High-water filling fire extinguishing material, preparation method, grouting system and construction process

Abstract

The application discloses a high-water filling fire extinguishing material, which comprises an A component and a B component, wherein the A component comprises cement 30 parts, suspending agent 0.9 parts and retarder 0.1-0.2 parts, and the B component comprises hemihydrate gypsum 30 parts and coagulant 0.135-0.48 parts. The application forms a synergistic compound system of the coagulant and the retarder, so that the high-water filling fire extinguishing material can still realize controllable adjustment of setting time under the condition of high water-cement ratio. The setting time range is controlled by controlling the adding proportion of the two compound additives. The application further discloses a preparation method, a grouting system and a construction process of the material. The A slurry and the B slurry are prepared and transported respectively, mixed in a spiral mixing pipe with different pitch sections, and output through a grouting pipeline.

Description

Technical Field

[0001] This application belongs to the technical field of high-water-filled fire extinguishing materials, specifically relating to a high-water-filled fire extinguishing material, its preparation method, grouting system, and construction process. Background Technology

[0002] High-water filling materials are inorganic cementitious materials developed in the 1980s. As pumpable support / fire extinguishing materials, they have gradually replaced easily exothermic and highly polluting polymer filling materials due to their advantages such as convenient material sourcing and low cost. They are widely used in mine support, filling, and fire extinguishing scenarios. This type of material is usually composed of two components, A and B. Component A is mostly silicate / sulfoaluminate cement + admixtures, and component B is mostly gypsum, lime + admixtures. The two components are mixed separately in a 1:1 mass ratio with the same water-cement ratio and then transported to the site for mixing and setting through pipelines. It has the characteristics of long-term non-setting, non-clogging, and pumpability.

[0003] In the prior art, although there are reports of adding retarders to component A and accelerators to component B, the retarders and accelerators in the prior art are mainly single components, and the existing high-water backfill materials generally have the problem of long and uncontrollable setting time. Summary of the Invention

[0004] In order to overcome the above-mentioned defects of the prior art, this application provides a high-water filling fire extinguishing material, a preparation method, a grouting system and a construction process to solve the problems of long setting time of current high-water filling materials, difficulty in adjusting according to grouting distance and construction conditions, resulting in high filling cost and poor filling effect.

[0005] To achieve the above objectives, this application provides the following technical solution: A high-water-filled fire extinguishing material includes component A and component B. Component A, by weight, comprises: The composition includes 30 parts cement, 0.9 parts suspending agent, and 0.1-0.2 parts retarder. The retarder in component A is a combination of sodium polyphosphate, sodium tripolyphosphate, and citric acid. Component B includes: The mixture contains 30 parts hemihydrate gypsum and 0.135-0.48 parts coagulant. The coagulant in component B is a combination of polyaluminum chloride, sodium silicate, and sodium sulfite.

[0006] In a preferred embodiment, the suspending agent in component A is organobentonite.

[0007] In a preferred embodiment, the hemihydrate gypsum in component B is building gypsum or power plant desulfurization gypsum.

[0008] In a preferred embodiment, the retarder is composed of 0.065 to 0.13 parts of sodium polyphosphate, 0.023 to 0.05 parts of sodium tripolyphosphate, and 0.012 to 0.02 parts of citric acid.

[0009] In a preferred embodiment, the coagulant is composed of 0.1 to 0.4 parts of polyaluminum chloride, 0.02 to 0.05 parts of sodium silicate, and 0.015 to 0.03 parts of sodium sulfite.

[0010] A method for preparing a high-water-filled fire extinguishing material includes the following steps: Weigh each component according to the formula, mix the suspending agent and retarder evenly, add them to water, and stir to make slurry A1; add the coagulant to water and stir to make slurry B1; Silicate cement was added to grout A1 and stirred to obtain grout A2; hemihydrate gypsum was added to grout B1 and stirred to obtain grout B2. After mixing slurry A2 and slurry B2 evenly, a high-water filling fire extinguishing material is prepared.

[0011] In a preferred embodiment, the mass ratio of the retarder in component A to the coagulant in component B is 0.208 to 1.481.

[0012] In a preferred embodiment, the stirring time is 1 to 2 minutes, the slurry A2 and slurry B2 are mixed in a 1:1 ratio, and the water-cement ratio of slurry A2 and slurry B2 is 2.5:1.

[0013] A high-water-filled fire extinguishing material grouting system includes a spiral mixing pipe and a first feeding section, a second feeding section, and a discharging section connected to the spiral mixing pipe; The spiral mixing tube is provided with a central axis turbulence rod and a spiral guide vane installed on the central axis turbulence rod. The spiral guide vane is provided with a premixing inlet section, a shearing section and an output section in sequence. The pitch of the premixing inlet section is greater than the pitch of the output section, and the pitch of the output section is greater than the pitch of the shearing section. The first feeding section includes a mixing tank for component A and a feeder and a water injection pipe disposed on the mixing tank for component A; The second feeding section includes a B-component mixing tank and a feeder and a water injection pipe disposed on the B-component mixing tank; The discharge section includes a grouting pipe.

