Anti-dispersion solid waste grouting filling material, preparation method and application thereof

Abstract

This invention belongs to the technical field of underground engineering grouting materials, and discloses an anti-dispersion solid waste grouting filler material, its preparation method, and its application. It includes grout A and grout B. Grout A, by mass, comprises the following components: 400-1000 parts fly ash, 500-1000 parts blast furnace slag, 100-500 parts silicate cement, 250-1200 parts water, 5-50 parts sodium hydroxide, and 10-50 parts PolyFury-I; PolyFury-I includes acrylamide and N,N,N',N'-tetramethylethylenediamine. Grout B, by mass, comprises water glass and PolyFury-II; PolyFury-II includes water glass, ammonium persulfate solution, xanthan gum, and carboxymethyl cellulose. This invention effectively improves the anti-dispersion properties of the grouting material in dynamic water flow, enhances the sealing effect of dynamic water flow, and solves the problem of insufficient sealing by traditional grouting materials.

Description

Technical Field

[0001] This invention belongs to the technical field of underground engineering grouting materials, specifically relating to an anti-dispersion solid waste grouting filling material, its preparation method, and its application. Background Technology

[0002] The statements herein provide only background information in relation to this invention and do not necessarily constitute prior art.

[0003] Industries such as coal mining can effectively reduce the risk of land subsidence through technologies such as solid backfilling, and have already achieved underground disposal of hundreds of millions of tons of coal-based solid waste annually.

[0004] As mining extends to deeper areas and regions with complex hydrogeology, grouting and backfilling projects often face interference from dynamic water environments such as high-velocity groundwater and fissure water inflow. Under dynamic water conditions, the bonding interface between the grout and the surrounding rock is easily damaged by shearing and segregation. Solid waste particles are difficult to retain effectively due to insufficient anti-dispersion properties, resulting in incomplete formation and uneven strength distribution of the backfill body. This not only reduces the compactness of the backfill but may also lead to the risk of groundwater pollution.

[0005] In addition, the disturbance of the grout setting and hardening process by moving water will prolong the initial setting time, exacerbate the material shrinkage rate, and cause seepage channels to form between the filling body and the surrounding rock, which seriously affects the long-term stability of the goaf.

[0006] Currently, the main approach to addressing the issue of slurry dispersion in dynamic water environments is to add a single antidispersant to increase slurry viscosity, thereby enhancing its erosion resistance. However, this method suffers from several problems: excessive introduction of the antidispersant significantly increases slurry viscosity, leading to a sharp decrease in fluidity and even increased pumping resistance and grouting pipe blockage. For example, while thickening antidispersants based on xanthan gum or carboxymethyl cellulose can improve antidispersibility, they significantly prolong the slurry's setting time and weaken its pumping efficiency. Conversely, antidispersants based on inorganic cementitious materials such as water glass are prone to early hardening or later strength loss in the slurry due to improper control of modulus or solid content. This "contradictory effect" between fluidity and antidispersibility severely restricts the practical application of existing solid waste-based grouting materials in dynamic water environments. Therefore, maintaining good fluidity while ensuring the slurry's antidispersibility has become a core challenge for technical optimization.

[0007] Under dynamic water conditions, the setting and hardening process of grouting materials is easily disturbed by water flow, leading to prolonged initial setting time and increased shrinkage rate. This, in turn, creates seepage channels between the filling material and the surrounding rock, affecting the stability of the goaf. In traditional technologies, shrinkage is often suppressed by adjusting the material ratio, but this leads to a decrease in solid waste utilization. This is because solid wastes such as fly ash and blast furnace slag have high shrinkage rates. Traditional methods of suppressing shrinkage often rely on adding non-solid waste components such as expanding agents or reducing the amount of high-shrinkage solid waste to balance shrinkage performance. Both of these methods reduce the proportion of solid waste in the material, thereby lowering the solid waste utilization rate. However, this invention provides an anti-dispersion solid waste grouting filling material, its preparation method, and its application, which reduces the hardening shrinkage rate while still meeting the solid waste utilization requirements, thus resolving this contradiction. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide an anti-dispersion solid waste grouting filling material, its preparation method, and its application. This grouting material possesses properties such as resistance to dispersion in dynamic water and high early strength, which is beneficial for realizing the high-value utilization of bulk solid waste and filling of extremely water-rich mines.

