A mine plugging enhancer and a preparation method thereof

Abstract

The application discloses a mine plugging reinforcing agent and a preparation method thereof, and belongs to the technical field of mine repairing materials, and comprises the following components: 20-40 parts of aluminate cement, 5-15 parts of early strength agent, 8-20 parts of expanding agent, 1-5 parts of activated nano silicon dioxide, 0.8-1.5 parts of fiber reinforcing material and 0.5-1.2 parts of dispersing agent. Through the synergistic effect of bacillus licheniformis fermentation product and aluminate cement, the application effectively solves the problem that cement-based grouting material is slow to solidify and difficult to quickly support the area in urgent need of reinforcement. Through the TA-Fe-KGM complex, the application effectively overcomes the defects that the plugging agent is susceptible to environmental temperature and humidity, and the solidification time and effect are difficult to control.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mine repair materials, in particular to a mine plugging enhancer and a preparation method thereof. BACKGROUND

[0002] In the process of mining, the complex geological structure inside the mine often causes problems such as residual holes, rock cracks and water gushing channels after coal seam gas extraction. If these conditions are not properly handled, the leakage of harmful gases such as gas will form an explosive environment, threatening the safety of underground workers; and the overflow of liquids, such as water gushing, not only will interfere with the normal mining process, but also may cause serious accidents such as mine collapse. Therefore, efficiently plugging these leakage points and enhancing the stability of the mine structure is of great significance to ensure safety in production and improve mining efficiency.

[0003] At present, various types of mine plugging materials have been applied to some extent, but all have significant defects. For example, the commonly used cement-based grouting material is widely used due to its relatively low cost and wide source. However, the cement-based material performs poorly in terms of setting speed, and it usually takes a long time to reach a certain strength, which cannot provide sufficient support force quickly for areas that need to be reinforced, easily leading to further loosening of the surrounding rock or soil due to the lack of effective support for a long time, increasing the risk of accidents.

[0004] Some inorganic gel plugging materials have obvious limitations when injected into small cracks or pores. Due to their large particle size or insufficient fluidity, they cannot fully penetrate into fine cracks, making it impossible to completely plug these small leakage channels, thus resulting in poor overall plugging effect. Once encountering high-pressure gas or liquid, these small cracks that have not been effectively plugged may become a breakthrough for leakage, leading to plugging failure.

[0005] In summary, the existing mine plugging materials are difficult to meet the complex and changing needs of mine operations in terms of setting speed, early strength performance and plugging effect of gas and liquid. Developing a new type of mine plugging enhancer that can accelerate the setting of grouting materials, significantly improve early strength, and efficiently seal gas and liquid overflow has become a key problem to be solved in the mining industry, which has important practical significance for promoting safe and efficient mining.

[0006] Based on this, the present application designs a mine plugging enhancer and a preparation method thereof to solve the above problems. SUMMARY

[0007] In view of the above-mentioned shortcomings of the prior art, the present application provides a mine plugging enhancer, which comprises the following components:

[0008] Aluminates cement 20-40 parts;

[0009] Early strength agent 5-15 parts; obtained by inoculating Bacillus licheniformis seed liquid into a culture medium prepared from , urea, fish peptone, yeast extract, , , glucose, sodium citrate and Tween80;

[0010] Expanding agent 8-20 parts; obtained by mixing, grinding and mixing boron mud, calcium carbide slag and humic acid sodium;

[0011] Activated nano-silicon dioxide 1-5 parts;

[0012] Fiber reinforced material 0.8-1.5 parts; composed of pretreated glass fiber and pretreated basalt fiber with a mass ratio of 0.3-0.7:0.5-1.6;

[0013] Dispersing agent 0.5-1.2 parts; obtained by loading TA-Fe-KGM complex on mica-based nano-carrier.

[0014] A preparation method of the mine plugging reinforcing agent, comprising the following steps:

[0015] S1. Preparation of early strength agent;

[0016] Dissolve , urea, fish peptone, yeast extract, , , glucose, sodium citrate, Tween80 in water to obtain a culture medium;

[0017] Inoculate Bacillus licheniformis seed liquid into the culture medium, shake culture and then ferment to obtain a fermentation broth;

[0018] After cooling the fermentation broth, add cationic polyacrylamide flocculation, centrifuge to collect the precipitate;

[0019] Add malt dextrin to the precipitate, spray dry and crush;

[0020] After adding silane coupling agent for mixing treatment, mix calcium nitrate, and the early strength agent is obtained;

[0021] S2. Fiber pretreatment;

[0022] Grind the glass fiber using a sand belt sander and dry it;

[0023] Mix nano-silicon dioxide with gelatin, add water to prepare a suspension, immerse the glass fiber in the suspension, and dry it after taking it out to obtain pretreated glass fiber;

[0024] Grind kaolin, add water to prepare a suspension, immerse the cleaned basalt fiber in the suspension, and dry it after taking it out to obtain pretreated basalt fiber;

[0025] S3. Activating nano-silica;

[0026] After mixing the nano-silica and calcium carbonate powder, ball milling and sieving, the activated nano-silica is obtained;

[0027] S4. Preparing dispersant;

[0028] Mixing mica tailings and industrial-grade hydrofluoric acid with stirring, spray drying to obtain mica-based nano-carrier;

[0029] Adding iron sulfate to konjac glucmannan solution to form Fe-KGM complex, adding tannic acid, stirring to form TA-Fe-KGM complex, adding mica-based nano-carrier dispersion liquid, and reacting to obtain dispersant;

[0030] S5. Preparing expansion agent;

[0031] Mixing boron mud, calcium carbide slag and sodium humate, grinding to obtain expansion agent;

[0032] S6. Raw material compounding;

[0033] Preparing the dispersant into a solution, stirring to make a uniform dispersion liquid, and adding the activated nano-silica into the dispersion liquid;

[0034] Adding pretreated glass fiber and pretreated basalt fiber into a blender, dry mixing to obtain mixed fiber, and adding the mixed fiber into the dispersion liquid;

[0035] Dry mixing aluminate cement, early strength agent and expansion agent, and wet mixing into the dispersion liquid to form a mixture;

[0036] Granulating and drying the mixture through a granulator to obtain a mine plugging reinforcing agent.

[0037] Further, S1 is specifically: 25-35 g / L , 15-25 g / L urea, 8-12 g / L fish peptone, 3-6 g / L yeast extract, 1-1.5 g / L , 0.5-1 g / L , 5-10 g / L glucose, 1-3 g / L sodium citrate, 0.1-0.3 g / L Tween 80, dissolving each component in deionized water to obtain a culture medium;

[0038] Taking the logarithmic growth phase of Bacillus licheniformis seed liquid, inoculating into the culture medium at a inoculation amount of 5-8 wt%, and culturing under the conditions of 35-38℃ and 180-200 r / min for 12-16 h, controlling the dissolved oxygen≥30%, and starting fermentation when the pH reaches 0.8-1.0, to obtain a fermentation liquor;

[0039] After the fermentation broth is cooled, add 0.05-0.1 wt% cationic polyacrylamide for flocculation, centrifuge at 4000-5000 r / min for 15-20 min to collect the precipitate, and wash it 3 times with deionized water.

