Wide fissure gushing water blocking-reinforcing grouting material, preparation method and construction technology thereof

Abstract

The present application relates to the technical field of building materials, in particular to a wide fissure gushing water plugging-reinforcing grouting material and a preparation method and construction process thereof. The plugging composite material realizes rapid plugging through rapid setting, early strength and erosion resistance. The reinforcing composite material has the effects of sustained growth of late strength, micro-expansion of volume, durability and resistance to dispersion. The plugging and reinforcing system is realized by the combined grouting construction process to realize safe and efficient construction and operation and maintenance of the tunnel. The plugging composite material is a cement-based material, and the reinforcing composite material is an alkali-activated material. The two types of materials have strong combination ability because: the calcium hydroxide separated from the cement-based material reacts with the active components in the alkali-activated material at the interface to generate calcium silicate hydrate gel, realizing chemical bonding and mutual separation of the two materials.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, specifically to grouting materials for sealing and reinforcing large fissures where water suddenly surges, as well as their preparation methods and construction processes. Background Technology

[0002] Tunnel water inrush has always been a difficult problem that plagues tunnel construction and daily safe operation. Due to the continuous supply of water from surface water, underground rivers, karst caves, etc., the connectivity between tunnels and groundwater, and the complexity of geological structures, water inrush disasters often occur at the junctions of wide fracture channels such as fault fissures. These disasters are characterized by large flow rates, high flow velocities, and high water pressure, which can easily lead to project delays and casualties.

[0003] Grouting is currently an effective method for controlling large-volume sudden water inrushes. Commonly used grouting materials include ordinary silicate cement single-liquid grout, cement-water glass two-liquid grout, and polyurethane-based chemical grout. Ordinary silicate cement single-liquid grout has an excessively long setting time and is easily diluted and dispersed by flowing water, making it difficult to retain effectively. Polyurethane-based chemical grouts need improvement in terms of long-term durability, environmental friendliness, and economy. Cement-water glass two-liquid grout has poor resistance to water dispersion; the setting speed is slowed down when the material comes into contact with water. In addition, cement-water glass grout also has problems such as small diffusion range, poor volume stability, and insufficient durability. Summary of the Invention

[0004] To overcome the above problems, this invention provides a grouting material for sealing and reinforcing water inrush in wide fissures, its preparation method, and construction process.

[0005] To achieve the above technical objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a grouting material for sealing and reinforcing water inrushes in wide fissures, the raw materials of which include: sealing composite material and reinforcing composite material; The sealing composite material is composed of sealing material and additives; the mass ratio of sealing material to additives is (1008~1222.5):(296.9~401.5). The reinforced composite material is composed of reinforcing materials and additives; the mass ratio of the reinforcing materials to the additives is (1045~1275):(296.9~401.5). The sealing material includes: a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water; the cementitious matrix material includes: silicate cement clinker, sulfoaluminate cement clinker, gypsum, mineral powder, and coal gangue powder; the composite early-strength agent includes: sodium sulfate, triethanolamine, calcium formate, and nano-hydrated calcium silicate powder (CSH). The reinforcing material includes: solid waste precursor, micro-expansion composite agent, polycarboxylate superplasticizer and water; the solid waste precursor includes: blast furnace slag, carbide slag, fly ash and tailings; the micro-expansion composite agent includes: steel slag, biomass ash, phosphogypsum, sodium carbonate and anhydrite powder. The additives include: a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent includes: water glass; the composite anti-dispersing agent includes: polyacrylamide, modified hydroxyethyl methyl cellulose ether, agar, sodium polyacrylate, and polyether polyol.

[0006] In one or more embodiments, the mass ratio of the cementitious matrix material, the composite early strength agent, the polycarboxylate superplasticizer and water in the sealing material is (570~740):(5~7.5):(3~5):(430~470).

[0007] In one or more embodiments, the mass ratio of silicate cement clinker, sulfoaluminate cement clinker, gypsum, mineral powder and coal gangue powder in the cementitious matrix material is (350~410):(30~60):(30~40):(60~90):(100~140).

[0008] In one or more embodiments, the mass ratio of sodium sulfate, triethanolamine, calcium formate and nano CSH powder in the composite early strength agent is (3~4):(0.2~0.3):(1~2):(0.8~1.2).

[0009] In one or more embodiments, the mass ratio of solid waste precursor, micro-expansion composite agent, polycarboxylate superplasticizer and water in the reinforcing material is (480~610):(93~132):(2~3):(470~530).

[0010] In one or more embodiments, the mass ratio of blast furnace slag, carbide slag, fly ash and tailings in the solid waste precursor is (270~330):(60~90):(40~60):(110~130).

[0011] In one or more embodiments, the mass ratio of steel slag, biomass ash, phosphogypsum, sodium carbonate and anhydrite powder in the micro-expansion composite agent is (30~40):(25~35):(10~15):(8~12):(20~30).

[0012] In one or more embodiments, the mass ratio of the quick-setting agent, the composite anti-dispersing agent and water in the additive is (260~340):(6.9~11.5):(30~50).

[0013] In one or more embodiments, the mass ratio of polyacrylamide, modified hydroxyethyl methyl cellulose ether, agar, sodium polyacrylate and polyether polyol in the composite anti-dispersant is (2~3):(1~2):(0.5~0.9):(0.4~0.6):(3~5).