[0014] A grouting process for high-water-filled fire extinguishing materials includes the following steps: Suspension agent, retarder and water are added to the A component mixing tank through a feeder and water injection pipe, and the mixture is stirred thoroughly for 1 to 2 minutes to obtain slurry A1; at the same time, coagulant and water are added to the B component mixing tank, and the mixture is stirred thoroughly for 1 to 2 minutes to obtain slurry B1.

[0015] Silicate cement is added to the A component mixing tank via a feeder and stirred thoroughly for 1-2 minutes to obtain slurry A2; hemihydrate gypsum is added to the B component mixing tank via a feeder and stirred thoroughly for 1-2 minutes to obtain slurry B2.

[0016] Slurry A2 and slurry B2 are injected into the spiral mixing pipe through independent pipelines and mixed evenly in a 1:1 ratio.

[0017] The mixed grout is output through the grouting pipe.

[0018] The technical effects and advantages of this application are as follows: 1. This application achieves a wide-range, continuous, and controllable adjustment of the setting time of high-water backfill materials in fire zones by constructing a cross-component synergistic compounding system between a specific retarder combination (sodium polyphosphate + sodium tripolyphosphate + citric acid) in component A and a specific accelerator combination (polyaluminum chloride + sodium silicate + sodium sulfite) in component B. Adding a retarder to the cement system in component A results in a retarding effect. Adding an accelerator to the gypsum system in component B ensures the pumping stability of the single-component grout while providing a reaction basis for rapid setting after subsequent mixing. Under the above technical solution, the de-retarding effect is activated after the grout is mixed, thereby achieving rapid setting of the material. By changing the addition ratio of the accelerator and retarder, the setting time can be controllably adjusted according to actual construction needs. According to the data from the examples, the initial setting time can be continuously adjusted between 29.3 min and 5.67 min, which can be matched according to different grouting distances and construction conditions.

[0019] 2. The high-water filling fire extinguishing material with adjustable setting time described in this application possesses excellent flow characteristics, enabling smooth pumping to different distances underground without the addition of extra additives. While ensuring sufficient fluidity, it also maintains good cohesion, preventing stratification and significantly improving construction adaptability and efficiency in complex underground goaf environments. The example shows a spread of 224–286 mm, indicating that the slurry maintains good flow and distribution capabilities while ensuring pumpability, making it suitable for grouting operations in complex mine environments.

[0020] This application exhibits good mechanical properties. The compressive strengths at 3 days, 7 days, and 28 days in Example 1 were 0.63–1.22 MPa, 0.963–1.7 MPa, and 1.07–2.19 MPa, respectively, meeting the basic requirements for paste filling.

[0021] 3. The raw materials for this application are widely available. The hemihydrate gypsum can be obtained from building gypsum, or from power plant desulfurization gypsum or industrial by-product gypsum through dehydration, and has certain value for the resource utilization of solid waste.

[0022] 4. This application adopts a slurry preparation method of "mixing the admixture with water first, and then adding cement and gypsum", which is conducive to the full dispersion of the admixture and more uniform reaction with the cementitious materials, thereby improving the slurry quality and the final filling effect.

[0023] 5. This application sets up a dual-liquid grouting system and a spiral mixing pipe structure. Through the cooperation of the premixing inlet section, the enhanced shearing section and the outlet section, as well as the central axis turbulence rod, the spiral guide vane and the guide truncated pyramid, uniform mixing of A and B grouts can be achieved without increasing the additional residence time.

[0024] 6. The central axis baffle rod of this application can be installed into or removed from the spiral mixing tube as a whole, and the mixing tube is equipped with a flushing interface, which facilitates the replacement of different mixing cores and cleaning after construction, thereby reducing the risk of residual slurry solidification and blockage.

[0025] 7. The spiral mixing pipe of this application utilizes the fluid kinetic energy during the slurry pumping process to achieve mixing, without the need for an external power source, making it more suitable for complex construction environments such as underground fire zones. Attached Figure Description

[0026] Figure 1 This is a schematic diagram illustrating the preparation method of the high-water-filled fire extinguishing material of this application.

[0027] Figure 2 This is a schematic diagram of the grouting system structure of this application.

[0028] Figure 3 for Figure 2 Schematic diagram of the feed end structure of the spiral mixing tube at point A.

[0029] Figure 4 The bar chart shows the condensation time of the embodiments and comparative examples of this application.

[0030] Figure 5 The above is a bar chart showing the expansion of the embodiments and comparative examples of this application.

[0031] Figure 6 This is a bar chart showing the compressive strength of an embodiment of this application.

[0032] Figure 7 This is a comparative bar chart of the compressive strength of this application.