[0009] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0010] In a first aspect, the present invention provides an anti-dispersion solid waste grouting filling material, comprising slurry A and slurry B; slurry A, by mass parts, comprises the following components: 400-1000 parts fly ash, 500-1000 parts blast furnace slag, 100-500 parts silicate cement, 250-1200 parts water, 5-50 parts sodium hydroxide and 10-50 parts PolyFury-I;

[0011] PolyFury-I contains acrylamide and N,N,N',N'-tetramethylethylenediamine (TEMED) in a mass ratio of 15-30:2-5.

[0012] Slurry B, by mass, includes the following components: 20-200 parts water glass, 5-50 parts PolyFury-II;

[0013] PolyFury-II contains water glass, ammonium persulfate solution, xanthan gum, and carboxymethyl cellulose in a mass ratio of 30-150:0.5-5:0.5-15:0.5-15.

[0014] Secondly, the present invention provides a method for preparing the anti-dispersion solid waste grouting filling material, comprising the following steps:

[0015] Fly ash, blast furnace slag, silicate cement, water, and sodium hydroxide are mixed evenly in proportion to obtain a mixed slurry;

[0016] PolyFury-I was added to the mixed slurry to obtain slurry A;

[0017] Water glass and PolyFury-II were mixed in a certain proportion to obtain slurry B.

[0018] Thirdly, the present invention provides the application of the anti-dispersion solid waste grouting filling material in grouting filling under dynamic water conditions.

[0019] The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:

[0020] This invention addresses the problem of grout materials being easily dispersed and diluted during grouting, thus failing to achieve a sealing effect. It provides an anti-dispersion performance optimizer that effectively improves the dynamic water resistance of the grouting material, increasing the anti-dispersion rate by over 80%, thereby enhancing the sealing effect in dynamic water and solving the problem of insufficient sealing by traditional grouting materials. Furthermore, it can reduce the hardening shrinkage rate through a water glass-slag activation system, while simultaneously meeting the dual requirements of the "Green Mine Construction Standard" for solid waste utilization rate and filling body strength.

[0021] The anti-dispersion solid waste grouting filling material provided by this invention innovatively adopts the synergistic mechanism of composite anti-dispersion agents PolyFury-Ⅰ and PolyFury-Ⅱ, which significantly improves the anti-dispersion performance of the slurry while effectively overcoming the problem of fluidity deterioration caused by the traditional use of anti-dispersion agents alone. It achieves rapid anchoring of slurry under dynamic water conditions, particle anti-migration and improved volume stability.

[0022] This invention uses fly ash, blast furnace slag, water glass, silicate cement, and sodium hydroxide to form a cementitious matrix. Based on the complementary chemical components, it synergistically activates the active components of coal-based solid waste, forming a stable mineral phase structure system, enabling the industrial application of bulk coal-based solid waste as a substitute for traditional silicate raw materials. This technical solution achieves reduced raw material costs and freed up mine storage space by optimizing the particle size distribution and reactivity ratio of solid waste. The preparation process uses a composite alkali activator of water glass and sodium hydroxide instead of silicate cement, reducing carbon emissions and energy consumption. Attached Figure Description

[0023] 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.

[0024] Figure 1 This is a schematic diagram of the components and mixing process of the two-liquid grouting material in an embodiment of the present invention.

[0025] Figure 2 This is a diagram showing the effect of dynamic water anti-dispersion test on the dynamic water anti-dispersion solid waste grouting filling material in the embodiment of the present invention. Detailed Implementation

[0026] It should be noted that the following detailed description is illustrative and intended to provide further explanation 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.

