Microbial mineralization solid waste-based three-level interpenetrating heat storage body and preparation method thereof

Abstract

The present application belongs to the technical field of solid waste resource utilization, and relates to a kind of microbial mineralization solid waste based three-level interpenetrating heat storage body and its preparation method.The heat storage body includes microporous silica skeleton, and the solid waste activation component loaded in its interior;The solid waste activation component includes three-level functional material and red mud matrix;With the total mass of solid waste activation component being 100%, red mud matrix accounts for 30%-50%, and three-level functional material accounts for 50%-70%;With the total mass of three-level functional material being 100%, three-level functional material includes: 50%-60% titanium dioxide quantum dots, 20%-30% gallium oxide exciton, 10%-20% activated phosphogypsum sulfate powder;Three-level functional material forms three-level interpenetrating network structure in microporous silica skeleton.In the prior art, there is a problem in the solid waste treatment method that cannot realize the application of solid waste reenergy storage field through quantum dot and exciton coupling mechanism in solid waste.

Description

Technical Field

[0001] This invention belongs to the field of solid waste resource utilization technology, specifically relating to a microbial mineralization solid waste-based three-stage interpenetrating thermal storage body and its preparation method. Background Technology

[0002] In existing technologies, the resource utilization of solid waste mainly focuses on the preparation of cementitious materials and the development of fluidized solidified soil. Typical examples include the technical solutions disclosed in patent documents CN118005360A and CN115340308A, which utilize the cementitious active components and stable chemical components in solid waste to achieve a certain degree of waste reuse, reducing energy consumption and carbon emissions. However, these technical approaches primarily rely on the macroscopic physicochemical properties of solid waste and have not yet been able to deeply explore the unique physical mechanisms and functional characteristics possessed at the microscopic structural level.

[0003] It is particularly noteworthy that existing technologies generally suffer from a lack of diversity in functional utilization pathways, with insufficient exploration of potential high-value-added functions such as energy storage and conversion of solid waste. Specifically, while CN118005360A achieves the synergistic utilization of various solid wastes and optimization of particle size distribution, its core technology still revolves around improving traditional engineering properties such as material density, flowability, and mechanical strength, without addressing functional applications in energy storage and conversion. CN115340308A, on the other hand, suppresses the influence of harmful components such as free calcium oxide and free magnesium oxide through pretreatment, improving the material's volume stability. However, it similarly fails to systematically study the potential quantum confinement effects, exciton coupling, and other microscopic physical mechanisms in solid waste, as well as their application potential in fields such as thermal energy storage and photoelectric conversion.

[0004] Therefore, existing solid waste resource utilization technologies are still mostly limited to traditional engineering applications such as building materials and landfill, and have failed to effectively utilize the unique physicochemical properties that solid waste may possess at the microscale, especially in terms of thermal energy storage and energy conversion efficiency. Summary of the Invention

[0005] To overcome the problem that existing solid waste treatment methods cannot achieve solid waste re-energy storage applications through quantum dot and exciton coupling mechanisms in solid waste, the present invention proposes a microbial mineralized solid waste-based three-level interpenetrating thermal energy storage body and its preparation method. By utilizing the quantum dot characteristics of specific elements in solid waste and combining them with exciton coupling mechanisms, a non-traditional phase change room temperature topological assembly process is achieved, thereby significantly improving the thermal storage performance and energy conversion efficiency of solid waste-based materials.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention discloses a three-stage interpenetrating thermal storage body based on microbial mineralization solid waste, comprising a microporous silica framework and various solid waste activation components loaded therein; The solid waste activation component comprises tertiary functional materials and a red mud matrix; based on the total mass of the solid waste activation component as 100%, the red mud matrix accounts for 30%-50% of the mass, and the tertiary functional materials account for 50%-70% of the mass. Based on the total mass of the tertiary functional materials as 100%, the tertiary functional materials include: 50%-60% titanium dioxide quantum dots, 20%-30% gallium oxide excitons, and 10%-20% activated phosphogypsum sulfate powder. The three-level functional materials interpenetrate and permeate each other within the microporous silica framework, forming a three-level interpenetrating network structure.