[0033] Figure 8 These are surface morphology diagrams of Embodiment 3 and Comparative Examples 9 and 12 of this application.

[0034] In the diagram: 1. Feeder; 2. Water injection pipe; 3. A-component mixing tank; 4. B-component mixing tank; 5. Slurry conveying pipe; 6. Grouting pump; 7. Spiral mixing pipe; 8. Flushing interface; 9. Central axis baffle; 10. Spiral guide vane; 11. Guide truncated cone; 12. Grouting pipe; 13-1. First ball valve; 13-2. Second ball valve; 13-3. Third ball valve. Detailed Implementation

[0035] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0036] like Figure 1 As shown, a high-water-filled fire extinguishing material includes component A and component B. Component A includes: 30 parts cement, 0.9 parts suspending agent, and 0.1-0.2 parts retarder. The suspending agent in Component A is organic bentonite, and the retarder in Component A is a combination of sodium polyphosphate, sodium tripolyphosphate, and citric acid.

[0037] Component B includes: 30 parts of hemihydrate gypsum and 0.135-0.48 parts of accelerator. The hemihydrate gypsum in Component B is building gypsum or power plant desulfurization gypsum. The accelerator in Component B is a combination of polyaluminum chloride, sodium silicate, and sodium sulfite.

[0038] The mass ratio of the retarder in component A to the accelerator in component B is 0.208–1.481. Specifically, the amount of sodium polyphosphate added is 0.065–0.13 parts, sodium tripolyphosphate is 0.023–0.05 parts, and citric acid is 0.012–0.02 parts; the amount of polyaluminum chloride added is 0.1–0.4 parts, sodium silicate is 0.02–0.05 parts, and sodium sulfite is 0.015–0.03 parts.

[0039] This application utilizes solid waste generated by current power plants as the main raw material, realizing the resource utilization of waste, reducing environmental pollution and alleviating the environmental burden. Furthermore, by mixing and stirring with cement, the advantages of each component are fully utilized, improving the overall performance of the material.

[0040] A method for preparing a high-water-filled fire extinguishing material includes the following steps: Weigh each component according to the formula, mix the suspending agent and retarder evenly, add them to a certain amount of water, stir for 1-2 minutes to make slurry A1; at the same time, add the coagulant to a certain amount of water, stir for 1-2 minutes to make slurry B1. Add a fixed amount of silicate cement to grout A1 and stir for 1-2 minutes to obtain grout A2; add a fixed amount of hemihydrate gypsum to grout B1 and stir for 1-2 minutes to obtain grout B2. After mixing slurry A2 and slurry B2 evenly, a high-water filling fire extinguishing material is prepared.

[0041] The mixing time is 1 to 2 minutes. Slurry A2 and slurry B2 are mixed in a 1:1 ratio. The water-cement ratio of slurry A2 and slurry B2 is 2.5:1. The water temperature is room temperature.

[0042] First, mix the suspending agent, retarder, and accelerator with water separately, then add cement and gypsum. This allows the admixtures to be more evenly dispersed in the aqueous phase. This method facilitates the full dispersion and dissolution of the admixtures in water, and promotes better reaction with cement and gypsum. It avoids the problem of uneven reaction of the admixtures when water is added after mixing the reagents with cement and gypsum, which can lead to poor results.

[0043] like Figure 2-3 The high-water-filled fire extinguishing material grouting system includes a spiral mixing pipe 7 and a first feeding section, a second feeding section, and a discharging section connected to the spiral mixing pipe 7; The spiral mixing tube 7 is provided with a central axis turbulence rod 9 and a spiral guide vane 10 installed on the central axis turbulence rod 9. The spiral guide vane 10 is provided with a premixing inlet section, a shearing section and an output section in sequence. The pitch of the premixing inlet section is greater than the pitch of the output section, and the pitch of the output section is greater than the pitch of the shearing section.

[0044] The first feeding section includes a component A mixing tank 3 and a feeder 1 and a water injection pipe 2 installed on the component A mixing tank 3; the second feeding section includes a component B mixing tank 4 and a feeder 1 and a water injection pipe 2 installed on the component B mixing tank 4; the component A mixing tank 3 and the component B mixing tank 4 are respectively connected to the spiral mixing pipe 7 through their respective independent slurry conveying pipes 5; the slurry conveying pipe 5 is equipped with a grouting pump 6, a first ball valve 13-1 and a second ball valve 13-2; the grouting pipe 12 is equipped with a third ball valve 13-3.

[0045] The inlets of components A and B are staggered along the circumference of the spiral mixing tube, and both inlets are tangential. The outer edge of the spiral guide vane 10 is in contact with the inner wall of the spiral mixing tube. The spiral direction of the guide truncated pyramid 11 is opposite to that of the spiral guide vane 10. This allows the central axial turbulence rod 9 to be installed into or removed from the spiral mixing tube 7 as a whole, making it easy to replace the mixing core with different structures.