[0014] In one or more embodiments, the specific surface area of ​​the silicate cement clinker in the sealing material is 400-550 m². 2 / kg, preferably 420 m 2 / kg.

[0015] In one or more embodiments, the sealing material contains sulfoaluminate cement clinker with a specific surface area ≥350 m². 2 / kg, preferably 400 m 2 / kg.

[0016] In one or more embodiments, the average particle size of the mineral powder, coal gangue powder, blast furnace slag, carbide slag, fly ash, tailings, steel slag, biomass ash, and phosphogypsum is 10-50 μm, preferably 30 μm.

[0017] In one or more embodiments, the water reduction rate of the polycarboxylate superplasticizer is not less than 40%.

[0018] In one or more embodiments, the water glass in the additive has a modulus of 2.0 to 2.8, preferably 2.4, and a Baume degree of 35 to 45°Bé, preferably 40°Bé.

[0019] In one or more embodiments, the polyacrylamide is anionic and has a molecular weight of 6 million to 12 million.

[0020] In one or more embodiments, the agar particle size is 80-100 mesh.

[0021] In one or more embodiments, the polyether polyol has a molecular weight of 400 to 2000.

[0022] A second aspect of the present invention provides a method for preparing the grouting material for sealing and reinforcing large fissures caused by sudden water inrush as described in the first aspect, comprising the following steps: (1) After the cementitious matrix material, composite early strength agent, polycarboxylate superplasticizer and water are mixed evenly, the sealing material is obtained; (2) After mixing the solid waste precursor, micro-expansion composite agent, polycarboxylate superplasticizer and water evenly, the reinforcement material is obtained; (3) After the quick-setting agent, the composite anti-dispersant agent and water are mixed evenly, the additive is obtained; (4) The sealing material and the additive are mixed in a specified mass ratio to obtain the sealing composite material; the reinforcing material and the additive are mixed in a specified mass ratio to obtain the reinforcing composite material.

[0023] In one or more embodiments, in step (1), the method of uniform mixing is stirring, the stirring rate is 100~150 rpm, and the stirring time is 3~8 min.

[0024] In one or more embodiments, in step (2), the method of uniform mixing is stirring, the stirring rate is 100~150 rpm, and the stirring time is 3~8 min.

[0025] In one or more embodiments, in step (3), the mixing is carried out by stirring, the temperature during stirring is 85~100℃, the stirring rate is 50~70 rpm, and the stirring time is 18~25 min.

[0026] A third aspect of the present invention provides a construction process for the grouting material for sealing and reinforcing large fissures that suddenly surges into water, as described in the first aspect, including sealing grouting and reinforcing grouting; The sealing grouting includes: reserving several drainage holes, injecting sealing composite material into the grouting holes of the area to be sealed, stopping the sealing grouting when the water outflow from the drainage holes is less than half of the original water outflow, increasing the grouting pressure to the limit pressure, and the grouting speed is less than half of the original grouting speed, and then carrying out reinforcement grouting. The reinforcement grouting process includes: injecting reinforcement composite material into the grouting holes of the area to be sealed; when the grouting pressure gradually increases to the limit final pressure, grouting is continued for a limit time and then the reinforcement grouting is stopped.

[0027] In one or more embodiments, the pressure is limited to 1-2 MPa higher than the hydrostatic pressure.

[0028] In one or more embodiments, the final pressure is defined to be 3-4 MPa higher than the hydrostatic pressure.

[0029] In one or more embodiments, when stopping the sealing grouting, the grouting rate is no more than 90 L / min.

[0030] In one or more embodiments, grouting is continued for more than 10 minutes, and when the grouting rate is less than one-quarter of the initial grouting rate at the time of reinforcement grouting, reinforcement grouting is stopped, and the grouting rate at the end of grouting is no more than 10 L / min.

[0031] The beneficial effects of this invention are as follows: (1) This invention provides a grouting material for sealing and reinforcing large fissures that can cause sudden water inrush, as well as its preparation method and construction process. The sealing composite material achieves rapid sealing through rapid setting, early strength, and erosion resistance. The reinforcing composite material has the effect of continuous growth in later strength, micro-expansion volume, durability, and anti-dispersion properties. Combined with the grouting construction process, it achieves water blocking and reinforcement system management, realizing safe and efficient construction and operation and maintenance of tunnels. The sealing composite material is a cement-based material, and the reinforcing composite material is an alkali-activated material. The two types of materials have strong bonding ability because: the calcium hydroxide precipitated in the cement-based material and the active components in the alkali-activated material react at the interface to generate hydrated calcium silicate gel, realizing the chemical bonding of the two materials and preventing them from separating from each other. The sealing composite material prepared by this invention has a flowability ≥25 cm, a gelation time ≥10 s in 20 s, an initial setting time ≥15 min in 25 min, a compressive strength ≥4 MPa in 12 h, and a dynamic water retention rate ≥90%; the reinforcement composite material has a flowability ≥28 cm, an initial setting time ≥20 min in 40 min, a compressive strength ≥10 MPa in 28 days, a volume change rate ≥0.02% in 28 days, and a dynamic water retention rate ≥85%.