[0007] Furthermore, the porosity of the microporous silica framework is 1.0-3.0 g / cm³. 3 The microporous silica particles in the microporous silica framework range in size from 100 to 300 nm.

[0008] Furthermore, the microstructure of the microbial mineralized solid waste-based three-level interpenetrating thermal storage body includes: a microporous silica framework, hollow nanopolyhedra, a two-level interpenetrating network, and sodium zeolite quantum dots embedded with europium ions distributed within the microporous silica framework; The bilevel interpenetrating network is a composite crystal of [FeO] and [NaF] nanoparticles containing bilevel interpenetration.

[0009] Furthermore, the nanoparticle composite crystal has a particle size of 2-3 mm; it has a polyhedral morphology and its surface has hollow pores and nanoscale pores.

[0010] This invention also discloses a method for preparing a three-stage interpenetrating thermal energy storage body based on microbial mineralized solid waste, comprising the following steps: Preparation of titanium dioxide quantum dots, gallium oxide excitons, and activated phosphogypsum sulfate powder; Weigh out titanium dioxide quantum dots, gallium oxide excimer, activated phosphogypsum sulfate powder and red mud, mix with deionized water, and then ultrasonically disperse and stir to form a uniform solid waste-based functional slurry. An anhydrous ethanol solution of tetraethyl orthosilicate was prepared, and hexadecyltrimethoxysilane was added under stirring to prepare a diluent. The above diluent was injected into a mold, sealed, and placed in an oven to dry, thereby obtaining a dried microporous silica framework. Solid waste-based functional slurry was injected into a microporous silica framework through a vacuum impregnation process to obtain a microporous silica framework loaded with solid waste-based functional slurry. The microporous silica framework loaded with solid waste-based functional slurry was subjected to ultraviolet irradiation under magnetic stirring to trigger exciton coupling and biomimetic reaction of microbial mineralization of various components in the slurry, thus obtaining the reaction precursor. The reaction precursor was cold-pressed at 200-400 MPa and held at that pressure for 5-15 minutes. After unloading, it was freeze-dried to obtain the microbial mineralized solid waste-based three-stage interpenetrating thermal storage body.

[0011] Furthermore, the preparation method of the titanium dioxide quantum dots specifically includes the following steps: Gold tailings are treated with dilute hydrochloric acid, filtered and washed, and polydimethyl sulfoxide is added to the filtrate. After standing, magnetic stirring and ultraviolet irradiation for 20–30 minutes, the mixture is centrifuged, washed and dried to obtain the final product.

[0012] Furthermore, the method for preparing gallium oxide excitons specifically includes the following steps: After air-drying, ball-milling, and sieving the red mud, it is dissolved in sodium hydroxide solution, treated in a water bath at 70-90℃, filtered, and washed to obtain a suspension. The suspension is mixed with ethylene glycol, wherein the mass ratio of ethylene glycol to the solids in the suspension is (1000-5000):1. The mixture is then irradiated with ultraviolet light for 20-30 minutes under a nitrogen atmosphere and stirring to obtain gallium oxide excitons.

[0013] Furthermore, the preparation process of the activated phosphogypsum sulfate powder is as follows: take phosphogypsum, grind it, sieve it, and dry it to constant weight to obtain activated phosphogypsum sulfate powder.

[0014] Compared with the prior art, the beneficial effects of the present invention are: This invention discloses a microbial mineralization solid waste-based three-stage interpenetrating thermal storage body, which innovatively utilizes three typical industrial solid wastes—gold tailings, red mud, and phosphogypsum—to achieve a resource-based "waste-to-waste" model. Specifically, gold tailings are used to prepare titanium dioxide quantum dots, red mud serves as both a matrix material and a preparation of gallium oxide excitons, and phosphogypsum, after activation, is used as a functional component. This multi-source solid waste synergistic utilization strategy effectively solves the problems of large solid waste accumulation, high disposal costs, and significant environmental risks in the non-ferrous smelting industry. The microbial mineralization solid waste-based three-stage interpenetrating thermal storage body of this invention effectively solves the problem of difficult resource utilization of solid waste in the non-ferrous smelting industry; it also enables the filling of mine voids or green belts in non-ferrous mining areas to restore ecological balance.