[0046] The discharge section includes grouting pipe 12.

[0047] Components A and B maintain good stability and pumpability during separate pulping and distribution stages. When A2 and B2 enter the spiral mixing tube 7, continuous diversion, shearing, and recombination occur under the action of the central axial baffle, spiral guide vanes, and guide prisms, achieving rapid and uniform mixing. Sodium polyphosphate, sodium tripolyphosphate, and citric acid in component A form a coagulation-retarding synergistic system with polyaluminum chloride, sodium silicate, and sodium sulfite in component B, preventing premature coagulation of the slurry before mixing and enabling rapid and controllable coagulation after mixing. The spiral mixing tube 7 utilizes the fluid kinetic energy during slurry pumping to complete the mixing process, requiring no external power supply.

[0048] The spiral mixing tube is divided into a premixing inlet section, a shear enhancement section, and an outlet section by different pitches. Furthermore, a central axis baffle, spiral guide vanes, and guide prisms are installed within the spiral mixing tube. After component A and component B slurries enter the spiral mixing tube, they sequentially pass through the static mixing elements, achieving continuous splitting, shearing, and recombination. This achieves uniform mixing without increasing the residence time. The central axis baffle, spiral guide vanes, and guide prisms can be installed or removed as a whole from the spiral mixing tube to allow for replacement of mixing cores with different pitches, blade heights, or number of sections. The spiral mixing pipe is equipped with a flushing port, which allows cleaning fluid to be introduced into the pipe after grouting to remove residual grout and prevent solidification and blockage. The spiral mixing pipe utilizes the fluid kinetic energy during the grout pumping process to achieve uniform mixing of component A and component B, avoiding the problem of uncontrollable setting time caused by insufficient mixing or power failure during long-distance transportation.

[0049] A grouting process for high-water-filled fire extinguishing materials includes the following steps: Suspension agent, retarder and water are added to component A mixing tank 3 through feeder 1 and water injection pipe 2, and stirred thoroughly for 1 to 2 minutes to obtain slurry A1; at the same time, coagulant and water are added to component B mixing tank 4, and stirred thoroughly for 1 to 2 minutes to obtain slurry B1.

[0050] Silicate cement is added to the A component mixing tank 3 through feeder 1 and stirred thoroughly for 1-2 minutes to obtain slurry A2; hemihydrate gypsum is added to the B component mixing tank 4 through feeder 1 and stirred thoroughly for 1-2 minutes to obtain slurry B2.

[0051] Slurry A2 and slurry B2 are injected into the spiral mixing pipe 7 through independent pipelines and mixed evenly in a 1:1 ratio.

[0052] The mixed slurry is output through grouting pipe 12.

[0053] Example 1 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.13 parts sodium polyphosphate, 0.05 parts sodium tripolyphosphate, and 0.02 parts citric acid.

[0054] Component B: 30 parts hemihydrate gypsum, 0.1 parts polyaluminum chloride, 0.02 parts sodium silicate, and 0.015 parts sodium sulfite.

[0055] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0056] Example 2 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.12 parts sodium polyphosphate, 0.045 parts sodium tripolyphosphate, and 0.02 parts citric acid.

[0057] Component B: 30 parts hemihydrate gypsum, 0.14 parts polyaluminum chloride, 0.025 parts sodium silicate, and 0.015 parts sodium sulfite.

[0058] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0059] Example 3 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.11 parts sodium polyphosphate, 0.04 parts sodium tripolyphosphate, and 0.02 parts citric acid.

[0060] Component B: 30 parts hemihydrate gypsum, 0.19 parts polyaluminum chloride, 0.03 parts sodium silicate, and 0.02 parts sodium sulfite.

[0061] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0062] Example 4 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.1 parts sodium polyphosphate, 0.035 parts sodium tripolyphosphate, and 0.02 parts citric acid.

[0063] Component B: 30 parts hemihydrate gypsum, 0.24 parts polyaluminum chloride, 0.035 parts sodium silicate, and 0.025 parts sodium sulfite.

[0064] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0065] Example 5 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.09 parts sodium polyphosphate, 0.032 parts sodium tripolyphosphate, and 0.018 parts citric acid.

[0066] Component B: 30 parts hemihydrate gypsum, 0.29 parts polyaluminum chloride, 0.045 parts sodium silicate, and 0.025 parts sodium sulfite.

[0067] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0068] Example 6 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.08 parts sodium polyphosphate, 0.028 parts sodium tripolyphosphate, and 0.017 parts citric acid.

[0069] Component B: 30 parts hemihydrate gypsum, 0.34 parts polyaluminum chloride, 0.05 parts sodium silicate, and 0.03 parts sodium sulfite.

[0070] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0071] Example 7 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.07 parts sodium polyphosphate, 0.025 parts sodium tripolyphosphate, and 0.015 parts citric acid.