[0027] In a first aspect, the present invention provides an anti-dispersion solid waste grouting filling material, comprising slurry A and slurry B; slurry A, by mass parts, comprises the following components: 400-1000 parts fly ash, 500-1000 parts blast furnace slag, 100-500 parts silicate cement, 250-1200 parts water, 5-50 parts sodium hydroxide and 10-50 parts PolyFury-I;

[0028] PolyFury-I contains acrylamide and N,N,N',N'-tetramethylethylenediamine (TEMED) in a mass ratio of 15-30:2-5.

[0029] Slurry B, by mass, includes the following components: 20-200 parts water glass, 5-50 parts PolyFury-II;

[0030] PolyFury-II contains water glass, ammonium persulfate solution, xanthan gum, and carboxymethyl cellulose in a mass ratio of 30-150:0.5-5:0.5-15:0.5-15.

[0031] In practical applications of grouting in flowing water, traditional solid waste materials exhibit poor resistance to dispersibility in flowing water. The grout is easily diluted or dispersed by flowing water, affecting its original proportions and functions. Furthermore, its setting time is slow, resulting in poor sealing effects against flowing water. Acrylamide, TEMED, and ammonium persulfate undergo a polymerization reaction to form polyacrylamide polymer chains, which can significantly increase the viscosity of cement particles in cement-based materials, thereby enhancing the grout's resistance to dispersibility in flowing water without excessively prolonging its initial setting time.

[0032] However, the formation water contains a variety of inorganic salts (mostly Na). + Ca 2+ Mg 2+ (etc.), inorganic salts (Na) + Ca 2+ Mg 2 +The concentration of certain substances can cause varying degrees of viscosity loss in the chemical weak gel in the grouting material, significantly affecting its dynamic water dispersibility. Furthermore, the interface between the organic matter generated by the polymerization reaction and the inorganic environment of the cement-based material is too pronounced, leading to a significant decrease in the strength of the material after setting. To address these issues, a cross-linked copolymer weak gel additive composed of carboxymethyl cellulose and xanthan gum is added. This not only effectively improves the salt resistance and high-temperature stability of the weak gel anti-dispersibility additive, achieving modification and optimization of the dynamic water anti-dispersibility optimizer for salt and high-temperature resistance, but also breaks down the interface between the inorganic and organic components, ensuring that the addition of the anti-dispersibility optimizer does not significantly affect the strength of the cement-based material.

[0033] The modulus of water glass is adjusted by regulating the amount of sodium hydroxide added, where the purity of the sodium hydroxide solid is greater than 99%. Water glass is inexpensive and has good compatibility, primarily serving to reduce costs and for dilution.

[0034] In some embodiments, the anti-dispersion solid waste grouting filling material comprises, by weight, the following components: 600-800 parts fly ash, 700-900 parts blast furnace slag, 200-500 parts silicate cement, and 500-1000 parts water.

[0035] In some embodiments, the mass percentage of acrylamide in PolyFury-I is 80-90%.

[0036] Preferably, the mass percentage of acrylamide in the PolyFury-I is 82-87%.

[0037] TEMED and ammonium persulfate act as oxidizers and reducers of acrylamide monomers, respectively. A certain amount of TEMED and ammonium persulfate can synthesize long-chain polymers from acrylamide monomers. When mixed with solid waste slurry, this significantly increases the viscosity of the cement slurry. When the amounts of TEMED and ammonium persulfate exceed a certain threshold, the polymerization reaction becomes rapid, also known as explosive polymerization, resulting in shorter polymer chains and reduced viscosity. When the amounts of TEMED and ammonium persulfate are below a certain threshold, the polymerization reaction slows down, and longer polymer chains cannot be formed. Ultimately, TEMED and ammonium persulfate contents of 5% and 8% respectively, the same as in the baseline anti-dispersion optimizer, were determined to be the most effective.

[0038] The amount of acrylamide added is positively correlated with the effect of the anti-dispersant optimizer, but excessive content will lead to violent polymerization reaction of the anti-dispersant and make it difficult to mix with cement-based materials.