[0015] Furthermore, this invention constructs a multi-level structural system consisting of a microporous silica framework, hollow nanopolyhedra, a two-level interpenetrating network, and sodium zeolite quantum dots. Among them, the tertiary functional materials (titanium dioxide quantum dots, gallium oxide excitons, and activated phosphogypsum sulfate powder) interpenetrate and permeate within the microporous framework, forming a stable interpenetrating network, which significantly improves the mechanical strength and thermal stability of the material.

[0016] Furthermore, the microporous silica framework (porosity 1.0-3.0 g / cm³) 3 The nanoparticle composite crystals (particle size 100-300 nm) provide abundant microporous structures, and the surface of the nanoparticle composite crystals (particle size 2-3 mm) has hollow pores and nanoscale pores, forming a multi-level pore system from micropores to mesopores. This multi-level pore structure is beneficial for mass and heat transfer, and improves the heat storage density and thermal response rate.

[0017] Furthermore, the titanium dioxide quantum dots and gallium oxide excitons introduced into the material exhibit excellent photothermal conversion performance, generating an exciton coupling effect under ultraviolet light irradiation, significantly enhancing the infrared radiation heat release capability. The sodium zeolite quantum dots embedded with europium ions further improve the material's luminescence performance and thermal stability, making the thermal storage medium promising for applications in solar thermal utilization, building energy conservation, and other fields.

[0018] This invention also discloses a method for preparing a three-stage interpenetrating thermal storage body based on microbial mineralization of solid waste. Through biomimetic reactions of microbial mineralization and exciton coupling technology, low-value industrial solid waste is transformed into a high-value-added material with thermal storage capabilities, realizing the transformation of solid waste from "end-of-pipe treatment" to "resource utilization." The prepared thermal storage body can be used for filling mining subsidence areas or constructing green belts in factory areas, solving the problem of solid waste disposal and achieving ecological restoration, forming a virtuous cycle of "solid waste-materials-ecology."

[0019] Through cold pressing at 200-400 MPa and freeze-drying processes, a dense three-dimensional network structure is formed inside the material, effectively suppressing volume changes and structural collapse during thermal cycling. The biomineralized layer formed by the biomimetic reaction of microbial mineralization further enhances the interfacial bonding strength and thermal stability of the material, ensuring long-term performance.

[0020] The entire preparation process employs mild conditions such as ultraviolet light irradiation and water bath treatment, avoiding high-energy-consuming processes such as high-temperature calcination, thus reducing energy consumption and carbon emissions. The biomimetic reaction of microbial mineralization simulates the natural mineralization process, making it environmentally friendly and in line with green manufacturing principles.

[0021] The thermal storage body prepared by this invention can be used not only for filling mining goaf areas and greening factory areas, but also for building energy-saving materials, solar thermal storage systems, and industrial waste heat recovery, with significant economic and environmental benefits. Through the resource utilization of solid waste, a unified economic, environmental, and social benefit is achieved. Attached Figure Description

[0022] Figure 1 An exploded view of the three-stage interpenetrating thermal storage structure of microbial mineralized solid waste; Figure 2 Diagram showing the microstructure and energy conversion; Figure 3 This is a schematic diagram of the apparatus corresponding to the preparation method.