[0072] Component B: 30 parts hemihydrate gypsum, 0.37 parts polyaluminum chloride, 0.05 parts sodium silicate, and 0.03 parts sodium sulfite.

[0073] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0074] Example 8 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.065 parts sodium polyphosphate, 0.023 parts sodium tripolyphosphate, and 0.012 parts citric acid.

[0075] Component B: 30 parts hemihydrate gypsum, 0.4 parts polyaluminum chloride, 0.05 parts sodium silicate, and 0.03 parts sodium sulfite.

[0076] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a 1:1 ratio and pumped to the work area through pipelines.

[0077] The difference from Examples 1-8 is that in Comparative Examples 1-8, the coagulant of component B is replaced with an equal amount of calcium formate, while the remaining raw materials and proportions remain the same as in the corresponding examples.

[0078] Comparative Example 9 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.13 parts sodium polyphosphate, 0.05 parts sodium tripolyphosphate, and 0.02 parts citric acid.

[0079] Component B: 30 parts of hemihydrate gypsum.

[0080] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Slurry B1 is an aqueous solution. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a pipeline and pumped to the work area in a 1:1 ratio.

[0081] Comparative Example 10 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite, 0.065 parts sodium polyphosphate, 0.023 parts sodium tripolyphosphate, and 0.012 parts citric acid.

[0082] Component B: 30 parts of hemihydrate gypsum.

[0083] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent and retarder are mixed with water and stirred for 1-2 minutes to obtain slurry A1. Slurry B1 is an aqueous solution. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a pipeline and pumped to the work area in a 1:1 ratio.

[0084] Comparative Example 11 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite.

[0085] Component B: 30 parts hemihydrate gypsum, 0.1 parts polyaluminum chloride, 0.02 parts sodium silicate, and 0.015 parts sodium sulfite.

[0086] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent is mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a pipeline and pumped to the work area in a 1:1 ratio.

[0087] Comparative Example 12 A high-water-filled fire extinguishing material with adjustable setting time, comprising two parts, A and B, and composed of the following raw materials in parts by weight: Component A: 30 parts silicate cement, 0.9 parts organic bentonite.

[0088] Component B: 30 parts hemihydrate gypsum, 0.4 parts polyaluminum chloride, 0.05 parts sodium silicate, and 0.03 parts sodium sulfite.

[0089] During construction, the water-cement ratio of both component A and component B is 2.5:1. First, a fixed amount of suspending agent is mixed with water and stirred for 1-2 minutes to obtain slurry A1. Then, the accelerator is mixed with water and stirred thoroughly for 1-2 minutes to obtain slurry B1. A fixed amount of silicate cement and hemihydrate gypsum are added to slurry A1 and slurry B1 respectively, and stirred thoroughly for 1-2 minutes to obtain slurry A2 and slurry B2. Finally, slurry A2 and slurry B2 are mixed in a pipeline and pumped to the work area in a 1:1 ratio.

[0090] Similar to Examples 1-8, Comparative Examples 1-12 used the same stirring method when preparing high-water materials.

[0091] Comparative Example 13 The difference from Example 3 is that the retarder in component A is replaced with an equal amount of boric acid. Component A consists of: 30 parts silicate cement, 0.9 parts organobentonite, and 0.17 parts boric acid (replacing 0.11 parts sodium polyphosphate, 0.04 parts sodium tripolyphosphate, and 0.02 parts citric acid). The accelerator in component B remains unchanged (0.19 parts polyaluminum chloride, 0.03 parts sodium silicate, and 0.02 parts sodium sulfite). The preparation method and testing conditions are consistent with Example 3.

[0092] Comparative Example 14 The difference from Example 3 is that the accelerator in component B is replaced with an equal amount of aluminum sulfate, while the retarder in component A remains unchanged (0.11 parts sodium polyphosphate, 0.04 parts sodium tripolyphosphate, and 0.02 parts citric acid). Component B consists of 30 parts hemihydrate gypsum and 0.24 parts aluminum sulfate (replacing 0.19 parts polyaluminum chloride, 0.03 parts sodium silicate, and 0.02 parts sodium sulfite). The preparation method and testing conditions are consistent with those of Example 3.

[0093] 1. Initial setting time test Referring to "MT / T420-1995 High-water Filler Materials", the initial setting time was tested using the 45° beaker tilt method to evaluate the changes in initial setting time under different concentrations. The initial setting times of the examples and comparative examples are shown in Table 1.

[0094] Table 1

[0095] The setting time data in Table 1 shows that the high-water filling fire extinguishing material of this application, by precisely controlling the addition of retarder and accelerator, can achieve a continuous and smooth adjustment of the initial setting time from 5.67 min to 29.3 min under high water-cement ratio conditions, adapting to various working conditions of downhole filling fire extinguishing. This flexibility allows for adjustment of the material's curing time according to the needs of different construction scenarios, avoiding premature or delayed setting, and ensuring the stability of the filling effect and the efficiency of construction.