[0039] In some embodiments, in PolyFury-II, the mass ratio of water glass, ammonium persulfate solution, xanthan gum, and carboxymethyl cellulose is 30-150:1-5:1-15:1-15.

[0040] Preferably, the mass fraction of the ammonium persulfate solution is 15-25%.

[0041] Preferably, in PolyFury-II, the mass percentage of carboxymethyl cellulose is 4-15% and the mass percentage of xanthan gum is 4-15%.

[0042] The polymer chains formed by acrylamide copolymerization have a clear organic-inorganic interface with the cementitious grout, and the ions in groundwater can cause some loss of viscosity. Adding carboxymethyl cellulose and xanthan gum can crosslink the organic polymer with the inorganic cementitious grout, offsetting the resulting strength loss and resisting the viscosity reduction effect of saline groundwater. However, excessive addition can slow down the cement hydration reaction, increase the setting time of the material, and reduce the 28-day strength of the cementitious aggregate.

[0043] In some embodiments, the fly ash is grade II or higher, with a fineness ≤15μm and a water requirement ratio ≤100%. The total mass of silicon dioxide, aluminum oxide, ferric oxide, calcium oxide, and magnesium oxide in the fly ash is ≥85%.

[0044] In some embodiments, the blast furnace slag is granulated blast furnace slag powder with a specific surface area ≥300 m². 2 / kg, vitreous content ≥80%, 28d activity index ≥95%, CaO content ≥35wt%, Al2O3 content ≤15wt%, water content ≤1.0%.

[0045] In some embodiments, the water glass has a modulus of 3.2, a solid content of 40%, a Baumé degree of 40, and a pH value of 9.

[0046] In some embodiments, the silicate cement does not deliquesce or clump.

[0047] In some embodiments, the method for calculating the amount of sodium hydroxide added when adjusting the modulus is as follows:

[0048] (1);

[0049] Wherein: X - the amount of sodium hydroxide added when adjusting the modulus;

[0050] The adjustment endpoint value of m-water glass modulus;

[0051] The mass of n-water glass;

[0052] The molar mass of sodium 62-oxide;

[0053] The molar mass of sodium hydroxide 40;

[0054] 9.2% sodium oxide content in water glass;

[0055] 3.2 - Modulus of water glass.

[0056] Secondly, the present invention provides a method for preparing the anti-dispersion solid waste grouting filling material, comprising the following steps:

[0057] Fly ash, blast furnace slag, silicate cement, water, and sodium hydroxide are mixed evenly in proportion to obtain a mixed slurry;

[0058] PolyFury-I was added to the mixed slurry to obtain slurry A;

[0059] Water glass and PolyFury-II were mixed in a certain proportion to obtain slurry B.

[0060] In some embodiments, grout A and grout B are mixed evenly before grouting.

[0061] Thirdly, the present invention provides the application of the anti-dispersion solid waste grouting filling material in grouting filling under dynamic water conditions.

[0062] The present invention will be further described below with reference to the embodiments.

[0063] Example 1

[0064] A method for preparing an anti-dispersion solid waste grouting filling material, such as Figure 1 As shown, it includes the following steps:

[0065] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 10 parts PolyFury-I, and 10 parts PolyFury-II.

[0066] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0067] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0068] Step 3: The preparation method of PolyFury-II is as follows:

[0069] Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 20%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir thoroughly to mix them to obtain PolyFury-II;

[0070] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0071] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0072] In step four, the blast furnace slag, fly ash, and silicate cement must be thoroughly mixed with water and sodium hydroxide to prevent problems such as excessively large local pores in the gel and reduced strength caused by uneven mixing.

[0073] Example 2

[0074] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0075] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 15 parts PolyFury-I, and 10 parts PolyFury-II.

[0076] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0077] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0078] Step 3: The preparation method of PolyFury-II is as follows:

[0079] Take 400g of water glass, 30g of ammonium persulfate solution (mass fraction of 25%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir thoroughly to mix them to obtain PolyFury-II;

[0080] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0081] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0082] Example 3

[0083] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0084] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 5 parts PolyFury-I, and 10 parts PolyFury-II.