[0040] Add 2-5 wt% maltodextrin to the precipitate, spray dry under conditions of inlet air temperature 150-160℃ and outlet air temperature 70-80℃, and then pulverize by airflow. ≤10μm ≤20μm;

[0041] Add 2-3 wt% silane coupling agent, treat in a high-speed mixer, and then mix with 5-10 wt% calcium nitrate to obtain an early strength agent.

[0042] Furthermore, the specific fermentation steps are as follows: maintain 35-38℃ for 0-24 hours, adjust the pH to 7.0-7.5 with HCl solution, and ensure DO ≥ 30%. ≥3.0;

[0043] Within 24-48 hours, adjust the temperature to 28-30℃, stop adding acid, and allow the pH to rise naturally to 8.5-9.0, while maintaining the dissolved oxygen (DO) at 20-30%.

[0044] Add 0.5-1 g / L within 48-72 hours. Reduce the stirring speed to 100-150 r / min and intermittently add 5-10 g / L of urea. When the residual... Fermentation was terminated when the concentration was ≤0.5g / L, yielding the fermentation broth.

[0045] Furthermore, the glass fiber pretreatment steps are as follows: using a belt sander, the glass fiber is passed through the sander at a speed of 5-10m / min, with a sander grit size of 200-400 mesh. The sanded glass fiber is then laid flat on the conveyor belt and passed through a drying channel equipped with an airflow blowing device at a speed of 0.5-1m / min. The temperature inside the drying channel is maintained at 60-80℃.

[0046] Nano-silica and gelatin are mixed at a mass ratio of 1:2-3, and deionized water is added to prepare a suspension of 1-3 wt%. Glass fibers are immersed in the suspension for 20-30 minutes, and then dried at 80-100℃ for 1-2 hours to obtain pretreated glass fibers.

[0047] Furthermore, the pretreatment steps for basalt fiber are as follows: place the basalt fiber in a steam cleaning device, introduce saturated steam at a pressure of 0.2-0.4 MPa and a temperature of 120-150℃, and treat for 15-25 minutes;

[0048] Kaolin is ground to a particle size of less than 20 μm, and deionized water is added to prepare a suspension of 15-20 wt%. Basalt fibers are immersed in the suspension for 15-20 min, removed and naturally dried at room temperature for 1-2 h, and then dried in an oven at 80-100 ℃ for 2-3 h to obtain pretreated basalt fibers.

[0049] Furthermore, S3 specifically involves mixing nano-silica and calcium carbonate powder in a mass ratio of 1-5:0.5-1, adding the mixture to a planetary ball mill, using zirconia balls with a diameter of 3-5 mm, and ball milling at a speed of 300-400 r / min for 2-3 hours with a ball-to-material ratio of 10-12:1. After ball milling, the mixture is passed through a 180-200 mesh sieve to obtain activated nano-silica.

[0050] Furthermore, S4 specifically involves mixing mica tailings with industrial-grade hydrofluoric acid at a solid-liquid ratio of 1:2-3, stirring in a water bath at 60-70℃ for 2-3 hours, repeatedly washing with deionized water until neutral, and then preparing a mica-based nanocarrier by spray drying.

[0051] Konjac glucomannan was prepared into a 1-3 wt% aqueous solution. Ferric sulfate was added to the KGM solution to make... The mass ratio of Fe-KGM to KGM is 1:8-12. Stir at room temperature for 30-60 min to form Fe-KGM complex. Add tannic acid at a mass ratio of Fe-KGM complex to tannic acid of 1:0.3-0.6. Continue stirring for 1-2 h to form TA-Fe-KGM complex. Under stirring conditions, slowly add the mica-based nanocarrier dispersion grafted with polymer. After the addition is complete, react at 40-50℃ for 2-3 h to obtain the dispersant.

[0052] Furthermore, S5 specifically involves: feeding boron mud, carbide slag, and sodium humate with a particle size ≤10μm into a planetary ball mill at a mass ratio of 40-60:20-35:15-30, using alumina balls as the grinding medium, with a ball-to-material ratio of 6-8:1, and mixing and grinding at 300-400r / min for 2-3 hours to obtain the expanding agent.

[0053] Furthermore, S6 specifically involves: adding ethanol to the dispersant to prepare a solution with a concentration of 5-10 wt%, stirring it for 10-15 minutes using a high-speed disperser at a speed of 1500-2000 r / min to prepare a uniform dispersion, slowly adding activated nano-silica to the dispersion, and continuing to stir for 20-30 minutes.

[0054] Add pretreated glass fiber and pretreated basalt fiber to a mixer and dry mix at 300-500 r / min for 5-10 min to obtain mixed fiber. Add the mixed fiber to a dispersion containing activated nano silica and stir at 100-200 r / min for 15-20 min.

[0055] Add aluminate cement, early strength agent and expansion agent to a high-strength mixer and dry mix at a speed of 200-300 r / min for 10-15 min. Add the dispersion containing fiber and nano silica to the mixer and increase the speed to 500-800 r / min. Wet mix for 20-30 min to form a mixture with good fluidity and plasticity.

[0056] The mixture is granulated using a granulator to produce particles with a diameter of 2-5 mm. The particles are then placed in a drying oven and dried at 60-80℃ for 2-3 hours to remove ethanol, thus obtaining a mining plugging enhancer.

[0057] Compared with the prior art, the beneficial effects of this invention are as follows:

[0058] 1. This invention effectively solves the problem of slow setting of cement-based grouting materials and difficulty in quickly supporting areas requiring reinforcement by utilizing the synergistic effect of Bacillus licheniformis fermentation products and aluminate cement. During fermentation, carbonic anhydrase catalyzes the decomposition of urea, generating calcium carbonate crystal nuclei that accelerate cement hydration and crystallization. Combined with the rapid hardening and early strength characteristics of aluminate cement, this significantly shortens the initial setting time, enabling rapid and effective support in emergency mine reinforcement scenarios, reducing the risk of surrounding rock or soil loosening and collapsing due to lack of support. Simultaneously, the fermentation products and calcium nitrate promote the rapid hydration of tricalcium aluminate to generate ettringite, while nano-silica fills the pores and participates in the pozzolanic reaction. The synergistic effect of these multiple components significantly enhances the early compressive strength of the material, meeting the rapid load-bearing requirements of mine operations.

[0059] 2. This invention effectively overcomes the shortcomings of sealants, which are easily affected by environmental temperature and humidity, and whose curing time and effect are difficult to control, through the TA-Fe-KGM complex. Konjac glucomannan (KGM) binds to water molecules through hydrogen bonds, buffering the effect of moisture on the cement matrix in high humidity environments and preventing dilution of hydration products; at low temperatures, its molecular chains form a stable network to maintain the hydration reaction. The coordination complex formed with KGM and tannic acid can reversibly adjust the system activity through changes in coordination bonds when temperature and humidity fluctuate, ensuring the stability of the solidification process. When compounded with an early-strength agent, KGM regulates the moisture distribution, creating conditions for the early-strength agent to function. The stable network structure of the complex ensures the continuous solidification promotion of the early-strength agent at low temperatures, achieving stable solidification performance in complex mining environments such as high humidity and low temperature, and avoiding problems such as incomplete solidification or slow solidification caused by environmental factors.