[0032] ① Rapid setting performance of the sealing composite material: Water glass can rapidly react with calcium hydroxide produced during the hydration of silicate cement clinker to generate insoluble calcium silicate gel and aluminosilicate gel. These gels instantly form a network structure, greatly shortening the setting time of the slurry. Simultaneously, the sulfoaluminate cement clinker in the formulation itself has rapid hydration characteristics, with a hydration reaction rate higher than that of ordinary silicate cement, enabling the rapid formation of hydration products such as ettringite in the early stages. The combined effect of these two factors causes the slurry to lose its fluidity and solidify within seconds to tens of seconds, thus achieving rapid setting.

[0033] ② High early strength of the sealing composite material: On the one hand, water glass and sulfoaluminate cement have a setting-promoting and early-strength effect on the cementitious matrix material, and both can significantly improve the early strength of ordinary silicate cement-based materials; on the other hand, due to the synergistic catalytic and nucleation-inducing effects of multiple components in the composite early-strength agent, sodium sulfate can accelerate the hydration reaction of cement minerals and promote the formation of ettringite and calcium hydroxide; triethanolamine, as a surfactant, can reduce the surface energy of cement particles and accelerate their dispersion and hydrolysis process; calcium formate can promote the hydration of C3S and reduce the concentration of calcium ions in the liquid phase, accelerating the precipitation of calcium silicate gel; nano-CSH powder can provide nucleation sites for the hydration products of minerals such as C4AF and C3S, inducing the growth of hydrated calcium silicate gel. This dual effect of "chemical excitation + physical nucleation" enables the material to obtain high mechanical properties in the early stage of the reaction.

[0034] ③ The sealing composite material achieves erosion resistance and rapid sealing in the event of sudden water inrush: a synergistic result of the thickening and rapid setting of the composite anti-dispersant agent. On the one hand, the composite anti-dispersant agent endows the slurry with anti-water dispersion ability. Polyacrylamide, modified hydroxyethyl methyl cellulose ether, and polyether polyol rapidly form a high-viscosity, high-elasticity, uniform three-dimensional network structure in water, improving the yield stress and cohesion of the slurry; agar forms a thermally reversible gel to enhance the internal skeleton; sodium polyacrylate improves the suspension stability of solid particles through electrostatic repulsion and entanglement. The combination of these multiple components causes the slurry to form a dense viscoelastic protective film when it encounters water, blocking the water flow from eroding the uncured slurry. On the other hand, the rapid-setting component water glass and the fast-hardening cementitious material sulfoaluminate cement clinker provide instantaneous curing ability. Together, they promote the rapid reaction and solidification of the slurry and seal the water passages.

[0035] ④ The sustained increase in strength of reinforced composite materials in later stages: This is mainly due to the long-term hydration reaction of solid waste precursors under the composite activation system. Blast furnace slag, fly ash, and tailings contain a large amount of active aluminosilicate minerals. Under the combined activation of alkaline Ca(OH)2 provided by carbide slag and sulfates and carbonates provided by phosphogypsum, anhydrite powder, and sodium carbonate in the micro-expansion composite agent, the hydration reaction can last for months to years, continuously generating products such as hydrated calcium silicate, hydrated calcium aluminate, and ettringite. Therefore, the strength continues to increase in later stages. In addition, dicalcium silicate and tricalcium silicate in steel slag can also be slowly hydrated, further supplementing the gel. This alkali-sulfur-salt multi-element activation mechanism makes the slurry structure increasingly dense with age, and the strength continues to increase, rather than reaching a peak and then stagnating in the early stages.

[0036] ⑤ The micro-expansion characteristics of the reinforced composite material originate from the synergistic volume expansion effect of multiple components in the micro-expansion composite agent. On the one hand, free calcium oxide and magnesium oxide in steel slag slowly hydrate upon contact with water to form Ca(OH)2 and Mg(OH)2, resulting in a significant volume increase. On the other hand, sulfate ions provided by phosphogypsum and anhydrite powder react with active calcium aluminate released from solid waste precursors to form ettringite, a process accompanied by crystallization expansion. In addition, calcium carbonate formed by the reaction of sodium carbonate with calcium ions may also produce a slight volume increase. By adjusting the proportions of each component, the expansion rate can be matched with the hardening shrinkage of the slurry, achieving moderate and stable micro-expansion, effectively compensating for drying shrinkage and cold shrinkage, and preventing cracking of the solidified body.

[0037] ⑥ The reinforced composite material possesses both durability and anti-dispersion properties, stemming from its dense, solidified structure and the composite anti-dispersion agent in its additives. Durability primarily arises from the low-calcium-to-silica ratio CSH gel, ettringite, and zeolite-like phases generated from the solid waste precursor under multi-element excitation. These phases exhibit extremely low permeability and excellent chemical stability, effectively resisting sulfate attack, acid and alkali corrosion, and chloride ion penetration. Simultaneously, the micro-expansion effect reduces internal micro-cracks, further enhancing durability and impermeability. Anti-dispersion properties mainly originate from the composite anti-dispersion agent (polyacrylamide, modified hydroxyethyl methyl cellulose ether, agar, sodium polyacrylate, polyether polyol) imparting high viscoelasticity and cohesion to the grout, making it less susceptible to being dispersed by water flow during underwater grouting. This results in a high grout retention rate, which, combined with its rapid setting and early strength characteristics, enables rapid sealing of water passages.