[0023] Among them, 1. Microporous silica framework; 2. Hollow nanopolyhedrons; 3. Bi-level interpenetrating network; 4. Sodium zeolite quantum dots; 5. Hollow nanopolyhedron surface pores; 6. [FeO] interpenetrating network; 7. [NaF] interpenetrating network; 8. Gold tailings acid washing unit; 9. Red mud alkali dissolution unit; 10. Phosphogypsum drying unit; 11. Titanium dioxide quantum dot synthesis kettle; 12. Gallium oxide exciton reactor; 13. Activated phosphogypsum storage tank; 14. Multifunctional mixing tank; 15. Microporous silica framework forming and drying unit; 16. Vacuum impregnation and ultraviolet mineralization reactor; 17. Cold pressing molding machine; 18. Freeze dryer. Detailed Implementation

[0024] The technical solution of this invention can not only effectively solve the limitations of solid waste resource utilization in the prior art, but also open up new application prospects for solid waste in the field of energy storage and conversion.

[0025] This invention provides a microbial mineralized solid waste-based three-stage interpenetrating thermal energy storage body with high thermal stability, applicable to building energy conservation, geological exploration and energy storage, and its preparation method.

[0026] The present invention discloses a microbial mineralized solid waste-based three-level interpenetrating thermal storage body, comprising a microporous silica framework and various solid waste activation components loaded therein; the solid waste activation components include three-level functional materials and a red mud matrix; based on the total mass of the solid waste activation components, the red mud matrix accounts for 30%-50% of the mass, and the three-level functional materials account for 50%-70% of the mass.

[0027] Based on the total mass of the tertiary functional materials as 100%, the tertiary functional materials include: 50%-60% titanium dioxide quantum dots, 20%-30% gallium oxide excitons, and 10%-20% activated phosphogypsum sulfate powder.

[0028] The titanium dioxide quantum dots, gallium oxide excitons, and activated phosphogypsum sulfate powder serve as tertiary functional materials, interpenetrating and permeating each other within the microporous silica framework to form a tertiary interpenetrating network structure; the red mud matrix fills the above network structure, together constituting a complete composite thermal storage body.

[0029] The porosity of the microporous silica framework is 1.0-3.0 g / cm³. 3 The microporous silica particles in the microporous silica framework range in size from 100 to 300 nm.

[0030] The preparation method of titanium dioxide quantum dots is as follows: The gold tailings were taken from the tailings of the gold mine in Xiadian Town, Zhaoyuan City, Shandong Province. X-ray diffraction analysis showed that its main mineral was pyrite (FeS), followed by quartz (SiO). Sulfuric acid corrosion: Weigh 2g of gold tailings, add 120mL of 3mol / L dilute hydrochloric acid, stir mechanically for 2h, filter and wash until neutral; Ultraviolet irradiation: After filtering the filtrate through a 350-mesh filter, add 1 ml of polydimethyl sulfoxide (DMSO) to the center of the filter membrane, stir and let stand for 30 min, then stir magnetically in the reaction vessel and irradiate with a 365 nm ultraviolet lamp for 20–30 minutes. Separation and purification: The reaction product was centrifuged at 5000 rpm for 15 min, washed three times with ethanol, and dried under vacuum to obtain titanium dioxide quantum dots.

[0031] The preparation method of gallium oxide excitons is as follows: 1. Red mud treatment: The residue was taken from the alluvial layer of the Aksu River upstream embankment in Kashgar City, southern Xinjiang Uygur Autonomous Region, air-dried and ball-milled to 200 mesh and then sieved to obtain sieved red mud; 2. Preparation of gallium oxide excitons: The sieved red mud was dissolved in 5 mol / L sodium hydroxide solution, and after being treated in a water bath at 70-90℃, it was filtered and washed to obtain a suspension. The suspension was mixed with ethylene glycol, wherein the mass ratio of ethylene glycol to the solids in the suspension was (1000-5000):1. The mixture was then irradiated with ultraviolet light for 20-30 minutes under a nitrogen atmosphere and stirring to obtain gallium oxide excitons.

[0032] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0033] Example 1 The microbial mineralized solid waste-based three-level interpenetrating thermal storage body includes a microporous silica framework and various solid waste activation components loaded inside it; the solid waste activation components include three-level functional materials and red mud matrix; based on the total mass of the solid waste activation components, the red mud matrix accounts for 30% and the three-level functional materials account for 70%.