[0085] Step 2: The synthesis and preparation method of PolyFury-Ⅰ is as follows:

[0086] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0087] Step 3: The preparation method of PolyFury-II is as follows:

[0088] Take 500g of water glass, 20g of ammonium persulfate solution (mass fraction of 15%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir thoroughly to mix them to obtain PolyFury-II;

[0089] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0090] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0091] Example 4

[0092] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0093] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 10 parts PolyFury-I, and 15 parts PolyFury-II.

[0094] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0095] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 25g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0096] Step 3: The preparation method of PolyFury-II is as follows:

[0097] Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 20%), 150g of xanthan gum, and 150g of carboxymethyl cellulose, and stir thoroughly to mix them to obtain PolyFury-II;

[0098] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0099] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0100] Example 5

[0101] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0102] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 10 parts PolyFury-I, and 5 parts PolyFury-II.

[0103] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0104] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 45g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0105] Step 3: The preparation method of PolyFury-II is as follows:

[0106] Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 22%), 100g of xanthan gum, and 150g of carboxymethyl cellulose, and stir them thoroughly to obtain PolyFury-II;

[0107] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly, and add PolyFury-Ⅰ to the above mixture to obtain slurry A;

[0108] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0109] Example 6

[0110] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0111] Step 1: Weigh the raw materials according to their mass fraction, including 600 parts fly ash, 600 parts blast furnace slag, 40 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 10 parts PolyFury-I, and 10 parts PolyFury-II.

[0112] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0113] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 40g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0114] Step 3: The preparation method of PolyFury-II is as follows:

[0115] Take 400g of water glass, 10g of ammonium persulfate solution (mass fraction of 20%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir thoroughly to mix them to obtain PolyFury-II;

[0116] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0117] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0118] Example 7

[0119] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0120] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 20 parts water glass, 200 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 20 parts PolyFury-I, and 20 parts PolyFury-II.

[0121] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0122] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0123] The synthesis and preparation method of PolyFury-II is as follows:

[0124] Step 3: Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 23%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir them thoroughly to obtain PolyFury-II solution.

[0125] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0126] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0127] Example 8

[0128] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0129] Step 1: Weigh the raw materials according to their mass fraction, including 700 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 300 parts silicate cement, 330 parts water, 10 parts sodium hydroxide, 10 parts PolyFury-I, and 10 parts PolyFury-II.

[0130] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0131] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I solution.

[0132] Step 3: The preparation method of PolyFury-II is as follows:

[0133] Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 24%), 50g of xanthan gum, and 50g of carboxymethyl cellulose, and stir thoroughly to mix them to obtain PolyFury-II;

[0134] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0135] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0136] Example 9

[0137] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0138] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 700 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 270 parts water, 20 parts sodium hydroxide, 10 parts PolyFury-I, and 10 parts PolyFury-II.

[0139] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0140] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0141] Step 3: The preparation method of PolyFury-II is as follows:

[0142] Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 20%), 150g of xanthan gum, and 150g of carboxymethyl cellulose, and stir thoroughly to mix them to obtain PolyFury-II.

[0143] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly, and add PolyFury-Ⅰ to the above mixture to obtain slurry A.

[0144] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0145] Example 10

[0146] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0147] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 15 parts sodium hydroxide, 15 parts PolyFury-I, and 15 parts PolyFury-II.

[0148] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0149] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0150] Step 3: The preparation method of PolyFury-II is as follows:

[0151] Take 600g of water glass, 10g of ammonium persulfate solution (mass fraction of 23%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir them thoroughly to obtain PolyFury-II;

[0152] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0153] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0154] Example 11

[0155] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0156] Step 1: Weigh the raw materials according to their mass fraction, including 500 parts fly ash, 500 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 5 parts sodium hydroxide, 10 parts PolyFury-I, and 10 parts PolyFury-II.