[0038] (2) The grouting material and combined grouting construction process of the present invention first reduces the water volume by using the water-blocking material, and then quickly switches to the high-strength reinforcement material to fully diffuse and bond in the crack, so as to achieve efficient grouting with seamless switching between water blocking and reinforcement materials. This is conducive to greatly improving the water-blocking effect and the surrounding rock reinforcement effect, and realizing safe and efficient construction and operation and maintenance of tunnels. Attached Figure Description

[0039] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0040] Figure 1 A schematic diagram of the grouting device used in the construction of a grouting material for sealing and reinforcing water inrushes in wide fissures. Detailed Implementation

[0041] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0042] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0043] In the following embodiments, The specific surface area of ​​silicate cement clinker is 420 m². 2 / kg; The specific surface area of ​​sulfoaluminate cement clinker is 400 m². 2 / kg; The average particle size of mineral powder, coal gangue powder, blast furnace slag, carbide slag, fly ash, tailings, steel slag, biomass ash and phosphogypsum is 30 μm. The water reduction rate of polycarboxylate superplasticizer shall not be less than 40%; Water glass has a modulus of 2.4 and a Baume degree of 40°Bé. Polyacrylamide is anionic with a molecular weight of 6 million to 12 million. The agar particle size is 80-100 mesh; The molecular weight of polyether polyols is 400~2000.

[0044] All quantities in the following examples are parts by weight.

[0045] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0046] Example 1 Grouting material for sealing and reinforcing water inrushes in wide fissures, the raw materials of which include: sealing composite materials and reinforcing composite materials; Among them, the sealing composite material is composed of sealing materials and additives; the reinforcement composite material is composed of reinforcement materials and additives. The sealing material consists of a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water. The cementitious matrix material comprises 350 parts silicate cement clinker, 45 parts sulfoaluminate cement clinker, 40 parts gypsum, 90 parts mineral powder, and 120 parts coal gangue powder. The composite early-strength agent comprises 3.5 parts sodium sulfate, 0.2 parts triethanolamine, 2 parts calcium formate, and 0.8 parts nano-CSH powder. The polycarboxylate superplasticizer consists of 4 parts water. The reinforcement material consists of a solid waste precursor, a micro-expansion composite agent, a polycarboxylate superplasticizer, and water. The solid waste precursor consists of 300 parts blast furnace slag, 60 parts calcium carbide slag, 60 parts fly ash, and 110 parts tailings. The micro-expansion composite agent consists of 35 parts steel slag, 25 parts biomass ash, 15 parts phosphogypsum, 12 parts sodium carbonate, and 20 parts anhydrite powder. The polycarboxylate superplasticizer consists of 2 parts, and water consists of 470 parts. The additives consist of a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent consists of 260 parts water glass; the composite anti-dispersing agent consists of 2 parts polyacrylamide, 1.5 parts modified hydroxyethyl methyl cellulose ether, 0.9 parts agar, 0.4 parts sodium polyacrylate, and 3 parts polyether polyol; and 40 parts water.

[0047] The preparation method and application include the following steps: (1) Silicate cement clinker, sulfoaluminate cement clinker, gypsum, mineral powder, coal gangue powder, sodium sulfate, triethanolamine, calcium formate, nano CSH powder, polycarboxylate superplasticizer and water are stirred at 120 rpm for 5 min to obtain the sealing material.

[0048] (2) Blast furnace slag, carbide slag, fly ash, tailings, steel slag, biomass ash, phosphogypsum, sodium carbonate, anhydrite powder, polycarboxylate superplasticizer and water are stirred at 120 rpm for 5 min to obtain the reinforcing material.

[0049] (3) Mix water glass, water, polyacrylamide, modified hydroxyethyl methyl cellulose ether, agar, sodium polyacrylate and polyether polyol and heat to 95°C. Stir at 60 rpm for 20 min to obtain the additive.

[0050] (4) The sealing material and the additive are mixed in a mass ratio of 1050:300 to obtain the sealing composite material; the reinforcing material and the additive are mixed in a mass ratio of 1050:300 to obtain the reinforcing composite material.

[0051] Example 2 Grouting material for sealing and reinforcing water inrushes in wide fissures, the raw materials of which include: sealing composite materials and reinforcing composite materials; Among them, the sealing composite material is composed of sealing materials and additives; the reinforcement composite material is composed of reinforcement materials and additives. The sealing material consists of a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water. The cementitious matrix material comprises 410 parts silicate cement clinker, 60 parts sulfoaluminate cement clinker, 35 parts gypsum, 60 parts mineral powder, and 140 parts coal gangue powder. The composite early-strength agent consists of 3 parts sodium sulfate, 0.3 parts triethanolamine, 1 part calcium formate, and 1 part nano-CSH powder. The polycarboxylate superplasticizer comprises 3 parts water, and the total water content is 470 parts. The reinforcement material consists of a solid waste precursor, a micro-expansion composite agent, a polycarboxylate superplasticizer, and water. The solid waste precursor consists of 270 parts blast furnace slag, 90 parts calcium carbide slag, 50 parts fly ash, and 130 parts tailings. The micro-expansion composite agent consists of 30 parts steel slag, 35 parts biomass ash, 12.5 parts phosphogypsum, 10 parts sodium carbonate, and 30 parts anhydrite powder. The polycarboxylate superplasticizer consists of 2.5 parts, and the water consists of 500 parts. The additives consist of a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent consists of 300 parts of water glass; the composite anti-dispersing agent consists of 3 parts of polyacrylamide, 1 part of modified hydroxyethyl methyl cellulose ether, 0.5 parts of agar, 0.5 parts of sodium polyacrylate, and 4 parts of polyether polyol; and 50 parts of water.