[0060] 3. This invention achieves excellent sealing performance through a multi-level structural design. The hydration of the expanding agent produces expansion products such as ettringite, which fill cracks and pores at the macroscopic level, blocking gas and liquid channels. Pre-treated glass fibers and basalt fibers form a three-dimensional network structure, trapping cement particles and enhancing adhesion to the rock mass, preventing the sealing material from detaching. Nano-silica, with its high specific surface area and activity, fills microscopic pores and participates in the volcanic ash reaction to generate a dense gel film, reducing material permeability. The synergistic effect of these multiple components forms a multi-level sealing system from macroscopic to microscopic, achieving efficient sealing for both gas leaks and liquid inrushes. This effectively solves the problem of poor sealing performance of traditional materials in two-phase media environments, significantly improving the safety and efficiency of mining operations. Detailed Implementation

[0061] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0062] Example 1: This example provides a method for preparing a mine-use sealing and reinforcing agent, including the following steps:

[0063] S1. Preparation of early strength agent;

[0064] At 35g / L 25g / L urea, 12g / L fish peptone, 6g / L yeast extract, 1.5g / L 1g / L The ratio of 10 g / L glucose, 3 g / L sodium citrate, and 0.3 g / L Lween 80 was used to dissolve each component in deionized water to obtain the culture medium (the culture medium was pre-sterilized at 121℃ for 20 minutes and then cooled to room temperature).

[0065] Take Bacillus licheniformis seed culture in the logarithmic growth phase and inoculate it into the culture medium at an inoculum rate of 8 wt%. Incubate at 38℃ and 200 r / min with shaking for 16 h, controlling dissolved oxygen ≥30%. Fermentation begins when the temperature reaches 1.0.

[0066] Fermentation stage: Maintain 38℃ for 0-24 hours, adjust pH to 7.5 with sterile HCl solution, and ensure DO ≥ 30%. ≥3.0;

[0067] Within 24-48 hours, adjust the temperature to 30℃, stop adding acid, and allow the pH to rise naturally to 9.0, while maintaining the dissolved oxygen (DO) at 30%.

[0068] Add 1g / L within 48-72 hours Reduce the stirring speed to 150 r / min and intermittently add 10 g / L urea. When the residual... Fermentation was terminated when the concentration was ≤0.5g / L, yielding the fermentation broth;

[0069] The fermentation broth was cooled to 25°C, and 0.1 wt% cationic polyacrylamide was added for flocculation. The precipitate was collected by centrifugation at 5000 r / min for 20 min and washed three times with deionized water.

[0070] Add 5 wt% maltodextrin to the precipitate, spray dry under conditions of 160°C inlet air temperature and 80°C outlet air temperature, and then pulverize by airflow. ≤10μm ≤20μm;

[0071] Add 3wt% silane coupling agent (KH-550) and treat in a high-speed mixer (5000r / min, 10min), then mix with 10wt% calcium nitrate to obtain the early strength agent;

[0072] S2. Fiber pretreatment;

[0073] Using a belt sander, glass fibers are fed through a conveyor belt at a uniform speed of 10 m / min. The sander has a grit size of 400 mesh. This physical sanding method increases the surface roughness of the glass fibers. The sanded glass fibers are then laid flat on the conveyor belt and passed through a drying channel at a speed of 1 m / min. The temperature inside the drying channel is maintained at 80℃. At the same time, airflow purging devices are installed on both sides of the channel (compressed air generated by an oil-free air compressor is filtered and dried, and then delivered to the purging nozzles through an air supply pipe). The airflow speed is 5 m / s, and the airflow direction is 30 degrees to the glass fiber conveying direction to remove the tiny fiber dust and moisture generated during sanding.

[0074] Nano-silica and gelatin were mixed at a mass ratio of 1:3, and deionized water was added to prepare a 3wt% suspension. Glass fibers were immersed in the suspension for 30 minutes. The active groups such as amino groups in the gelatin molecules could combine with the hydroxyl groups on the surface of nano-silica, and an adsorption layer was formed on the surface of the glass fibers. After being removed, the glass fibers were dried at 100℃ for 2 hours to obtain pretreated glass fibers.

[0075] Basalt fibers were placed in a steam cleaning device and saturated steam at a pressure of 0.4 MPa and a temperature of 150°C was introduced for 25 minutes.

[0076] Kaolin was ground to a particle size of less than 20 μm, and deionized water was added to prepare a 20 wt% suspension. Basalt fiber was immersed in the suspension for 20 min, removed and naturally dried at room temperature for 2 h, and then placed in an oven at 100 ℃ for 3 h to obtain pretreated basalt fiber.

[0077] S3. Nano-silica activation;

[0078] Nano-silica and calcium carbonate powder (particle size ≤10μm) with a mass ratio of 5:1 were mixed and added to a planetary ball mill. Zirconia balls with a diameter of 5mm were used to ball mill the mixture at a speed of 400r / min for 3h with a ball-to-material ratio of 12:1. After ball milling, the mixture was passed through a 200-mesh sieve to obtain activated nano-silica.

[0079] S4. Preparation of dispersants;

[0080] Mica tailings were mixed with industrial-grade hydrofluoric acid (50% by mass) at a solid-liquid ratio of 1:3 and stirred in a 70°C water bath for 3 hours. The hydrofluoric acid was used to erode the silicon and aluminum oxides in the mica tailings to achieve preliminary extraction and activation of the components. The mixture was repeatedly washed with deionized water until neutral and then spray-dried (air inlet temperature 200°C) to prepare mica-based nanocarriers.

[0081] Konjac glucomannan (KGM) was prepared into a 3 wt% aqueous solution. Ferric sulfate was then added to the KGM solution to... The Fe-KGM complex was formed by stirring at room temperature for 60 min with KGM at a mass ratio of 1:12. Tannic acid was then added at a mass ratio of 1:0.6 to the Fe-KGM complex, and stirring continued for 2 h. The phenolic hydroxyl groups in the tannic acid reacted with... A coordination reaction occurs to form a TA-Fe-KGM complex. Under stirring conditions, a mica-based nanocarrier dispersion (15% solid content) grafted with polymer is slowly added dropwise. After the addition is complete, the reaction is carried out at 50°C for 3 hours. The TA-Fe-KGM complex interacts with the polymer chains on the surface of the mica-based nanocarrier through hydrogen bonding and electrostatic interaction, encapsulating and stabilizing the nanocarrier to obtain a dispersant.

[0082] S5. Preparation of the expanding agent;

[0083] Boron mud, carbide slag, and sodium humate with a particle size ≤10μm were fed into a planetary ball mill at a mass ratio of 60:35:30, with alumina balls as the grinding medium and a ball-to-material ratio of 8:1. The mixture was ground at 400r / min for 3h to obtain the expanding agent.

[0084] S6. Weigh the raw materials;

[0085] 40 parts of aluminate cement; aluminate cement has the characteristics of rapid hardening and early strength, which can significantly shorten the setting time of grouting materials, thereby effectively preventing further leakage of gas and liquid;

[0086] 15 parts of early-strength agent; promotes cement hydration reaction, and in areas of the mine where a support structure needs to be formed quickly, it can enable the cement to have a certain strength in the early stage, ensuring operational safety;

[0087] 20 parts of expansion agent; it expands in volume during hydration, compensating for shrinkage during material hardening, improving adhesion to cracks or hole walls, and preventing secondary leakage;

[0088] Five parts of activated nano-silica; Nano-silica has extremely high specific surface area and activity, which can fill the pores of cement stone, improve the microstructure, and enhance the density and strength of the material. In the sealing of micropores or cracks, nano-silica can effectively improve the sealing performance of the sealing material.