[0034] Based on the total mass of the tertiary functional materials being 100%, the tertiary functional materials include: 55% titanium dioxide quantum dots, 25% gallium oxide excitons, and 20% activated phosphogypsum sulfate powder.

[0035] See Figure 1 The method for preparing a three-stage interpenetrating thermal energy storage body based on microbial mineralized solid waste of the present invention includes the following steps: S1. Functional component pretreatment: S1.1 Preparation of titanium dioxide quantum dots: Weigh 2g of gold tailings, add 120mL of 3mol / L dilute hydrochloric acid, stir mechanically for 2 hours, filter and wash until neutral; the gold tailings are rich in heavy metal ions such as europium and terbium; After filtering the filtrate through a 350-mesh filter, 1 ml of polydimethyl sulfoxide (DMSO) was added dropwise to the center of the filter membrane. After stirring, the mixture was allowed to stand for 30 min, then transferred to a reaction vessel and magnetically stirred. The mixture was then irradiated with a 365 nm UV lamp for 20 min. The reaction product was centrifuged at 5000 rpm for 15 min, washed three times with ethanol, and vacuum dried to obtain titanium dioxide quantum dots for later use. S1.2 Preparation of gallium oxide excitons: Red mud was air-dried and ball-milled to 200 mesh and then sieved. The sieved red mud was dissolved in 5 mol / L sodium hydroxide solution and stirred for 2 h. Then, it was placed in an 80℃ water bath, filtered, and washed three times with deionized water to obtain a suspension. Then, 40 mL of ethylene glycol and 2.5 mg of the above suspension were added to the reaction vessel, and nitrogen gas was introduced for backflushing for 48 h. The mixture was then irradiated with a 365 nm ultraviolet lamp for 20 minutes under stirring to obtain gallium oxide excitons for later use. S1.3 Pretreatment of phosphogypsum sulfate: Grind phosphogypsum to 200 mesh and sieve it. Dry it at 105℃ to constant weight to remove water of crystallization and obtain activated phosphogypsum sulfate powder for later use.

[0036] S2. Preparation of mixed slurry: To prepare 100g of activated solid waste component, the following materials were weighed: 30g of red mud matrix and 70g of tertiary functional material. The 70g of tertiary functional material consisted of 38.5g (70g × 55%) of titanium dioxide quantum dots, 17.5g (70g × 25%) of gallium oxide excitons, and 14g (70g × 20%) of activated phosphogypsum sulfate powder. The above materials were mixed with an appropriate amount of deionized water and subjected to ultrasonic dispersion and high-speed mechanical stirring for 2 hours to form a homogeneous solid waste-based functional slurry.

[0037] S3. Preparation and loading of microporous silica framework: Prepare a 5 wt% tetraethyl orthosilicate (TEOS) anhydrous ethanol solution, and add hexadecyltrimethoxysilane (CTMOS) under stirring to prepare a TEOS / CTMOS mass ratio of 5:1 dilution. The above diluted solution was injected into a mold, sealed, and then placed in an oven at 60°C for 12 hours to dry, yielding a dried microporous silica framework (density approximately 1.8 g / cm³). 3 ); Subsequently, the solid waste-based functional slurry prepared by S2 was injected into the microporous silica framework through a vacuum impregnation process to ensure that the slurry was fully impregnated into the microporous silica framework.

[0038] S4, Microbial mineralization reaction: The microporous silica framework loaded with solid waste-based functional slurry was transferred into a reactor and irradiated with a 365nm ultraviolet lamp for 25 minutes under magnetic stirring to trigger the exciton coupling and microbial mineralization biomimetic reaction of the components in the slurry, thus obtaining the reaction precursor. S5. Cold pressing and post-processing: The reaction precursor was placed in a mold, cold-pressed at 300 MPa and held for 10 min, unloaded and then freeze-dried (pre-freezing temperature -40℃, drying for 24 h) to finally obtain the microbial mineralized solid waste-based three-stage interpenetrating thermal storage body.