[0052] The preparation method of the grouting material for sealing and reinforcing water inrush in wide fissures is the same as in Example 1.

[0053] Example 3 Grouting material for sealing and reinforcing water inrushes in wide fissures, the raw materials of which include: sealing composite materials and reinforcing composite materials; Among them, the sealing composite material is composed of sealing materials and additives; the reinforcement composite material is composed of reinforcement materials and additives. The sealing material consists of a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water. The cementitious matrix material comprises 380 parts silicate cement clinker, 30 parts sulfoaluminate cement clinker, 30 parts gypsum, 90 parts mineral powder, and 120 parts coal gangue powder. The composite early-strength agent comprises 4 parts sodium sulfate, 0.2 parts triethanolamine, 2 parts calcium formate, and 1 part nano-CSH powder. The polycarboxylate superplasticizer consists of 4 parts water and 450 parts water. The reinforcing material consists of a solid waste precursor, a micro-expansion composite agent, a polycarboxylate superplasticizer, and water. The solid waste precursor consists of 300 parts blast furnace slag, 75 parts calcium carbide slag, 50 parts fly ash, and 130 parts tailings. The micro-expansion composite agent consists of 40 parts steel slag, 30 parts biomass ash, 15 parts phosphogypsum, 12 parts sodium carbonate, and 25 parts anhydrite powder. The polycarboxylate superplasticizer consists of 2 parts, and the water consists of 470 parts. The additives consist of a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent consists of 300 parts water glass; the composite anti-dispersing agent consists of 2 parts polyacrylamide, 2 parts modified hydroxyethyl methyl cellulose ether, 0.5 parts agar, 0.4 parts sodium polyacrylate, and 3 parts polyether polyol; and 30 parts water.

[0054] The preparation method of the grouting material for sealing and reinforcing water inrush in wide fissures is the same as in Example 1.

[0055] Example 4 Grouting material for sealing and reinforcing water inrushes in wide fissures, the raw materials of which include: sealing composite materials and reinforcing composite materials; Among them, the sealing composite material is composed of sealing materials and additives; the reinforcement composite material is composed of reinforcement materials and additives. The sealing material consists of a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water. The cementitious matrix material comprises 380 parts silicate cement clinker, 30 parts sulfoaluminate cement clinker, 30 parts gypsum, 75 parts mineral powder, and 105 parts coal gangue powder. The composite early-strength agent comprises 4 parts sodium sulfate, 0.25 parts triethanolamine, 1.5 parts calcium formate, and 1.2 parts nano-CSH powder. The polycarboxylate superplasticizer consists of 5 parts, and water is 430 parts. The reinforcement material consists of a solid waste precursor, a micro-expansion composite agent, a polycarboxylate superplasticizer, and water. The solid waste precursor consists of 270 parts blast furnace slag, 90 parts calcium carbide slag, 60 parts fly ash, and 120 parts tailings. The micro-expansion composite agent consists of 30 parts steel slag, 20 parts biomass ash, 12.5 parts phosphogypsum, 10 parts sodium carbonate, and 25 parts anhydrite powder. The polycarboxylate superplasticizer consists of 2 parts, and the water consists of 470 parts. The additives consist of a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent consists of 340 parts of water glass; the composite anti-dispersing agent consists of 2.5 parts of polyacrylamide, 2 parts of modified hydroxyethyl methyl cellulose ether, 0.7 parts of agar, 0.6 parts of sodium polyacrylate, and 5 parts of polyether polyol; and 30 parts of water.

[0056] The preparation method of the grouting material for sealing and reinforcing water inrush in wide fissures is the same as in Example 1.

[0057] Example 5 Grouting material for sealing and reinforcing water inrushes in wide fissures, the raw materials of which include: sealing composite materials and reinforcing composite materials; Among them, the sealing composite material is composed of sealing materials and additives; the reinforcement composite material is composed of reinforcement materials and additives. The sealing material consists of a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water. The cementitious matrix material comprises 380 parts silicate cement clinker, 45 parts sulfoaluminate cement clinker, 35 parts gypsum, 75 parts mineral powder, and 120 parts coal gangue powder. The composite early-strength agent comprises 3.5 parts sodium sulfate, 0.2 parts triethanolamine, 1.5 parts calcium formate, and 0.8 parts nano-CSH powder. The polycarboxylate superplasticizer consists of 4 parts water. The reinforcing material consists of a solid waste precursor, a micro-expansion composite agent, a polycarboxylate superplasticizer, and water. The solid waste precursor consists of 330 parts blast furnace slag, 60 parts calcium carbide slag, 50 parts fly ash, and 120 parts tailings. The micro-expansion composite agent consists of 35 parts steel slag, 35 parts biomass ash, 12.5 parts phosphogypsum, 10 parts sodium carbonate, and 30 parts anhydrite powder. The polycarboxylate superplasticizer consists of 2 parts, and the water consists of 470 parts. The additives consist of a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent consists of 260 parts of water glass; the composite anti-dispersing agent consists of 2.5 parts of polyacrylamide, 1 part of modified hydroxyethyl methyl cellulose ether, 0.7 parts of agar, 0.5 parts of sodium polyacrylate, and 3 parts of polyether polyol; and 40 parts of water.