[0096] Under the same formulation, replacing the accelerator with calcium formate resulted in an overall prolonged initial setting time, with the shortest being only 12.7 min, failing to meet the requirement for extremely rapid setting (<10 min). Furthermore, the linearity of adjustment and stability of the calcium formate system were inferior to those of polyaluminum chloride. The absence of either an accelerator or a retarder alone caused the initial setting time to deviate from the reasonable range (too slow or too fast), accompanied by deterioration in spread, proving that both must be used synergistically to achieve optimal performance. Therefore, the type of accelerator is a key factor determining the controllability of setting time. The accelerator selected in this application is significantly superior to conventional accelerators in terms of adjustment range, acceleration efficiency, and compatibility with retarders.

[0097] 2. Extensibility Test High-water backfill materials have a high solids content, resulting in poor fluidity. To maintain appropriate fluidity, it is usually necessary to increase the water content or adjust the mix ratio. Taking a cement ratio of 10%-20% as an example, the water-cement ratio is typically controlled between 0.5-1.5:1, but even so, the slurry remains quite viscous. Due to insufficient fluidity, pipe blockage may occur during the pumping and injection process, especially in goaf areas, where the material is difficult to diffuse evenly, resulting in uneven filling and affecting the filling effect. In addition, due to the high solids content, the amount of material required per unit volume is large, leading to a significant increase in construction costs.

[0098] To verify the scalability of the materials in this application, the fluidity was evaluated with reference to GB / T 50080-2016 "Standard for Test Methods of Performance of Ordinary Concrete Mixtures". The scalability of the examples and comparative examples is shown in Table 2.

[0099] Table 2

[0100] As can be seen from Table 2, the composite system of retarder and accelerator in this application maintains a pumpable spread of 224-286 mm throughout the entire process of adjusting the initial setting time (5.67-29.3 min), and the change is smooth and controllable.

[0101] When calcium formate was used to replace the coagulant combination, the spread dropped sharply to 193-217 mm in high-proportion sections requiring rapid setting, below the pumping limit, easily causing pipe blockage accidents. Using a retarder alone resulted in excessive spread (279-358 mm), slurry bleeding and segregation, and an inability to form a uniform filling body; using a coagulant alone resulted in insufficient spread (182-234 mm), leading to inadequate fluidity. Therefore, the spread data further confirms that only the synergistic combination of polyaluminum chloride and a retarder can achieve a wide range of controllable adjustment of setting time while ensuring good fluidity; calcium formate and other single-component systems cannot meet the spread requirements for downhole filling and fire extinguishing.

[0102] Therefore, the material of this application has better fluidity, enabling it to be pumped smoothly and maintain appropriate fluidity in complex mine environments. By precisely controlling the addition amounts of suspending agents, accelerators, and retarders, stratification can be avoided while ensuring sufficient fluidity, thereby improving the efficiency and quality of downhole filling operations.

[0103] 3. Compressive strength test Existing high-water backfill materials have poor compressive compaction. After filling, excessive pressure can cause cracks in the material, affecting the pressure-bearing capacity of the backfill area, creating new air leakage channels, and impacting mine safety. Moreover, with prolonged use, the material may age and weather due to humidity and temperature, leading to further strength reduction and affecting the stability and safety of the mine.

[0104] To verify the compressive strength of the material in this application, standard specimens with dimensions of 70.7 mm × 70.7 mm × 70.7 mm were prepared in accordance with "MT / T420-1995 High-Moisture Filling Materials". Axial loads were applied on a servo press until failure, the maximum bearing capacity was recorded, and the compressive strength value was calculated. The compressive strengths of the examples and comparative examples at 3 days, 7 days, and 28 days are shown in Table 3.

[0105] Table 3

[0106] As can be seen from the table above, the compound system composed of polyaluminum chloride, sodium silicate, and sodium sulfite as accelerators and retarders in this application can achieve a 3-day compressive strength of 0.63~1.22 MPa, a 7-day strength of 0.96~1.70 MPa, and a 28-day strength of 1.07~2.19 MPa within a wide range of initial setting time (5.67~29.3 min) and spread (224~286 mm), meeting the strength requirements of mine filling fire extinguishing materials.

[0107] Under the same ratio, the 7-day and 28-day compressive strength of the polyaluminum chloride system were higher than those of the calcium formate system, with the 28-day strength being 32% to 63% higher, indicating that polyaluminum chloride has a better effect on enhancing later strength than calcium formate.

[0108] Using retarders alone leads to a significant decrease in strength (only 0.72~1.00 MPa at 28 days), which fails to meet engineering requirements; while using accelerators alone can achieve higher early strength, the spread is severely insufficient (182~234 mm), making pumping construction impossible, and the later strength is still lower than in the example.