[0089] 1.5 parts of fiber-reinforced material; pretreated glass fiber and pretreated basalt fiber with a mass ratio of 0.7:1.6 are selected; the basalt fiber is 15 mm long and 35 μm in diameter; the glass fiber is 12 mm long and 30 μm in diameter; the fiber-reinforced material has toughness, prevents crack propagation, and improves the impact resistance of the sealing material;

[0090] 1.2 parts of dispersant; effectively improves the dispersibility of raw materials, enhances the uniformity and flowability of materials, ensures thorough mixing of raw materials during preparation, and guarantees stable performance of reinforcing agents;

[0091] S7. Raw material compounding;

[0092] Add the dispersant to ethanol to prepare a 10wt% solution. Stir the solution at 2000r / min for 15min using a high-speed disperser to prepare a uniform dispersion. Slowly add the activated nano-silica to the dispersion and continue stirring for 30min to fully disperse the nano-silica and avoid agglomeration.

[0093] Pretreated glass fiber and pretreated basalt fiber were added to a mixer and dry-mixed at 500 r / min for 10 min to obtain mixed fiber. The mixed fiber was then added to a dispersion containing activated nano silica and stirred at 200 r / min for 20 min to allow the fiber surface to uniformly adsorb the dispersion and enhance the interfacial bonding force between the fiber and other raw materials.

[0094] Add aluminate cement, early strength agent and expansion agent to a high-pressure mixer and dry mix at 300 r / min for 15 min to ensure that the cement and admixtures are in full contact. Add the dispersion containing fiber and nano silica to the mixer and increase the speed to 800 r / min. Wet mix for 30 min to ensure that the raw materials are evenly distributed in the cement matrix and form a mixture with good fluidity and plasticity.

[0095] The mixture is granulated using a granulator to produce particles with a diameter of 5 mm. The particles are then placed in a drying oven and dried at 80°C for 3 hours to remove ethanol, thereby increasing the particle strength and facilitating storage and transportation, thus obtaining a mining plugging reinforcing agent.

[0096] Example 2: This example provides a method for preparing a mine-use sealing and reinforcing agent, including the following steps:

[0097] S1. Preparation of early strength agent;

[0098] At 25g / L 15g / L urea, 8g / L fish peptone, 3g / L yeast extract, 1g / L 0.5g / L The ratio of 5 g / L glucose, 1 g / L sodium citrate, and 0.1 g / L Lween 80 was used to dissolve each component in deionized water to obtain the culture medium (the culture medium was pre-sterilized at 121℃ for 20 minutes and then cooled to room temperature).

[0099] Take Bacillus licheniformis seed culture in the logarithmic growth phase and inoculate it into the culture medium at an inoculum rate of 5 wt%. Incubate at 35℃ and 180 r / min with shaking for 12 h, controlling dissolved oxygen ≥30%. Fermentation begins when the pH reaches 0.8;

[0100] Fermentation stage: Maintain 35℃ for 0-24 hours, adjust pH to 7.0 with sterile HCl solution, and ensure DO ≥ 30%. ≥3.0;

[0101] Within 24-48 hours, adjust the temperature to 28℃, stop adding acid, and allow the pH to rise naturally to 8.5, while keeping the dissolved oxygen (DO) at 20%.

[0102] Add 0.5g / L within 48-72 hours. Reduce the stirring speed to 100 r / min and intermittently add 5 g / L urea. When the residual... Fermentation was terminated when the concentration was ≤0.5g / L, yielding the fermentation broth;

[0103] The fermentation broth was cooled to 25°C, and 0.05 wt% cationic polyacrylamide was added for flocculation. The precipitate was collected by centrifugation at 4000 r / min for 15 min and washed three times with deionized water.

[0104] Add 2 wt% maltodextrin to the precipitate, spray dry under conditions of inlet air temperature 150℃ and outlet air temperature 70℃, and then pulverize by airflow. ≤10μm ≤20μm;

[0105] Add 2wt% silane coupling agent (KH-550) and treat in a high-speed mixer (5000r / min, 10min), then mix with 5wt% calcium nitrate to obtain the early strength agent;

[0106] S2. Fiber pretreatment;

[0107] Using a belt sander, glass fibers are fed through a conveyor belt at a uniform speed of 5 m / min. The sander has a grit size of 200 mesh. This physical sanding increases the surface roughness of the glass fibers. The sanded glass fibers are then laid flat on the conveyor belt and passed through a drying channel at a speed of 0.5 m / min. The temperature inside the drying channel is maintained at 60°C. At the same time, airflow purging devices are installed on both sides of the channel (compressed air generated by an oil-free air compressor is filtered and dried, and then delivered to the purging nozzles through an air supply pipe). The airflow speed is 5 m / s, and the airflow direction is 30 degrees to the glass fiber conveying direction to remove the fine fiber dust and moisture generated during sanding.

[0108] Nano-silica and gelatin were mixed at a mass ratio of 1:2, and deionized water was added to prepare a 1wt% suspension. Glass fibers were immersed in the suspension for 20 minutes. The active groups such as amino groups in the gelatin molecules could combine with the hydroxyl groups on the surface of nano-silica, and an adsorption layer was formed on the surface of the glass fibers. After being removed, the glass fibers were dried at 80°C for 1 hour to obtain pretreated glass fibers.

[0109] Basalt fibers were placed in a steam cleaning device and saturated steam at a pressure of 0.2 MPa and a temperature of 120°C was introduced for 15 minutes.

[0110] Kaolin was ground to a particle size of less than 20 μm, and deionized water was added to prepare a 15 wt% suspension. Basalt fiber was immersed in the suspension for 15 min, removed and naturally dried at room temperature for 1 h, and then placed in an oven at 80 ℃ for 2 h to obtain pretreated basalt fiber.

[0111] S3. Nano-silica activation;

[0112] Nano-silica and calcium carbonate powder (particle size ≤10μm) with a mass ratio of 1:0.5 were mixed and added to a planetary ball mill. Zirconia balls with a diameter of 3mm were used, and the mixture was ball-milled at 300r / min for 2h with a ball-to-material ratio of 10:1. After ball milling, the mixture was passed through an 180-mesh sieve to obtain activated nano-silica.

[0113] S4. Preparation of dispersants;

[0114] Mica tailings were mixed with industrial-grade hydrofluoric acid (40% by mass) at a solid-liquid ratio of 1:2 and stirred in a 60°C water bath for 2 hours. The hydrofluoric acid was used to erode the silicon and aluminum oxides in the mica tailings to achieve preliminary extraction and activation of the components. The mixture was repeatedly washed with deionized water until neutral and then spray-dried (inlet air temperature 180°C) to prepare mica-based nanocarriers.