[0058] The preparation method of the grouting material for sealing and reinforcing water inrush in wide fissures is the same as in Example 1.

[0059] Example 6 Grouting material for sealing and reinforcing water inrushes in wide fissures, the raw materials of which include: sealing composite materials and reinforcing composite materials; Among them, the sealing composite material is composed of sealing materials and additives; the reinforcement composite material is composed of reinforcement materials and additives. The sealing material consists of a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water. The cementitious matrix material comprises 410 parts silicate cement clinker, 45 parts sulfoaluminate cement clinker, 40 parts gypsum, 75 parts mineral powder, and 100 parts coal gangue powder. The composite early-strength agent comprises 3.5 parts sodium sulfate, 0.25 parts triethanolamine, 2 parts calcium formate, and 1.2 parts nano-CSH powder. The polycarboxylate superplasticizer consists of 4 parts water. The reinforcement material consists of a solid waste precursor, a micro-expansion composite agent, a polycarboxylate superplasticizer, and water. The solid waste precursor consists of 300 parts blast furnace slag, 60 parts calcium carbide slag, 40 parts fly ash, and 130 parts tailings. The micro-expansion composite agent consists of 40 parts steel slag, 30 parts biomass ash, 15 parts phosphogypsum, 12 parts sodium carbonate, and 25 parts anhydrite powder. The polycarboxylate superplasticizer consists of 3 parts, and the water consists of 530 parts. The additives consist of a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent consists of 340 parts water glass; the composite anti-dispersing agent consists of 2 parts polyacrylamide, 1.5 parts modified hydroxyethyl methyl cellulose ether, 0.9 parts agar, 0.6 parts sodium polyacrylate, and 5 parts polyether polyol; and 30 parts water.

[0060] The preparation method of the grouting material for sealing and reinforcing water inrush in wide fissures is the same as in Example 1.

[0061] Comparative Example 1 Compared with Example 1, the sulfoaluminate cement clinker in the sealing composite material was completely replaced with silicate cement clinker, while the other components and preparation methods were the same as in Example 1.

[0062] Comparative Example 2 Compared with Example 1, the sealing composite material does not contain triethanolamine, and the other components and preparation methods are the same as in Example 1.

[0063] Comparative Example 3 Compared with Example 1, the sealing composite material does not contain nano-CSH powder, and the other components and preparation methods are the same as in Example 1.

[0064] Comparative Example 4 Compared with Example 1, the reinforced composite material does not contain fly ash, and the other components and preparation methods are the same as in Example 1.

[0065] Comparative Example 5 Compared with Example 1, the reinforced composite material does not contain steel slag, and the other components and preparation methods are the same as in Example 1.

[0066] Comparative Example 6 Compared with Example 1, the reinforced composite material does not contain phosphogypsum, and the other components and preparation methods are the same as in Example 1.

[0067] Comparative Example 7 Compared to Example 1, the additives do not contain polyacrylamide, while the other components and preparation methods are the same as in Example 1.

[0068] Comparative Example 8 Compared with Example 1, the additives do not contain modified hydroxyethyl methyl cellulose ether, and the other components and preparation methods are the same as in Example 1.

[0069] Comparative Example 9 Compared with Example 1, the additives do not contain polyether polyols, and the other components and preparation methods are the same as in Example 1.

[0070] Comparative Example 10 Compared with Example 1, the content of triethanolamine in the sealing composite material was adjusted to 1 part, while the other components and preparation methods were the same as in Example 1.

[0071] Comparative Example 11 Compared with Example 1, the agar content in the additives was adjusted to 2 parts and sodium polyacrylate to 1 part, while the other components and preparation methods were the same as in Example 1.

[0072] The working performance of the sealing composite materials in each embodiment and comparative example was tested, including flowability, gelation time, initial setting time, 12-hour compressive strength and dynamic water retention rate (flow rate 1.5 m / s). The results are shown in Table 1.

[0073] The working performance of the reinforced composite materials in each embodiment and comparative example was tested, including flowability, initial setting time, 28-day compressive strength, 28-day volume change rate, and dynamic water retention rate (flow rate 1.5 m / s). The results are shown in Table 2.

[0074] The performance testing method is as follows: 1. The fluidity test was conducted according to the method in GB / T 8077-2012 "Test Method for Homogeneity of Concrete Admixtures", using a metal truncated cone mold with an upper and lower diameter of 36 mm and 60 mm respectively and a height of 60 mm.

[0075] 2. The gelation time was tested using the inverted cup method. The two components were weighed into different beakers and quickly mixed evenly. Timing was started from the end of mixing. The beakers were tilted at about 45° until the surface of the slurry no longer showed obvious flow. The time at this point was recorded as the gelation time.