[0157] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0158] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0159] Step 3: The preparation method of PolyFury-II is as follows:

[0160] Take 400g of water glass, 10g of ammonium persulfate solution (mass fraction of 20%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir them thoroughly to obtain PolyFury-II.

[0161] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0162] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0163] Example 12

[0164] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0165] Step 1: Weigh the raw materials according to their mass fraction, including 600 parts fly ash, 400 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 10 parts PolyFury-I, and 10 parts PolyFury-II.

[0166] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0167] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0168] Step 3: The preparation method of PolyFury-II is as follows:

[0169] Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 20%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir them thoroughly to obtain PolyFury-II.

[0170] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0171] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0172] Example 13

[0173] A method for preparing an anti-dispersion solid waste grouting filling material includes the following steps:

[0174] Step 1: Weigh the raw materials according to their mass fraction, including 400 parts fly ash, 600 parts blast furnace slag, 30 parts water glass, 100 parts silicate cement, 300 parts water, 10 parts sodium hydroxide, 10 parts PolyFury-I, and 10 parts PolyFury-II.

[0175] Step 2: The preparation method of PolyFury-Ⅰ is as follows:

[0176] Take 300g of acrylamide, dilute it to a 20% acrylamide solution, add 35g of N,N,N',N'-tetramethylethylenediamine, stir thoroughly to dissolve it, and obtain PolyFury-I.

[0177] Step 3: The preparation method of PolyFury-II is as follows:

[0178] Take 300g of water glass, 10g of ammonium persulfate solution (mass fraction of 20%), 100g of xanthan gum, and 100g of carboxymethyl cellulose, and stir them thoroughly to obtain PolyFury-II.

[0179] Step 4: Mix the weighed blast furnace slag, fly ash, silicate cement, water and sodium hydroxide evenly. Weigh PolyFury-I according to the solid content ratio and add PolyFury-I to the above mixture to obtain slurry A.

[0180] PolyFury-II was added to the weighed water glass and stirred thoroughly to mix it, resulting in slurry B.

[0181] Comparative Example 1

[0182] The difference from Example 1 is that PolyFury-Ⅱ is omitted, while everything else is the same as Example 1.

[0183] Comparative Example 2

[0184] The difference from Example 1 is that ammonium persulfate in PolyFury-II is omitted, while everything else is the same as in Example 1.

[0185] Comparative Example 3

[0186] The difference from Example 1 is that xanthan gum in PolyFury-II is omitted, while everything else is the same as in Example 1.

[0187] Comparative Example 4

[0188] The difference from Example 1 is that carboxymethyl cellulose in PolyFury-II is omitted, while everything else is the same as in Example 1.

[0189] Comparative Example 5

[0190] The difference from Example 1 is that acrylamide in PolyFury-I is omitted, while everything else is the same as in Example 1.

[0191] Comparative Example 6

[0192] The difference from Example 1 is that N,N,N',N'-tetramethylethylenediamine in PolyFury-I is omitted; otherwise, it is the same as Example 1.

[0193] Comparative Example 7

[0194] The difference from Example 1 is that water glass is omitted, but everything else is the same as in Example 1.

[0195] Comparative Example 8

[0196] The difference from Example 1 is that water glass is replaced with an equal amount of silicate cement, while everything else is the same as in Example 1.

[0197] Comparative Example 9

[0198] The difference from Example 1 is that PolyFury-II is replaced with an equal amount of PolyFury-I, while everything else is the same as in Example 1.

[0199] Comparative Example 10

[0200] The difference from Example 1 is that PolyFury-Ⅰ is replaced with PolyFury-Ⅱ in equal amounts, while everything else is the same as in Example 1.

[0201] Comparative Example 11

[0202] The difference from Example 1 is that acrylamide is replaced with an equal amount of N,N,N',N'-tetramethylethylenediamine, while everything else is the same as in Example 1.