[0039] The reaction process of S5 is as follows: The reaction precursor obtained in the previous step is placed in a mold for pre-pressing and fixation, and then cold-pressed. After unloading, a composite crystal containing two-level interpenetrating [FeO] and [NaF] nanoparticles is obtained, namely a solid waste-based nanocomposite material. The particle size of the nanocomposite material is 2-3 mm. The nanomaterial has a polyhedral morphology and a large number of hollow pores and nanoscale pores on its surface.

[0040] The microstructure of the obtained thermal storage body is as follows Figure 1 , Figure 2 As shown, it mainly comprises: a microporous silica framework 1, a hollow nanopolyhedron 2 serving as an energy storage container, a two-level interpenetrating network 3 serving as a highly efficient heat conduction channel, and sodium zeolite quantum dots 4 embedded with europium ions serving as the energy conversion center. Its energy transfer path is as follows: incident light energy is captured by the sodium zeolite quantum dots 4 and converted into heat energy, which is then rapidly conducted through the channels formed by the [FeO] interpenetrating network 6 and the [NaF] interpenetrating network 7, and finally stored in the hollow nanopolyhedron 2.

[0041] This invention mixes modified tailings, phosphogypsum, and red mud and places them under ultraviolet light. Through excited-state dynamic competition, stable europium ion radiation clusters are preferentially formed. Based on the bio-like mineral superstructure, a sodium zeolite quantum dot / bipolar interpenetrating nanocomposite material embedded with europium ions is constructed.

[0042] The microbial mineralized solid waste-based three-stage interpenetrating thermal energy storage body proposed in this invention is a macroscopic blackbody system that integrates high-efficiency energy conversion and storage and can realize "aser-in-a-box".

[0043] The term "aser-in-a-box" refers to a laser-like structure formed by embedding the separate radiation layer and gain medium of a laser in a quartz box.

[0044] Specifically, the three-level interpenetrating thermal energy storage of this invention utilizes the simulation of the three-level nested structure in natural biomolecules and incorporates europium ions into the resonant energy transfer network therein to maximize the conversion and utilization efficiency of solar energy.

[0045] The structure was demonstrated to achieve efficient solar energy conversion and utilization through a combination of simulation and experimental testing, achieving a photothermal conversion efficiency of 68.7%. Furthermore, the thermal stability of the thermal storage body was good after 15,000 cycles of loading.

[0046] Example 2 The difference between this embodiment and Embodiment 1 lies in the ratio of the solid waste activation components: The red mud matrix accounts for 40% of the total mass of the activated solid waste components, and the tertiary functional materials account for 60%. Based on the total mass of the tertiary functional materials, the composition is: 50% titanium dioxide quantum dots, 30% gallium oxide excitons, and 20% activated phosphogypsum sulfate powder. In the preparation method, the cold pressing pressure is 250 MPa, and the holding pressure is 8 min.

[0047] Example 3 The difference between this embodiment and Embodiment 1 lies in the ratio of the solid waste activation components: The red mud matrix accounts for 50% of the total mass of the activated solid waste components, and the tertiary functional materials account for 50%. Based on the total mass of the tertiary functional materials, the composition is: 60% titanium dioxide quantum dots, 20% gallium oxide excitons, and 20% activated phosphogypsum sulfate powder. In the preparation method, the cold pressing pressure is 350 MPa, and the holding pressure is 12 min.

[0048] like Figure 1 The diagram shown is an exploded view of the three-stage interpenetrating thermal storage structure based on microbial mineralized solid waste. The macroscopic carrier and support structure of the microporous silica framework thermal storage body has a porous network.

[0049] The tertiary functional material interpenetrating network is a functional network formed by the interpenetration of titanium dioxide quantum dots, gallium oxide excitons, and activated phosphogypsum.

[0050] The red mud matrix serves as a continuous matrix, filling a three-level functional material interpenetrating network.