[0076] 3. Initial setting time test: The test was conducted according to the method in GB / T 1346-2011 "Standard Water Requirement, Setting Time and Soundness Test Methods for Cement". The testing instrument used was the new national standard Vicat apparatus, and the initial setting time of the freshly mixed grout was tested using an initial setting needle. Flexural-compressive ratio: The compressive strength and flexural strength of the material were tested according to the method in GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)". The flexural-compressive ratio was calculated by dividing the flexural strength by the compressive strength.

[0077] 4. The compressive strength test shall be conducted in accordance with the method in GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)".

[0078] 5. Dynamic water retention rate test: A fixed mass of sealing material is placed in the groove, and dynamic water is set to flush the sealing material at a flow rate of 1.5 m / s. After 30 minutes, the flushing is stopped, and the mass retention rate of the sealing material is weighed and calculated, which is the dynamic water retention rate.

[0079] 6. The volume change rate is referenced in GB / T 45778-2025 "Test Method for Chemical Shrinkage of Cement Paste". Chemical shrinkage is characterized by measuring the absolute volume change inside the cement paste caused by the hydration reaction.

[0080] Table 1. Performance of the sealing composite materials in each embodiment and comparative example.

[0081] Table 2. Performance of the reinforced composite materials in each embodiment and comparative example.

[0082] Comparative Example 1 data shows that replacing all sulfoaluminate cement clinker in the sealing composite material with silicate cement clinker significantly prolongs the initial setting time of the material, while 12 The compressive strength and water retention rate decreased. Data from Comparative Examples 2 and 3 showed that the absence of triethanolamine or nano-CSH powder in the sealing composite material significantly increased the initial setting time, while slightly decreasing the early compressive strength and water retention rate. Data from Comparative Example 4 showed that the absence of fly ash in the reinforcing composite material prolonged the initial setting time, significantly reduced the 28-day compressive strength, and also decreased the water retention rate. Data from Comparative Examples 5 and 6 showed that the absence of steel slag or phosphogypsum in the reinforcing composite material mainly caused the material to change from slight volume expansion to volume shrinkage, while also reducing mechanical properties. Data from Comparative Examples 7, 8, and 9 showed that the absence of polyacrylamide, modified hydroxyethyl methyl cellulose ether, or polyether polyol in the additives significantly reduced the water retention rate of both the sealing and reinforcing composite materials. Data from Comparative Example 10 showed that when the triethanolamine content in the sealing composite material was outside the limits of this invention, the gelation time and initial setting time changed significantly, completing gelation and curing within 10 seconds, while the material's flowability test could not be performed. h The compressive strength is significantly reduced; the data of Comparative Example 11 show that when the content of agar and sodium polyacrylate in the additives is not within the limits of this invention, the fluidity of the sealing composite material is significantly reduced, the setting time is greatly extended, the early compressive strength and water retention rate are greatly reduced, and the fluidity of the reinforced composite material is reduced, the initial setting time is extended, and the later strength and water retention rate are greatly reduced.

[0083] Example 7 Figure 1 A schematic diagram of the grouting device used in the construction of a grouting material for sealing and reinforcing water inrushes in wide fissures.

[0084] Construction technology for sealing and reinforcing grouting materials for large fissures that suddenly gull into water, including sealing grouting and reinforcing grouting; The sealing grouting process includes: reserving several drainage holes, injecting sealing composite material into the grouting holes of the area to be sealed (simultaneously injecting sealing material and additives, with a mass ratio of sealing material to additives of 1050:300), stopping sealing grouting when the water outflow from the drainage holes is less than half of the original water outflow, increasing the grouting pressure to the limit pressure, and the grouting speed is less than half of the original grouting speed, and then proceeding with reinforcement grouting; The reinforcement grouting includes: injecting reinforcement composite material into the grouting hole of the area to be sealed (simultaneously injecting reinforcement material and additives, with a mass ratio of reinforcement material to additives of 1050:300), and stopping the reinforcement grouting after the grouting pressure is gradually increased to the limited final pressure and the grouting continues for a limited time.

[0085] Among them, the pressure is limited to be 1~2 MPa higher than the hydrostatic pressure; The final pressure is limited to be 3-4 MPa higher than the hydrostatic pressure.

[0086] When stopping the sealing grouting, the grouting rate should not exceed 90 L / min.

[0087] Continue grouting for more than 10 minutes, and when the grouting rate is less than one-quarter of the initial grouting rate at the end of the reinforcement grouting stage, stop the reinforcement grouting. The grouting rate at the end of the grouting should not exceed 10 L / min.

[0088] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. Grouting material for sealing and reinforcing water inrushes in wide fissures, characterized in that: Its raw materials include: sealing composite materials and reinforcing composite materials; The sealing composite material is composed of sealing material and additives; the mass ratio of sealing material to additives is (1008~1222.5):(296.9~401.5). The reinforced composite material is composed of reinforcing material and additives; the mass ratio of reinforcing material to additives is (1045~1275):(296.9~401.5). The sealing material includes: a cementitious matrix material, a composite early-strength agent, a polycarboxylate superplasticizer, and water; the cementitious matrix material includes: silicate cement clinker, sulfoaluminate cement clinker, gypsum, mineral powder, and coal gangue powder; the composite early-strength agent includes: sodium sulfate, triethanolamine, calcium formate, and nano-hydrated calcium silicate powder; The reinforcing material includes: solid waste precursor, micro-expansion composite agent, polycarboxylate superplasticizer and water; the solid waste precursor includes: blast furnace slag, carbide slag, fly ash and tailings; the micro-expansion composite agent includes: steel slag, biomass ash, phosphogypsum, sodium carbonate and anhydrite powder. The additives include: a quick-setting agent, a composite anti-dispersing agent, and water; the quick-setting agent includes: water glass; the composite anti-dispersing agent includes: polyacrylamide, modified hydroxyethyl methyl cellulose ether, agar, sodium polyacrylate, and polyether polyol.