[0203] Comparative Example 12

[0204] The difference from Example 1 is that xanthan gum is replaced with an equal amount of carboxymethyl cellulose, while everything else is the same as in Example 1.

[0205] Comparative Example 13

[0206] The difference from Example 1 is that ammonium persulfate is replaced with an equal amount of carboxymethyl cellulose, while everything else is the same as in Example 1.

[0207] Performance testing

[0208] The anti-dispersion solid waste grouting filling materials prepared in Examples 1-13 and Comparative Examples 1-13 were tested using the following methods:

[0209] The initial setting time and final setting time of the material were determined using an ISO standard Vicat apparatus.

[0210] The fluidity of the slurry was tested according to the method in GB / T8077-2012 "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.

[0211] The viscosity of the material was measured using an NDJ-4 rotary viscometer.

[0212] The water retention rate of the implemented materials was measured using an anti-dispersion test device, such as... Figure 2 As shown;

[0213] The detailed test steps for the anti-dispersion experiment are as follows:

[0214] Test equipment:

[0215] Dynamic water flushing simulation device (refer to) Figure 2 It includes an adjustable tilt glass plate (1000 mm long × 300 mm wide), a constant flow water supply system, a flow rate sensor (range 0.1–5.0 m / s), and an electronic balance (accuracy 0.1 g).

[0216] Test steps:

[0217] 1. Sample preparation

[0218] After mixing slurry A and slurry B in the specified ratio, immediately take 500±5 g of slurry and spread it evenly in the center area of ​​the glass plate (spreading area: 200 mm × 150 mm, thickness 10 mm).

[0219] 2. Device parameter settings

[0220] Adjust the tilt angle of the glass plate to 30±1°;

[0221] Adjust the water flow velocity to 1.2 ± 0.1 m / s;

[0222] The water temperature should be controlled at 20±2℃.

[0223] 3. The process of flushing with flowing water

[0224] Start the constant flow water supply system, and let the water flow down evenly from the top of the glass plate to continuously rinse the sample for 3 minutes.

[0225] Collect the slurry residue that flows out from the bottom of the glass plate, filter it through a 0.15 mm sieve, and dry it at 105°C to constant weight.

[0226] 4. Retention rate calculation

[0227] Flow retention rate (%) = W1 / W0 × 100%;

[0228] In the formula:

[0229] W0: Initial slurry solid mass (g);

[0230] W1: Total solid mass (g) of the hardened body on the glass plate and the residue trapped by the screen after rinsing.

[0231] The compressive strength of the material was tested under standard curing and underwater molding curing conditions, and the ratio of water strength to land strength was calculated.

[0232] The standard curing conditions refer to the routine curing of materials in a controlled temperature and humidity environment, simulating an ideal curing environment.

[0233] Specific parameters:

[0234] 1. Temperature: 20±2℃;

[0235] 2. Relative humidity: >95%;

[0236] 3. Maintenance period: Typically, the intensity is tested at 7 days and 28 days;

[0237] 4. Operating Procedures:

[0238] (1) After the specimens are formed, they are placed in a curing box / constant temperature room to avoid moisture evaporation.

[0239] (2) The curing water should be saturated lime water (Ca(OH)2) to prevent carbon dioxide corrosion.

[0240] The underwater molding and curing conditions refer to simulating a dynamic water environment to test the molding performance and strength development of materials under the action of water flow.

[0241] Specific parameters:

[0242] 1. Water temperature: 5-25℃;

[0243] 2. Water flow velocity: 0.5-3.0 m / s;

[0244] 3. Maintenance methods:

[0245] (1) Place the specimen in a constant flow water tank and immerse it completely in the flowing water.

[0246] (2) After curing to the target age (e.g., 7d / 28d), remove it, wipe the surface dry and perform a pressure test.

[0247] The water-land strength ratio is the ratio of "compressive strength after underwater curing" to "compressive strength after surface curing".

[0248] The test and calculation results are shown in Tables 1 and 2.