[0109] When retarder is used in conjunction with polyaluminum chloride, it not only does not reduce strength, but also achieves a 28-day strength higher than that of calcium formate system by regulating hydration rate and optimizing pore structure (for example, Example 8 is 39% higher than Comparative Example 8), thus achieving a perfect balance between fluidity, setting time and strength.

[0110] Analysis of experimental results in this application: Whether the setting time of high-water backfill materials can be controlled mainly depends on the selection of accelerators and retarders. Existing accelerators are mainly divided into organic accelerators and inorganic salt accelerators, while existing retarders are mainly divided into hydroxycarboxylic acids and their salts and inorganic salts. In this application, through research on several commercially available accelerators and retarders, it was found that adding inorganic salt retarders sodium polyphosphate and sodium tripolyphosphate, and organic carboxylic acid retarders (citric acid) to silicate cement and organobentonite (component A); and adding inorganic salt accelerators (polyaluminum chloride, sodium silicate, and sodium sulfite) to hemihydrate gypsum (component B), with a water-cement ratio of 2.5:1, can achieve an adjustable setting time of 5-30 minutes. Figure 8 As shown, the coagulants polyaluminum chloride, sodium silicate, and sodium sulfite in this application have a faster dissolution rate and ion diffusion rate after mixing materials A and B. Therefore, they can form a large number of ettringite crystal nuclei in a short time, forming needle-like or spatial network structures, which enables the slurry of materials A and B to coagulate after mixing. It can also improve the early structural stability of the slurry. Organic bentonite acts as a dispersant and suspending agent in slurry A, and also plays a certain role in promoting coagulation and reducing the initial setting time. Sodium polyphosphate, sodium tripolyphosphate, and citric acid play a role in retarding coagulation. After being added to slurry A, it can prevent the slurry from thickening or agglomerating rapidly, which is beneficial for subsequent pumping. At the same time, the polyaluminum chloride, sodium silicate, and sodium sulfite added to material B play a role in retarding coagulation. Before mixing, material A will not coagulate rapidly. After mixing, the desired setting time and effect can be achieved by adding different proportions.

[0111] The above comparative data shows that when the specific retarder combination of this application remains unchanged, simply replacing the accelerator with the conventional accelerator calcium formate will result in a comprehensive deterioration of the material's overall performance.

[0112] Specifically, when the retarder composition of component A was kept exactly the same, and only the type of accelerator in component B was changed, in Comparative Examples 1-8, the accelerator in component B was replaced by an equal amount of the conventional accelerator calcium formate instead of the polyaluminum chloride, sodium silicate, and sodium sulfite used in this application, while the retarder composition of component A remained unchanged. Experimental results showed that when only the type of accelerator was changed, the overall performance of the material deteriorated significantly: the expansion of the high-acceleration zone dropped sharply from 224 mm to 193 mm, below the pumpable lower limit; the shortest setting time was only 12.7 min, which could not meet the requirement of rapid setting within 10 minutes; and the 28-day compressive strength decreased by 32%-63% (see Tables 1-3). Figure 4-7 From a chemical mechanism perspective, calcium formate can only provide Ca²⁺. + Ions, unlike the coagulant combination in this application, cannot provide multiple ions (Al³⁺). + SiO3² - SO3² - Therefore, it is difficult to effectively "break down" the effects of polyphosphates and citric acid on Ca²⁺. + and Al³ + The complexation effect leads to insufficient "de-retardation and coagulation" effect.

[0113] When the accelerator combination in component B was kept completely identical, and the state of the retarder in component A was changed, comparative examples 11-12 removed the retarder in component A, retaining only the suspending agent, while keeping the accelerator combination in component B unchanged. Experimental results showed that when the specific retarder combination of this application was completely absent from component A, the material's spread dropped sharply to 182-234 mm, resulting in insufficient flowability (see Table 2). Figure 5 This leads to pumping difficulties. From a chemical mechanism perspective, the complexing effect of the retarder is key to inhibiting early hydration of slurry A and ensuring its pumpability. When the retarder is absent, slurry A begins to hydrate during stirring and pumping, and even if component B contains the correct combination of accelerators, the lost fluidity cannot be recovered.

[0114] When the retarder composition of component A was kept completely identical, and the presence of the accelerator in component B was changed, comparative examples 9-10 removed the accelerator from component B while keeping the retarder composition of component A unchanged. Experimental results showed that when there was no accelerator in component B, the setting time of the material was significantly prolonged to 26-63.7 min, the spread increased to 279-358 mm, bleeding and segregation occurred in the slurry, and the 28-day strength decreased to 0.72-1.00 MPa (see Tables 1-3). Figure 4-7 From a chemical mechanism perspective, the multi-component ions provided by the coagulant are essential for "breaking" the complexation effect of the retarder and restarting hydration. Without the coagulant, the inhibitory effect of the retarder on hydration will persist, and the formation rate of ettringite and hydrated calcium silicate cannot be restored.