[0115] Konjac glucomannan (KGM) was prepared into a 1 wt% aqueous solution. Ferric sulfate was then added to the KGM solution to... The Fe-KGM complex was formed by stirring at room temperature for 30 minutes with KGM at a mass ratio of 1:8. Tannic acid was then added at a mass ratio of 1:0.3 to the Fe-KGM complex, and stirring continued for 1 hour. The phenolic hydroxyl groups in the tannic acid reacted with... A coordination reaction occurs to form a TA-Fe-KGM complex. Under stirring conditions, a mica-based nanocarrier dispersion (10% solid content) grafted with polymer is slowly added dropwise. After the addition is complete, the reaction is carried out at 40°C for 2 hours. The TA-Fe-KGM complex interacts with the polymer chains on the surface of the mica-based nanocarrier through hydrogen bonding and electrostatic interaction, encapsulating and stabilizing the nanocarrier to obtain a dispersant.

[0116] S5. Preparation of the expanding agent;

[0117] Boron mud, carbide slag, and sodium humate with a particle size ≤10μm were fed into a planetary ball mill at a mass ratio of 40:20:15, with alumina balls as the grinding medium and a ball-to-material ratio of 6:1. The mixture was ground at 300r / min for 2h to obtain the expanding agent.

[0118] S6. Weigh the raw materials;

[0119] 20 parts of aluminate cement; aluminate cement has the characteristics of rapid hardening and early strength, which can significantly shorten the setting time of grouting materials, thereby effectively preventing further leakage of gas and liquid;

[0120] Five parts of early-strength agent; promotes cement hydration reaction, and in areas of the mine where a support structure needs to be formed quickly, it can enable the cement to have a certain strength in the early stage, ensuring operational safety;

[0121] Eight parts of expanding agent; it expands in volume during hydration, compensating for shrinkage during material hardening, improving adhesion to cracks or hole walls, and preventing secondary leakage.

[0122] One part of activated nano-silica; Nano-silica has extremely high specific surface area and activity, which can fill the pores of cement stone, improve the microstructure, and enhance the density and strength of the material. In the sealing of micropores or cracks, nano-silica can effectively improve the sealing performance of the sealing material.

[0123] 0.8 parts of fiber-reinforced material; pretreated glass fiber and pretreated basalt fiber with a mass ratio of 0.3:0.5 are selected; the basalt fiber is 5 mm long and 15 μm in diameter; the glass fiber is 4 mm long and 12 μm in diameter; the fiber-reinforced material has toughness, prevents crack propagation, and improves the impact resistance of the sealing material;

[0124] 0.5 parts of dispersant; can effectively improve the dispersibility of raw materials, enhance the uniformity and flowability of materials, ensure that the raw materials are fully mixed during the preparation process, and ensure the stability of the reinforcing agent performance;

[0125] S7. Raw material compounding;

[0126] Add the dispersant to ethanol to prepare a 5 wt% solution. Stir the solution at 1500 r / min for 10 min using a high-speed disperser to prepare a uniform dispersion. Slowly add the activated nano-silica to the dispersion and continue stirring for 20 min to fully disperse the nano-silica and avoid agglomeration.

[0127] Pretreated glass fiber and pretreated basalt fiber are added to a mixer and dry-mixed at 300-500 r / min for 5 min to obtain mixed fiber. The mixed fiber is then added to a dispersion containing activated nano silica and stirred at 100 r / min for 15 min to allow the fiber surface to uniformly adsorb the dispersion and enhance the interfacial bonding force between the fiber and other raw materials.

[0128] Add aluminate cement, early strength agent and expansion agent to a high-pressure mixer and dry mix at 200 r / min for 10 min to ensure that the cement and admixtures are in full contact. Add the dispersion containing fiber and nano silica to the mixer and increase the speed to 500 r / min. Wet mix for 20 min to ensure that the raw materials are evenly distributed in the cement matrix and form a mixture with good fluidity and plasticity.

[0129] The mixture is granulated using a granulator to produce particles with a diameter of 2 mm. The particles are then placed in a drying oven and dried at 60°C for 2 hours to remove ethanol, thereby increasing the particle strength and facilitating storage and transportation, thus obtaining a mine-use sealing and reinforcing agent.

[0130] Example 3: This example provides a method for preparing a mine-use plugging and reinforcing agent, including the following steps:

[0131] S1. Preparation of early strength agent;

[0132] At 32g / L 21g / L urea, 9g / L fish peptone, 5g / L yeast extract, 1.2g / L 0.7g / L The medium was prepared by dissolving 7 g / L glucose, 2 g / L sodium citrate, and 0.2 g / L sodium citrate in a ratio of 80 L / L to deionized water to obtain the culture medium (the culture medium was pre-sterilized at 121℃ for 20 minutes and then cooled to room temperature).

[0133] Take Bacillus licheniformis seed culture in the logarithmic growth phase and inoculate it into the culture medium at an inoculum rate of 6 wt%. Incubate at 36℃ and 180 r / min with shaking for 15 h, controlling dissolved oxygen ≥30%. Fermentation begins when the pH reaches 0.9;

[0134] Fermentation stage: Maintain 36℃ for 0-24 hours, adjust pH to 7.3 with sterile HCl solution, and ensure DO ≥ 30%. ≥3.0;

[0135] Within 24-48 hours, adjust the temperature to 30℃, stop adding acid, and allow the pH to rise naturally to 8.7, while keeping the dissolved oxygen (DO) at 25%.

[0136] Add 0.6 g / L within 48-72 hours. Reduce the stirring speed to 120 r / min and intermittently add 8 g / L urea. When the residual Fermentation was terminated when the concentration was ≤0.5g / L, yielding the fermentation broth;

[0137] The fermentation broth was cooled to 25°C, and 0.08 wt% cationic polyacrylamide was added for flocculation. The precipitate was collected by centrifugation at 4300 r / min for 18 min and washed three times with deionized water.

[0138] Add 3 wt% maltodextrin to the precipitate, spray dry under conditions of inlet air temperature 157℃ and outlet air temperature 77℃, and then pulverize by airflow. ≤10μm ≤20μm;

[0139] Add 2.8wt% silane coupling agent (KH-550) and treat in a high-speed mixer (5000r / min, 10min), then mix with 8wt% calcium nitrate to obtain the early strength agent;

[0140] S2. Fiber pretreatment;

[0141] Using a belt sander, glass fibers are fed through a conveyor belt at a uniform speed of 6 m / min. The sander has a grit size of 300 mesh. This physical sanding increases the surface roughness of the glass fibers. The sanded glass fibers are then laid flat on the conveyor belt and passed through a drying channel at a speed of 0.7 m / min. The temperature inside the drying channel is maintained at 70°C. At the same time, airflow purging devices are installed on both sides of the channel (compressed air generated by an oil-free air compressor is filtered and dried, and then delivered to the purging nozzles through an air supply pipe). The airflow speed is 5 m / s, and the airflow direction is 30 degrees to the glass fiber conveying direction to remove the fine fiber dust and moisture generated during sanding.

[0142] Nano-silica and gelatin were mixed at a mass ratio of 1:2, and deionized water was added to prepare a 2wt% suspension. Glass fibers were immersed in the suspension for 26 minutes. The active groups such as amino groups in the gelatin molecules could combine with the hydroxyl groups on the surface of nano-silica, and an adsorption layer was formed on the surface of the glass fibers. After being removed, the glass fibers were dried at 95°C for 2 hours to obtain pretreated glass fibers.

[0143] Basalt fibers were placed in a steam cleaning device and saturated steam at a pressure of 0.2 MPa and a temperature of 140°C was introduced for 22 minutes.