[0249] Table 1. Performance test results of the slurries prepared in Examples 1-13

[0250]

[0251] Table 2. Performance test results of the slurries prepared in Comparative Examples 1-13

[0252]

[0253] The anti-dispersion solid waste grouting filling material provided by this invention has been verified by experiments to have the following outstanding technical effects: 1) Excellent anti-dispersion performance: The grout retention rate under dynamic water conditions is significantly better than that of conventional grouting materials (retention rate ≤70%), which can effectively inhibit grout loss and ensure the reliability of underwater grouting; 2) Stable water-land strength ratio: The compressive strength after 28 days of underwater curing is much larger than that after standard curing, indicating that the material can still be fully hydrated and form a dense structure in the underwater environment; 3) Adjustable setting characteristics: By adjusting the ratio of water glass to sodium hydroxide, the initial setting time can be precisely controlled to meet the needs of different engineering conditions; 4) Optimized rheological properties: The initial viscosity of the grout is controlled within the range of 500~900 mPa·s, which has both high fluidity and erosion resistance, and is suitable for grouting construction under complex geological conditions; 5) Significant resource utilization benefits: Using industrial solid waste as the main raw material, the material cost is reduced while realizing the efficient resource utilization of solid waste.

[0254] This invention effectively solves the technical problems of traditional grouting materials such as easy dispersion and insufficient strength development in underwater environments by innovatively optimizing the synergistic mechanism of solid waste-based cementitious materials and polymer additives. It has significant technical advancement and engineering application value.

[0255] 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. A grouting filler material for anti-dispersion solid waste, characterized in that: It includes slurry A and slurry B; slurry A, by mass, includes the following components: 600-800 parts fly ash, 700-900 parts blast furnace slag, 200-500 parts silicate cement, 500-1000 parts water, 5-50 parts sodium hydroxide and 10-50 parts PolyFury-I; PolyFury-I contains acrylamide and N,N,N',N'-tetramethylethylenediamine in a mass ratio of 15-30:2-5; the mass percentage of acrylamide is 80-90%. Slurry B, by mass, includes the following components: 20-200 parts water glass, 5-50 parts PolyFury-II; PolyFury-II contains water glass, ammonium persulfate solution, xanthan gum, and carboxymethyl cellulose in a mass ratio of 30-150:1-5:0.5-15:0.5-15.

2. The anti-dispersion solid waste grouting filling material according to claim 1, characterized in that: In PolyFury-Ⅱ, the mass fraction of the ammonium persulfate solution is 15-25%, the mass percentage of carboxymethyl cellulose is 4-15%, and the mass percentage of xanthan gum is 4-15%.

3. The anti-dispersion solid waste grouting filling material according to claim 1, characterized in that: In PolyFury-II, the mass ratio of water glass, ammonium persulfate solution, xanthan gum, and carboxymethyl cellulose is 50-150:2-5:4-15:4-15.

4. The anti-dispersion solid waste grouting filling material according to claim 1, characterized in that: The calculation method for the amount of sodium hydroxide added when adjusting the modulus is as follows: （1）； Wherein: X - the amount of sodium hydroxide added when adjusting the modulus; m - The key value for adjusting the water glass modulus; The mass of n-water glass; The molar mass of sodium 62-oxide; The molar mass of sodium hydroxide 40; 9.2% sodium oxide content in water glass; 3.2 - Modulus of water glass.

5. The preparation method of the anti-dispersion solid waste grouting filling material according to any one of claims 1-4, characterized in that: Includes the following steps: Fly ash, blast furnace slag, silicate cement, water, and sodium hydroxide are mixed evenly in proportion to obtain a mixed slurry; PolyFury-I was added to the mixed slurry to obtain slurry A; Water glass and PolyFury-II were mixed in a certain proportion to obtain slurry B.

6. The preparation method of the anti-dispersion solid waste grouting filling material according to claim 5, characterized in that: Before grouting, mix grout A and grout B thoroughly.

7. The application of the anti-dispersion solid waste grouting filling material according to any one of claims 1-4 in grouting filling under dynamic water conditions.

Images