[0115] In summary, the cross-component synergistic compounding system of this application is not a simple component stacking or conventional optimization, but a system design based on the "complexation-de-retardation" chemical mechanism. In component A, sodium polyphosphate, sodium tripolyphosphate, and citric acid complex Ca²⁺... + and Al³ + To inhibit early hydration, polyaluminum chloride, sodium silicate, and sodium sulfite in component B provide multi-component ions that "break" the complexation and restart hydration after mixing—a specific chemical compatibility exists between them. Through a synergistic "complexation-de-retardation" mechanism, a continuous, smooth, and adjustable setting time is achieved within the range of 5.67–29.3 min, while maintaining a pumpable spread of 224–286 mm and mechanical properties of 1.07–2.19 MPa at 28 days. This conclusion is... Figures 4-8 The data in Tables 1-3 are consistent with the experimental data.

[0116] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

[0117] Finally: The above description is only a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A high-water-filling fire extinguishing material, characterized in that, Including component A and component B, and calculated by weight, component A includes: The mixture contains 30 parts cement, 0.9 parts suspending agent, and 0.1-0.2 parts retarder. The retarder in component A is a combination of sodium polyphosphate, sodium tripolyphosphate, and citric acid. Component B includes: The mixture contains 30 parts hemihydrate gypsum and 0.135-0.48 parts coagulant. The coagulant in component B is a combination of polyaluminum chloride, sodium silicate, and sodium sulfite.

2. The high-water-filled fire extinguishing material according to claim 1, characterized in that, The suspending agent in component A is organic bentonite.

3. The high-water-filled fire extinguishing material according to claim 1, characterized in that, The hemihydrate gypsum in component B is either building gypsum or power plant desulfurization gypsum.

4. The high-water-filled fire extinguishing material according to claim 1, characterized in that, The retarder comprises 0.065 to 0.13 parts of sodium polyphosphate, 0.023 to 0.05 parts of sodium tripolyphosphate, and 0.012 to 0.02 parts of citric acid.

5. The high-water-filled fire extinguishing material according to claim 1, characterized in that, The coagulant comprises 0.1 to 0.4 parts of polyaluminum chloride, 0.02 to 0.05 parts of sodium silicate, and 0.015 to 0.03 parts of sodium sulfite.

6. A method for preparing a high-water-filled fire extinguishing material according to any one of claims 1-5, characterized in that, Includes the following steps: Weigh each component according to the formula, mix the suspending agent and retarder evenly, add them to water, and stir to make slurry A1; add the coagulant to water and stir to make slurry B1; Silicate cement was added to grout A1 and stirred to obtain grout A2; hemihydrate gypsum was added to grout B1 and stirred to obtain grout B2. After mixing slurry A2 and slurry B2 evenly, a high-water filling fire extinguishing material is prepared.

7. The method for preparing a high-water-filled fire extinguishing material according to claim 6, characterized in that, The stirring time is 1 to 2 minutes. Slurry A2 and slurry B2 are mixed in a 1:1 ratio, and the water-cement ratio of slurry A2 and slurry B2 is 2.5:

1.

8. A high-water-filling fire extinguishing material grouting system, characterized in that, It includes a spiral mixing tube (7) and a first feed section, a second feed section, and a discharge section connected to the spiral mixing tube (7); The spiral mixing tube (7) is provided with a central axis turbulence rod (9) and a spiral guide vane (10) installed on the central axis turbulence rod (9). The spiral guide vane (10) is provided with a premixing inlet section, a shearing section and an output section in sequence. The pitch of the premixing inlet section is greater than the pitch of the output section, and the pitch of the output section is greater than the pitch of the shearing section. The first feeding section includes a mixing tank (3) for component A and a feeder (1) and a water injection pipe (2) disposed on the mixing tank (3) for component A; The second feeding section includes a B component mixing tank (4) and a feeder (1) and a water injection pipe (2) disposed on the B component mixing tank (4); The discharge section includes a grouting pipe (12).

9. A grouting process for a high-water-filled fire extinguishing material prepared using the high-water-filled fire extinguishing material preparation method according to claim 6, characterized in that, Includes the following steps: Suspension agent, retarder and water are added to the A component mixing tank (3) through the feeder (1) and water injection pipe (2), and the mixture is stirred for 1 to 2 minutes to obtain slurry A1; at the same time, coagulant and water are added to the B component mixing tank (4), and the mixture is stirred for 1 to 2 minutes to obtain slurry B1. Silicate cement is added to the A component mixing tank (3) through the feeder (1) and stirred thoroughly for 1 to 2 minutes to obtain slurry A2; hemihydrate gypsum is added to the B component mixing tank (4) through the feeder 1 and stirred thoroughly for 1 to 2 minutes to obtain slurry B2. Slurry A2 and slurry B2 are injected into the spiral mixing pipe (7) through independent pipelines and mixed evenly in a 1:1 ratio. The mixed slurry is output through the grouting pipe (12).

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