[0144] Kaolin was ground to a particle size of less than 20 μm, and deionized water was added to prepare a 16 wt% suspension. Basalt fibers were immersed in the suspension for 17 min, removed and naturally dried at room temperature for 2 h, and then placed in an oven at 85 ℃ for 2.5 h to obtain pretreated basalt fibers.

[0145] S3. Nano-silica activation;

[0146] Nano-silica and calcium carbonate powder (particle size ≤10μm) with a mass ratio of 4:0.7 were mixed and added to a planetary ball mill. Zirconia balls with a diameter of 4mm were used to ball mill the mixture at a speed of 360r / min for 2h with a ball-to-material ratio of 11:1. After ball milling, the mixture was passed through a 200-mesh sieve to obtain activated nano-silica.

[0147] S4. Preparation of dispersants;

[0148] Mica tailings were mixed with industrial-grade hydrofluoric acid (46% by mass) at a solid-liquid ratio of 1:2 and stirred in a water bath at 62°C for 2 hours. The hydrofluoric acid was used to erode the silicon and aluminum oxides in the mica tailings to achieve preliminary extraction and activation of the components. The mixture was repeatedly washed with deionized water until neutral and then spray-dried (inlet air temperature 188°C) to prepare mica-based nanocarriers.

[0149] Konjac glucomannan (KGM) was prepared into a 2 wt% aqueous solution. Ferric sulfate was then added to the KGM solution to... The Fe-KGM complex was formed by stirring at room temperature for 40 min with KGM at a mass ratio of 1:11. Tannic acid was then added at a mass ratio of 1:0.5 to the Fe-KGM complex, and stirring continued for 1 h. The phenolic hydroxyl groups in the tannic acid reacted with... A coordination reaction occurs to form a TA-Fe-KGM complex. Under stirring conditions, a mica-based nanocarrier dispersion (12% solid content) grafted with polymer is slowly added dropwise. After the addition is complete, the reaction is carried out at 43℃ for 2 hours. The TA-Fe-KGM complex interacts with the polymer chains on the surface of the mica-based nanocarrier through hydrogen bonding and electrostatic interaction, encapsulating and stabilizing the nanocarrier to obtain a dispersant.

[0150] S5. Preparation of the expanding agent;

[0151] Boron mud, carbide slag, and sodium humate with a particle size ≤10μm were fed into a planetary ball mill at a mass ratio of 52:28:20. Alumina balls were used as the grinding medium, and the ball-to-material ratio was 7:1. The mixture was ground at 380r / min for 2h to obtain the expanding agent.

[0152] S6. Weigh the raw materials;

[0153] 32 parts of aluminate cement; aluminate cement has the characteristics of rapid hardening and early strength, which can significantly shorten the setting time of grouting materials, thereby effectively preventing further leakage of gas and liquid;

[0154] 12 parts of early-strength agent; promotes cement hydration reaction, and in areas of the mine where a support structure needs to be formed quickly, it can enable the cement to have a certain strength in the early stage, ensuring operational safety;

[0155] 12 parts of expansion agent; it expands in volume during hydration, compensates for shrinkage during material hardening, improves adhesion to cracks or hole walls, and prevents secondary leakage.

[0156] Three parts of activated nano-silica; nano-silica has extremely high specific surface area and activity, which can fill the pores of cement stone, improve the microstructure, and enhance the density and strength of the material. In the sealing of micropores or cracks, nano-silica can effectively improve the sealing performance of the sealing material.

[0157] 1.2 parts of fiber-reinforced material; pretreated glass fiber and pretreated basalt fiber with a mass ratio of 0.4:1.2 are selected; the basalt fiber is 10 mm long and 20 μm in diameter; the glass fiber is 8 mm long and 22 μm in diameter; the fiber-reinforced material is used to enhance the toughness of the material, prevent crack propagation, and improve the impact resistance of the sealing material.

[0158] Dispersant 0.8 parts; can effectively improve the dispersibility of raw materials, enhance the uniformity and flowability of materials, ensure that the raw materials are fully mixed during the preparation process, and ensure the stability of the reinforcing agent performance;

[0159] S7. Raw material compounding;

[0160] Add the dispersant to ethanol to prepare a solution with a concentration of 8wt%. Stir the solution at 1700r / min for 12min using a high-speed disperser to prepare a uniform dispersion. Slowly add the activated nano-silica to the dispersion and continue stirring for 24min to fully disperse the nano-silica and avoid agglomeration.

[0161] Pretreated glass fiber and pretreated basalt fiber were added to a mixer and dry-mixed at 400 r / min for 8 min to obtain mixed fiber. The mixed fiber was added to a dispersion containing activated nano silica and stirred at 160 r / min for 17 min to make the fiber surface uniformly adsorb the dispersion and enhance the interfacial bonding force between the fiber and other raw materials.

[0162] Add aluminate cement, early strength agent and expansion agent to a high-pressure mixer and dry mix at 270 r / min for 12 min to ensure that the cement and admixtures are in full contact. Add the dispersion containing fiber and nano silica to the mixer and increase the speed to 700 r / min. Wet mix for 22 min to ensure that each raw material is evenly distributed in the cement matrix and form a mixture with good fluidity and plasticity.

[0163] The mixture is granulated using a granulator to produce particles with a diameter of 4 mm. The particles are then placed in a drying oven and dried at 75°C for 2.5 hours to remove ethanol, thereby increasing the particle strength and facilitating storage and transportation, thus obtaining a mine-use sealing and reinforcing agent.

[0164] Comparative Example 1: The difference between this comparative example and Example 3 is that, in the preparation of the early strength agent, the Bacillus licheniformis seed liquid was not fermented after being inoculated into the culture medium, but was directly cooled and cationic polyacrylamide was added for flocculation.

[0165] Comparative Example 2: The difference between this comparative example and Example 3 is that, in the preparation of the dispersant, konjac glucomannan was replaced with unprocessed and purified konjac flour.

[0166] Comparative Example 3: The difference between this comparative example and Example 3 is that konjac glucomannan was replaced with unprocessed and purified konjac flour, and Bacillus licheniformis seed liquid was inoculated into the culture medium but not fermented.

[0167] Experimental Example: 1. The initial setting time of the mine-use sealing and reinforcing agent (belonging to the category of ultra-fast hardening cement) prepared according to GB / T1346-2011 standard at 25℃ and 50% humidity was tested. (i.e., the time it takes to lose fluidity, in seconds) and the initial setting time at 2°C and 95% humidity. (s).

[0168] The results are shown in Table 1;

[0169] Table 1

[0170]

[0171] As shown in the table above, this invention involves inoculating the seed liquid of Bacillus licheniformis into a solution containing... Urea, fish peptone, yeast extract, , The culture medium made of glucose, sodium citrate and Tween 80 was fermented, which significantly improved the initial coagulation rate.

[0172] The TA-Fe-KGM complex formed by processed and purified konjac glucomannan, ferric sulfate, and tannic acid effectively improves the stability of coagulation performance under low temperature and high humidity conditions.

[0173] When combined, the two have a synergistic effect on improving the initial setting rate and the stability of solidification performance under low temperature and high humidity conditions.

