included triethanolamine dodecylbenzenesulfonate and sodium dodecyldimethylbenzenesulfonate in a mass ratio of 1:1.

[0048] The sealing base material is mixed with water at a water-cement ratio of 0.6 to obtain material A slurry. The material A slurry and the active mixed solution are sprayed on the surface of the confined space at a volume ratio of 1:1 under the action of a double-liquid spraying pump to obtain the sealing material.

[0049] Example 2

[0050] This embodiment has the following differences compared to embodiment 1: 93 parts by mass of sulphoaluminate gelling material, 1 part of crystallization nucleating agent, 2 parts of dispersant, and 2 parts of crystallization accelerator are weighed; 33 parts of in-situ polymerization monomer, 2 parts of initiator, and 1 part of emulsifier are weighed; and the mixture is stirred for 20 minutes to obtain an active mixed solution.

[0051] Example 3

[0052] This embodiment has the following differences compared to embodiment 1: 95 parts by mass of sulphoaluminate gelling material, 2 parts of crystallization nucleating agent, 1 part of dispersant, and 2 parts of crystallization accelerator are weighed; 36 parts of in-situ polymerization monomer, 1 part of initiator, and 2 parts of emulsifier are weighed; and the mixture is stirred for 20 minutes to obtain an active mixed solution.

[0053] Example 4

[0054] This embodiment has the following differences compared to embodiment 1: 98 parts by mass of sulphoaluminate gelling material, 1 part of crystallization nucleating agent, 2 parts of dispersant, and 1 part of crystallization accelerator are weighed; 40 parts by mass of in-situ polymerization monomer, 2 parts of initiator, and 2 parts of emulsifier are weighed; the mixture is stirred for 20 minutes to obtain an active mixed solution.

[0055] Example 5

[0056] This embodiment has the following differences compared to embodiment 1: 90 parts by mass of sulphoaluminate gelling material, 2 parts of crystallization nucleating agent, 1 part of dispersant, and 1 part of crystallization accelerator are weighed; 38 parts by mass of in-situ polymerization monomer, 2 parts of initiator, and 1 part of emulsifier are weighed; the mixture is stirred for 20 minutes to obtain an active mixed solution.

[0057] Experimental example

[0058] The sealing materials in each embodiment were tested after use, and the results are shown in Table 1.

[0059] Table 1 Performance results of the sealing materials in the embodiment

[0060]

[0061] It can be seen from the results in Table 1 that the sealing material provided by the present application is a high-crystallinity sealing material with outstanding sealing effect and strength.

[0062] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0063] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A sealing material for underground space energy storage, characterized in that: The invention comprises the following components in parts by mass: 30-40 parts of in-situ polymerization monomers, 1-2 parts of initiator, 1-2 parts of crystallization nucleating agent, 1-3 parts of crystallization accelerator, 1-2 parts of dispersant, 1-2 parts of emulsifier and 90-100 parts of gelling material; the in-situ polymerization monomers comprise 4,4'-diphenylenediamine, pentachloroaniline, 2-chloroaniline and 3-fluoroaniline in a mass ratio of 2:1:4:

1.

2. The sealing material according to claim 1, characterized in that: The initiator includes ammonium pyrosulfate and ammonium pyrosulfite in a mass ratio of 4:

1.

3. The sealing material according to claim 1, characterized in that: The crystal nucleating agent comprises nano nickel ferrite and nano silicon nitride powder in a mass ratio of 1:

1.

4. The sealing material according to claim 1, characterized in that: The crystallization accelerator comprises cellulose triacetate and cellulose nitroate in a mass ratio of 3:

1.

5. The sealing material according to claim 1, characterized in that: The emulsifier comprises triethanolamine dodecylbenzenesulfonate and sodium dodecyldimethylbenzenesulfonate in a mass ratio of 1:

1.

6. The sealing material according to claim 1, characterized in that: The dispersant is monomethyl sebacate.

7. The sealing material according to any one of claims 1 to 6, characterized in that: The gelling material is a sulphoaluminate gelling material.

8. A method for preparing a sealed material for underground space energy storage, characterized in that: The following steps are involved: Sulphoaluminate gelling material, crystallization nucleating agent, dispersant and crystallization accelerator are mixed uniformly according to stoichiometric amount to obtain a closed base material; The in-situ polymerization monomer, initiator and emulsifier are mixed according to stoichiometric amount to obtain an active mixed solution; The sealing base material is mixed with water at a water-cement ratio of 0.6 to obtain a slurry A; the slurry A and the active mixed solution are sprayed at a volume ratio of 1:1 to obtain the sealing material according to any one of claims 1 to 7.

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