[0051] The energy storage container, with its hollow nanopolyhedral core, has a hollow internal structure for storing thermal energy. The core energy storage container demonstrates the final location where the thermal energy is stored.

[0052] The two-level interpenetrating network microscopic high-speed heat conduction channels are composed of interpenetrating [FeO] and [NaF] nanocrystals. These microscopic high-speed heat conduction channels demonstrate the path of heat energy conduction from quantum dots to the energy storage container.

[0053] Sodium zeolite quantum dot energy conversion centers are embedded with europium ions (Eu). 3+ The energy conversion center is responsible for capturing and converting light energy; it demonstrates the process of receiving light energy and converting it into heat energy.

[0054] The surface pores are distributed in nanoscale pores on the surface of hollow nanopolyhedra, which are used to enhance mass and heat transfer.

[0055] The preparation method of the microbial mineralized solid waste-based three-stage interpenetrating thermal energy storage body of the present invention is divided into three major stages: raw material pretreatment, functional material synthesis, and compounding and molding. The materials are processed in the following order: "raw material pretreatment → functional material synthesis → mixing → framework preparation and loading → mineralization reaction → cold pressing → freeze drying". Figure 3 The devices shown are used to process the heat storage material, which is then used to obtain the final product.

[0056] Figure 3 In this process, the gold tailings acid washing unit 8, the red mud alkali dissolution unit 9, and the phosphogypsum drying unit 10 constitute the raw material pretreatment; the gold tailings acid washing unit 8 and the titanium dioxide quantum dot synthesis kettle 11 are used for the preparation of titanium dioxide quantum dots; the red mud alkali dissolution unit 9 and the gallium oxide exciton reactor 12 (providing N2 atmosphere and magnetic stirring) are used for the preparation of gallium oxide excitons; the phosphogypsum drying unit 10 is used for the pretreatment of phosphogypsum sulfate, and the activated phosphogypsum storage tank 13 is used to store activated phosphogypsum sulfate powder.

[0057] The multifunctional mixing tank 14 is connected to the titanium dioxide quantum dot synthesis vessel 11, the gallium oxide exciton reactor 12, and the activated phosphogypsum storage tank 13 for the preparation of mixed slurry.

[0058] The microporous silica framework forming and drying apparatus 15 is used to prepare dried microporous silica frameworks.

[0059] Vacuum impregnation and ultraviolet mineralization reactor 16 is used to inject the solid waste-based functional slurry prepared in S2 into the microporous silica framework through a vacuum impregnation process, ensuring that the slurry is fully impregnated into the microporous silica framework; the microporous silica framework loaded with solid waste-based functional slurry is transferred into a reactor and irradiated with a 365nm ultraviolet lamp for 25 minutes under magnetic stirring to trigger the exciton coupling and microbial mineralization biomimetic reaction of each component in the slurry, thereby obtaining the reaction precursor.

[0060] The cold pressing molding machine 17 is used to place the reaction precursor in the mold, cold press it under a pressure of 300MPa and hold it for 10 minutes. The freeze dryer 18 is used to freeze dry it after unloading, and finally obtain the microbial mineralized solid waste-based three-stage interpenetrating heat storage body.

Claims

1. A three-stage interpenetrating thermal storage body based on microbial mineralization solid waste, characterized in that, It includes a microporous silica framework and solid waste activation components loaded inside the microporous silica framework; The solid waste activation component includes tertiary functional materials and red mud matrix; Based on the total mass of the activated solid waste components being 100%, the red mud matrix accounts for 30%-50% of the mass, and the tertiary functional materials account for 50%-70% of the mass. Based on the total mass of the tertiary functional materials as 100%, the tertiary functional materials include: 50%-60% titanium dioxide quantum dots, 20%-30% gallium oxide excitons, and 10%-20% activated phosphogypsum sulfate powder. The three-level functional materials interpenetrate and permeate each other within the microporous silica framework, forming a three-level interpenetrating network structure.