2. The grouting material for sealing and reinforcing large fissures and sudden water inrush as described in claim 1, characterized in that, In the sealing material, the mass ratio of cementitious matrix material, composite early strength agent, polycarboxylate superplasticizer and water is (570~740):(5~7.5):(3~5):(430~470); In the cementitious matrix material, the mass ratio of silicate cement clinker, sulfoaluminate cement clinker, gypsum, mineral powder and coal gangue powder is (350~410):(30~60):(30~40):(60~90):(100~140). In the composite early strength agent, the mass ratio of sodium sulfate, triethanolamine, calcium formate and nano-hydrated calcium silicate powder is (3~4):(0.2~0.3):(1~2):(0.8~1.2).

3. The grouting material for sealing and reinforcing large fissures and sudden water inrush as described in claim 1, characterized in that, In the reinforcement material, the mass ratio of solid waste precursor, micro-expansion composite agent, polycarboxylate superplasticizer and water is (480~610):(93~132):(2~3):(470~530). In the solid waste precursors, the mass ratio of blast furnace slag, carbide slag, fly ash and tailings is (270~330):(60~90):(40~60):(110~130). In the micro-expansion composite agent, the mass ratio of steel slag, biomass ash, phosphogypsum, sodium carbonate and anhydrite powder is (30~40):(25~35):(10~15):(8~12):(20~30).

4. The grouting material for sealing and reinforcing large fissures and sudden water inrush as described in claim 1, characterized in that, In the additives, the mass ratio of quick-setting agent, composite anti-dispersant agent and water is (260~340):(6.9~11.5):(30~50); In the composite anti-dispersant, the mass ratio of polyacrylamide, modified hydroxyethyl methyl cellulose ether, agar, sodium polyacrylate and polyether polyol is (2~3):(1~2):(0.5~0.9):(0.4~0.6):(3~5).

5. The grouting material for sealing and reinforcing large fissures and sudden water inrush as described in claim 1, characterized in that, In sealing materials, silicate cement clinker has a specific surface area of ​​400~550 m². 2 / kg; Specific surface area of ​​sulfoaluminate cement clinker ≥350 m² 2 / kg.

6. The grouting material for sealing and reinforcing large fissures and sudden water inrush as described in claim 1, characterized in that, The average particle size of mineral powder, coal gangue powder, blast furnace slag, carbide slag, fly ash, tailings, steel slag, biomass ash and phosphogypsum is 10~50 μm. The water glass in the additive has a modulus of 2.0 to 2.8 and a Baumé degree of 35 to 45 °Bé.

7. The grouting material for sealing and reinforcing large fissures and sudden water inrush as described in claim 1, characterized in that, Polyacrylamide is anionic with a molecular weight of 6 million to 12 million. The agar particle size is 80-100 mesh; The molecular weight of polyether polyols is 400~2000.

8. The preparation method of the grouting material for sealing and reinforcing large fissures caused by sudden water inrush as described in any one of claims 1 to 7, characterized in that, Includes the following steps: (1) After the cementitious matrix material, composite early strength agent, polycarboxylate superplasticizer and water are mixed evenly, the sealing material is obtained; (2) After mixing the solid waste precursor, micro-expansion composite agent, polycarboxylate superplasticizer and water evenly, the reinforcement material is obtained; (3) After the quick-setting agent, the composite anti-dispersant agent and water are mixed evenly, the additive is obtained; (4) The sealing material and the additive are mixed in a specified mass ratio to obtain the sealing composite material; the reinforcing material and the additive are mixed in a specified mass ratio to obtain the reinforcing composite material.

9. The construction process of the grouting material for sealing and reinforcing large fissures with sudden water inrush as described in any one of claims 1 to 7, characterized in that, This includes sealing grouting and reinforcement grouting; The sealing grouting includes: reserving several drainage holes, injecting sealing composite material into the grouting holes of the area to be sealed, stopping the sealing grouting when the water outflow from the drainage holes is less than half of the original water outflow, increasing the grouting pressure to the limit pressure, and the grouting speed is less than half of the original grouting speed, and then carrying out reinforcement grouting. The reinforcement grouting process includes: injecting reinforcement composite material into the grouting holes of the area to be sealed; when the grouting pressure gradually increases to the limit final pressure, grouting is continued for a limit time and then the reinforcement grouting is stopped.

10. The construction process as described in claim 9, characterized in that, The pressure is limited to be 1~2 MPa higher than the hydrostatic pressure; The final pressure is limited to be 3-4 MPa higher than the hydrostatic pressure. When stopping the sealing grouting, the grouting rate should not exceed 90 L / min; Continue grouting for more than 10 minutes, and when the grouting rate is less than one-quarter of the initial grouting rate at the end of the reinforcement grouting stage, stop the reinforcement grouting. The grouting rate at the end of the grouting should not exceed 10 L / min.

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