[0174] The principle is as follows: Bacillus licheniformis thrives in environments rich in... Fermentation in a culture medium containing urea and other components involves the secretion of carbonic anhydrase, a enzyme produced during metabolic activity. This anhydrase plays a crucial catalytic role, promoting the breakdown of urea into... and . Rapidly and in the system A chemical reaction occurs, generating calcium carbonate crystal nuclei. These nuclei provide the initial framework for the crystallization of cement hydration products, greatly accelerating the crystallization process and effectively shortening the initial setting time. Aluminate cement itself possesses the characteristics of rapid hardening and early strength; its mineral components can quickly initiate a hydration reaction upon contact with water, further promoting the rapid setting of the entire system.

[0175] Konjac glucomannan (KGM), as a hydrophilic polymer, forms numerous hydrogen bonds with water molecules due to the abundance of hydroxyl groups on its molecular chains. In high-humidity environments, it can buffer the excessive wetting of the cement matrix by water, preventing excessive dilution of hydration products and hindering solidification. At low temperatures, the flexibility of KGM molecular chains decreases, exhibiting a more ordered arrangement and constructing a relatively stable three-dimensional network structure. This maintains the continuous advancement of the cement hydration reaction and prevents the reaction from stagnating or being delayed due to lower temperatures. A stable TA-Fe-KGM complex is formed through coordination with the hydroxyl groups of KGM and the phenolic hydroxyl groups of tannic acid (TA). When the temperature and humidity fluctuate, the coordination bonds can be reversibly broken and recombined to flexibly adjust the microstructure and reactivity of the system, ensuring that the solidification process is not disturbed by the environment and achieves initial solidification stably and efficiently.

[0176] The calcium carbonate nuclei generated by the accelerator provide numerous starting sites for cement hydration, accelerating the formation of hydration products. The TA-Fe-KGM complex, with its regulation of water molecules and stable network structure, ensures a relatively stable reaction environment in the early stages of cement hydration, providing a suitable microenvironment for the accelerator's effect. In high-humidity environments, KGM adsorbs excessive moisture, preventing it from interfering with the formation of calcium carbonate nuclei in the accelerator and the cement hydration reaction. In low-temperature environments, the TA-Fe-KGM complex maintains the system's reactivity, allowing the accelerator to continuously exert its setting-promoting effect, jointly promoting rapid cement setting and significantly increasing the initial setting rate.

[0177] 2. The compressive strength of the mine sealing and reinforcing agent prepared according to GB / T17671-2021 was tested at 2℃ and 95% humidity for 2h, 4h, 8h and 24h after curing.

[0178] The results are shown in Table 2;

[0179] Table 2

[0180]

[0181] As shown in the table above, inoculating the Bacillus licheniformis seed liquid into a culture medium made from the above raw materials and then fermenting it significantly improved the early compressive strength.

[0182] The principle is as follows: The fermentation products of Bacillus licheniformis in the early-strength agent, besides generating calcium carbonate crystal nuclei to accelerate initial setting, also act together with calcium nitrate in the cement hydration reaction. The calcium nitrate releases [resources / products] after dissolving. On the one hand, it provides sufficient raw materials for the formation of cement hydration products, and on the other hand, it promotes the hydration reaction of tricalcium aluminate, rapidly generating a large amount of ettringite. Tettringite grows in the form of needle-like or rod-like crystals, which interweave to form a dense network structure, giving the material high early strength.

[0183] 3. The impermeability grade of the examples and comparative examples was tested according to GB50164-2011 standard (P8 indicates that it can resist hydrostatic pressure above 0.8MPa, and concrete with an impermeability grade ≥P6 is impermeable concrete).

[0184] Gas permeability (mD: millidarcy) was measured according to API Std 65-2 (2010) standard.

[0185] The results are shown in Table 3;

[0186] Table 3

[0187]

[0188] As shown in the table above, the mine sealing and reinforcing agent prepared by this invention exhibits excellent sealing performance in both gaseous and liquid two-phase media environments and has excellent anti-leakage capability.

[0189] The principle is as follows: During hydration, components in the expanding agent, such as boron mud and carbide slag, undergo complex chemical reactions to generate products like ettringite, which has expanding properties. As the reaction proceeds, the ettringite crystals continuously grow, causing volume expansion and tightly filling defects such as rock cracks and pores. This macroscopically blocks the flow channels of gas and liquid, forming the first physical barrier. Sodium humate, as an expanding regulator, precisely controls the rate of the expansion reaction, ensuring that the expansion process is synchronized with the cement setting and hardening process, avoiding secondary leakage problems caused by expansion that is too early or too late.

[0190] Glass fiber and basalt fiber form a three-dimensional network structure within the material. When used for sealing, the fiber network effectively traps cement particles, reducing the loss of cement slurry under pressure and improving the slurry's impermeability. At cracks or pores, the fibers enhance the bond strength between the sealing material and the surrounding rock mass through bridging and anchoring, preventing the sealing material from detaching under gas or liquid pressure and maintaining the stability of the sealing structure.

[0191] Nano-silica further optimizes the sealing performance of materials at the microscale. Its ability to fill micropores significantly reduces the internal porosity of the material, resulting in a marked decrease in gas permeability. Simultaneously, the gel generated from the reaction of nano-silica with volcanic ash not only fills the pores but also forms a dense gel film on the pore surface, further blocking the permeation of gases and liquids. After the components are combined, a multi-level sealing system is formed, from the macroscopic filling of the expanding agent and the network reinforcement of the fibers to the microscopic densification of nano-silica.

[0192] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A mine-use sealing and reinforcing agent, characterized in that, Includes the following components: 20-40 parts of aluminate cement; Early-strength agent 5-15 parts; inoculated with Bacillus licheniformis seed liquid by... Urea, fish peptone, yeast extract, , It was obtained by fermentation in a medium made of glucose, sodium citrate and Tween 80; 8-20 parts of expanding agent; It is obtained by mixing and grinding boron mud, carbide slag and sodium humate; 1-5 parts of activated nano-silica; 0.8-1.5 parts of fiber-reinforced material; composed of pretreated glass fiber and pretreated basalt fiber in a mass ratio of 0.3-0.7:0.5-1.6; Dispersant 0.5-1.2 parts; It was obtained by loading TA-Fe-KGM complex onto a mica-based nanocarrier; A method for preparing a mine-use sealing and reinforcing agent, characterized by comprising the following steps: S1. Preparation of early strength agent; Will Urea, fish peptone, yeast extract, , Glucose, sodium citrate, and Tween 80 are dissolved in water to obtain the culture medium; Bacillus licheniformis seed culture was inoculated into a culture medium, shaken, and then fermented to obtain a fermentation broth; After the fermentation broth is cooled, cationic polyacrylamide is added for flocculation, and the precipitate is collected by centrifugation. Add maltodextrin to the precipitate, then spray dry and pulverize. After adding a silane coupling agent and mixing it with calcium nitrate, an early strength agent is obtained. S2. Fiber pretreatment; Use a belt sander to sand the glass fiber and then dry it; Nano-silica is mixed with gelatin and water is added to prepare a suspension. Glass fibers are immersed in the suspension, removed and dried to obtain pretreated glass fibers. Kaolin was ground and mixed with water to prepare a suspension. The washed basalt fibers were immersed in the suspension, removed and dried to obtain pretreated basalt fibers. S3. Nano-silica activation; After mixing nano-silica and calcium carbonate powder, the mixture is ball-milled and sieved to obtain activated nano-silica. S4. Preparation of dispersants; Mica tailings were mixed and stirred with industrial-grade hydrofluoric acid, and then spray-dried to obtain mica-based nanocarriers. Ferric sulfate was added to the konjac glucomannan solution to form a Fe-KGM complex. Tannic acid was added and stirred to form a TA-Fe-KGM complex. Mica-based nanocarrier dispersion was added dropwise, and the reaction yielded a dispersant. S5. Preparation of the expanding agent; Boron mud, carbide slag, and sodium humate are mixed and ground to obtain an expanding agent; S6. Raw material compounding; The dispersant is prepared into a solution and stirred to form a uniform dispersion. Activated nano-silica is then added to the dispersion. Pretreated glass fiber and pretreated basalt fiber are added to a mixer and dry-mixed to obtain mixed fiber. The mixed fiber is then added to a dispersion. Aluminate cement, early strength agent and expansion agent are dry-mixed, and then the dispersion liquid is added and wet-mixed to form a mixture; The mixture is granulated and dried using a granulator to obtain a mine-use sealing and reinforcing agent.

2. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, S1 specifically refers to: 25-35g / L 15-25 g / L urea, 8-12 g / L fish peptone, 3-6 g / L yeast extract, 1-1.5 g / L 0.5-1g / L The medium is prepared by dissolving the components in deionized water at a ratio of 5-10 g / L glucose, 1-3 g / L sodium citrate, and 0.1-0.3 g / L LT (within 80) to obtain the culture medium. Take seed culture of Bacillus licheniformis in the logarithmic growth phase and inoculate it into the culture medium at an inoculum rate of 5-8 wt%. Incubate at 35-38℃ and 180-200 r / min with shaking for 12-16 h, controlling dissolved oxygen ≥30%. Fermentation begins when the temperature reaches 0.8-1.0, yielding a fermentation broth; After the fermentation broth is cooled, add 0.05-0.1 wt% cationic polyacrylamide for flocculation, centrifuge at 4000-5000 r / min for 15-20 min to collect the precipitate, and wash it 3 times with deionized water. Add 2-5 wt% maltodextrin to the precipitate, spray dry under conditions of inlet air temperature 150-160℃ and outlet air temperature 70-80℃, and then pulverize by airflow. ≤10μm ≤20μm; Add 2-3 wt% silane coupling agent, treat in a high-speed mixer, and then mix with 5-10 wt% calcium nitrate to obtain an early strength agent.

3. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, The specific fermentation steps are as follows: maintain a temperature of 35-38℃ for 0-24 hours, adjust the pH to 7.0-7.5 with HCl solution, and ensure DO ≥ 30%. ≥3.0; Within 24-48 hours, adjust the temperature to 28-30℃, stop adding acid, and allow the pH to rise naturally to 8.5-9.0, while maintaining the dissolved oxygen (DO) at 20-30%. Add 0.5-1 g / L within 48-72 hours. Reduce the stirring speed to 100-150 r / min and intermittently add 5-10 g / L of urea. When the residual... Fermentation was terminated when the concentration was ≤0.5g / L, yielding the fermentation broth.

4. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, The specific steps of glass fiber pretreatment are as follows: using a belt sander, the glass fiber is passed through the sander at a speed of 5-10m / min, the sander has a grit size of 200-400 mesh, the sanded glass fiber is laid flat on the conveyor belt, and passes through the drying channel equipped with an airflow blowing device at a speed of 0.5-1m / min, the temperature in the drying channel is maintained at 60-80℃. Nano-silica and gelatin are mixed at a mass ratio of 1:2-3, and deionized water is added to prepare a suspension of 1-3 wt%. Glass fibers are immersed in the suspension for 20-30 minutes, and then dried at 80-100℃ for 1-2 hours to obtain pretreated glass fibers.

5. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, The specific pretreatment steps for basalt fiber are as follows: place the basalt fiber in a steam cleaning device, introduce saturated steam at a pressure of 0.2-0.4 MPa and a temperature of 120-150℃, and treat for 15-25 minutes; Kaolin is ground to a particle size of less than 20 μm, and deionized water is added to prepare a suspension of 15-20 wt%. Basalt fibers are immersed in the suspension for 15-20 min, removed and naturally dried at room temperature for 1-2 h, and then dried in an oven at 80-100 ℃ for 2-3 h to obtain pretreated basalt fibers.

6. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, S3 specifically involves mixing nano-silica and calcium carbonate powder in a mass ratio of 1-5:0.5-1, adding the mixture to a planetary ball mill, using zirconia balls with a diameter of 3-5 mm, and ball milling at a speed of 300-400 r / min for 2-3 hours with a ball-to-material ratio of 10-12:

1. After ball milling, the mixture is passed through a 180-200 mesh sieve to obtain activated nano-silica.

7. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, S4 specifically involves mixing mica tailings with industrial-grade hydrofluoric acid at a solid-liquid ratio of 1:2-3, stirring in a water bath at 60-70℃ for 2-3 hours, repeatedly washing with deionized water until neutral, and then preparing mica-based nanocarriers by spray drying. Konjac glucomannan was prepared into a 1-3 wt% aqueous solution. Ferric sulfate was added to the KGM solution to make... The mass ratio of Fe-KGM to KGM is 1:8-12. Stir at room temperature for 30-60 min to form Fe-KGM complex. Add tannic acid at a mass ratio of Fe-KGM complex to tannic acid of 1:0.3-0.6 and continue stirring for 1-2 h to form TA-Fe-KGM complex. Under stirring conditions, slowly add the mica-based nanocarrier dispersion grafted with polymer. After the addition is complete, react at 40-50℃ for 2-3 h to obtain the dispersant.

8. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, S5 specifically involves feeding boron mud, carbide slag, and sodium humate with a particle size ≤10μm into a planetary ball mill at a mass ratio of 40-60:20-35:15-30, using alumina balls as the grinding medium, with a ball-to-material ratio of 6-8:1, and mixing and grinding at 300-400r / min for 2-3 hours to obtain the expanding agent.

9. The preparation method of the mine-use plugging and reinforcing agent according to claim 1, characterized in that, S6 specifically involves: adding ethanol to the dispersant to prepare a solution with a concentration of 5-10 wt%, stirring it for 10-15 minutes using a high-speed disperser at a speed of 1500-2000 r / min to prepare a uniform dispersion, slowly adding activated nano-silica to the dispersion, and continuing to stir for 20-30 minutes. Add pretreated glass fiber and pretreated basalt fiber to a mixer and dry mix at 300-500 r / min for 5-10 min to obtain mixed fiber. Add the mixed fiber to a dispersion containing activated nano silica and stir at 100-200 r / min for 15-20 min. Add aluminate cement, early strength agent and expansion agent to a high-strength mixer and dry mix at a speed of 200-300 r / min for 10-15 min. Add the dispersion containing fiber and nano silica to the mixer and increase the speed to 500-800 r / min. Wet mix for 20-30 min to form a mixture with good fluidity and plasticity. The mixture is granulated using a granulator to produce particles with a diameter of 2-5 mm. The particles are then placed in a drying oven and dried at 60-80℃ for 2-3 hours to remove ethanol, thus obtaining a mining plugging enhancer.

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