2. The three-stage interpenetrating thermal storage body based on microbial mineralization solid waste according to claim 1, characterized in that, The porosity of the microporous silica framework is 1.0-3.0 g / cm³. 3 The microporous silica particles in the microporous silica framework range in size from 100 to 300 nm.

3. The three-stage interpenetrating thermal storage body based on microbial mineralization solid waste according to claim 1, characterized in that, The microstructure of the microbial mineralized solid waste-based three-level interpenetrating thermal storage body includes: a microporous silica framework, hollow nanopolyhedra, a two-level interpenetrating network, and sodium zeolite quantum dots embedded with europium ions distributed within the microporous silica framework; The bilevel interpenetrating network is a composite crystal of [FeO] and [NaF] nanoparticles containing bilevel interpenetration.

4. The three-stage interpenetrating thermal storage body based on microbial mineralization solid waste according to claim 3, characterized in that, The nanoparticle composite crystal has a particle size of 2-3 mm; it has a polyhedral morphology and its surface has hollow pores and nanoscale pores.

5. A method for preparing a three-stage interpenetrating thermal energy storage body based on microbial mineralized solid waste as described in any one of claims 1-4, characterized in that, Includes the following steps: Preparation of titanium dioxide quantum dots, gallium oxide excitons, and activated phosphogypsum sulfate powder; Weigh out titanium dioxide quantum dots, gallium oxide excimer, activated phosphogypsum sulfate powder and red mud, mix with deionized water, and then ultrasonically disperse and stir to form a uniform solid waste-based functional slurry. An anhydrous ethanol solution of tetraethyl orthosilicate was prepared, and hexadecyltrimethoxysilane was added under stirring to prepare a diluent. The above diluent was injected into a mold, sealed, and placed in an oven to dry, thereby obtaining a dried microporous silica framework. Solid waste-based functional slurry was injected into a microporous silica framework through a vacuum impregnation process to obtain a microporous silica framework loaded with solid waste-based functional slurry. The microporous silica framework loaded with solid waste-based functional slurry was subjected to ultraviolet irradiation under magnetic stirring to trigger exciton coupling and biomimetic reaction of microbial mineralization of various components in the slurry, thus obtaining the reaction precursor. The reaction precursor was cold-pressed at 200-400 MPa and held at that pressure for 5-15 minutes. After unloading, it was freeze-dried to obtain the microbial mineralized solid waste-based three-stage interpenetrating thermal storage body.

6. The method for preparing a three-stage interpenetrating thermal energy storage body based on microbial mineralized solid waste according to claim 5, characterized in that, The specific preparation method of the titanium dioxide quantum dots Includes the following processes: Gold tailings were treated with dilute hydrochloric acid, filtered and washed, and polydimethyl sulfoxide was added to the filtrate. After standing, magnetic stirring and ultraviolet irradiation for 20–30 minutes, titanium dioxide quantum dots were obtained by centrifugation, washing and drying.

7. The method for preparing a three-stage interpenetrating thermal storage body based on microbial mineralized solid waste according to claim 5, characterized in that, The method for preparing gallium oxide excitons specifically includes the following steps: After air-drying, ball-milling, and sieving the red mud, it is dissolved in sodium hydroxide solution, treated in a water bath at 70-90℃, filtered, and washed to obtain a suspension. The suspension is mixed with ethylene glycol and irradiated with ultraviolet light for 20-30 minutes under a nitrogen atmosphere and stirring to obtain gallium oxide excitons.

8. The method for preparing a three-stage interpenetrating thermal storage body based on microbial mineralized solid waste according to claim 7, characterized in that, The mass ratio of ethylene glycol to solids in the suspension is (1000-5000):

1.

9. The method for preparing a three-stage interpenetrating thermal storage body based on microbial mineralized solid waste according to claim 5, characterized in that, The preparation process of the activated phosphogypsum sulfate powder is as follows: take phosphogypsum, grind it, sieve it, and dry it to constant weight to obtain activated phosphogypsum sulfate powder.

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