Green press-slurry and grouting material based on industrial solid waste and preparation method thereof

Abstract

The application discloses a kind of green pressure grouting material based on industrial solid waste and preparation method thereof, it is related to light building material technical field.A kind of green pressure grouting material based on industrial solid waste, by following mass parts of raw materials composition: industrial solid waste base cementing material 50-80 parts, active activator 5-15 parts, dispersing agent 0.5-3 parts, retarder 0.1-1.5 parts, water 30-50 parts, stabilizing reinforcing agent 5-10 parts;The industrial solid waste base cementing material is at least one in slag, fly ash, steel slag.The application uses industrial solid waste to replace traditional cement base material, significantly reduces resource consumption and carbon emission, realizes solid waste high-value utilization;Through the molecular interface regulation and control of stabilizing reinforcing agent and the synergistic effect of multiple components, the slurry fluidity, compressive strength and long-term stability are significantly improved, and the setting time is reasonably regulated to match the construction demand.

Description

Technical Field

[0001] This invention relates to the field of lightweight building materials technology, specifically to a green grouting material based on industrial solid waste and its preparation method. Background Technology

[0002] In the field of building materials, grouting materials are widely used in many scenarios such as infrastructure construction, tunnel engineering, and bridge reinforcement, playing a crucial role in filling pores, fixing components, and enhancing structural stability. Traditional grouting materials are mainly based on cement, with various chemical admixtures added to improve their performance. However, these materials have many problems. On the one hand, cement production is energy-intensive and produces large amounts of carbon emissions, which contradicts the current concept of green and sustainable development; on the other hand, their performance improvement potential is limited, making it difficult to meet the stringent requirements of some special projects for high strength, high fluidity, and durability.

[0003] Meanwhile, with the rapid development of industry, the amount of industrial solid waste such as slag, fly ash, and steel slag is increasing dramatically. Most of this solid waste is simply dumped or landfilled, not only occupying a large amount of land resources but also potentially causing environmental pollution such as soil and water pollution. How to effectively treat and reuse industrial solid waste has become an urgent problem to be solved. Against this backdrop, the development of a green grouting material based on industrial solid waste is particularly important. Applying it to the grouting field of lightweight building materials can not only realize the resource utilization of industrial solid waste, reduce dependence on natural resources, and reduce environmental pollution, but also leverage the characteristics of industrial solid waste itself to develop new building materials with better performance and lower costs, providing the construction industry with more environmentally friendly and efficient solutions and promoting the sustainable development of the entire industry. Summary of the Invention

[0004] The present invention aims to provide a green grouting material based on industrial solid waste and its preparation method, so as to realize the resource utilization of solid waste and meet the engineering demand for high-performance and environmentally friendly materials.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is: a green grouting material based on industrial solid waste, which is composed of the following raw materials in parts by weight: 50-80 parts of industrial solid waste-based cementitious material, 5-15 parts of active activator, 0.5-3 parts of dispersant, 0.1-1.5 parts of retarder, 30-50 parts of water, and 5-10 parts of stabilizing and reinforcing agent.

[0006] The industrial solid waste-based cementitious material is at least one of slag, fly ash, and steel slag.

[0007] The stabilizing and reinforcing agent has the structure shown in Formula 1:

[0008]

[0009] R1 is selected from: methyl, ethyl, tert-butyl, phenyl, methoxy.

[0010] Furthermore, the aforementioned green grouting material based on industrial solid waste is composed of the following raw materials in parts by weight: 65 parts of industrial solid waste-based cementitious material, 10 parts of active activator, 2 parts of dispersant, 0.8 parts of retarder, 40 parts of water, and 8 parts of stabilizing and reinforcing agent. Furthermore, the specific surface area of ​​the industrial solid waste-based cementitious material is 400-600 m². 2 / kg.

[0011] Furthermore, the active activator is selected from sodium hydroxide and / or sodium silicate.

[0012] Furthermore, the dispersant is sodium lignosulfonate.

[0013] Furthermore, the retarder is one of sodium gluconate, citric acid, or borax.

[0014] Furthermore, the stabilizing agent is selected from any one of the compounds shown in the following structures:

[0015]

[0016] Furthermore, the method for synthesizing the stabilizing and reinforcing agent is as follows:

[0017]

[0018] Step 1: Raw material 1 and raw material 2 are synthesized into intermediate 1 via a Suzuki coupling reaction;

[0019] Step 2: Intermediate 1 and raw material 3 are synthesized by Buchwald-Hartwig aromatic amination reaction to obtain a stabilizing and reinforcing agent.

[0020] A method for preparing a green grouting material based on industrial solid waste includes the following steps:

[0021] S1. Pretreatment: The industrial solid waste-based cementitious material is dried, crushed, and then ground to a specific surface area ≥ 400 m². 2 / kg;

[0022] S2. Mixing: Dry mix the pretreated industrial solid waste-based cementitious material with the active activator, dispersant, retarder, and stabilizer according to the specified ratio for 3-5 minutes to obtain a mixed dry material;

[0023] S3. Pulping: Add water to the mixed dry material and mix at a stirring speed of 600-1000 r / min for 5-10 min to obtain a green grouting material based on industrial solid waste.

[0024] Furthermore, the grinding time is 30-60 minutes.

[0025] Furthermore, the drying process is carried out at 70-80°C for 1-2 hours.

[0026] Furthermore, the initial fluidity of the green grouting material based on industrial solid waste is ≥260mm, the fluidity loss rate is ≤10% after 30min, the initial setting time is ≥2h, and the compressive strength is ≥30MPa after 28d.

[0027] Furthermore, the aforementioned green grouting material based on industrial solid waste is applied in the field of lightweight building materials.

[0028] The green grouting material based on industrial solid waste described in this invention has significant advantages in the field of lightweight building materials: by using industrial solid waste such as slag and fly ash to replace traditional cement substrates, it realizes the resource utilization of solid waste, reduces land occupation and environmental pollution, and also reduces production energy consumption and carbon emissions, which is in line with the concept of green and sustainable development; its unique stabilizing and reinforcing agent and optimized ratio endow the material with high fluidity and low flow loss rate, ensuring high filling and operability during construction, while the retarder controls the initial setting time and 28-day compressive strength to take into account both the construction window and structural strength requirements, making it particularly suitable for pore filling and reinforcement of lightweight structures; in addition, the low cost of industrial solid waste significantly reduces the economic cost of materials, providing an environmentally friendly, high-performance and cost-effective solution for lightweight buildings.

[0029] The stabilizing and reinforcing agent described in this invention contains aromatic rings, which can bind to the surface of industrial solid waste particles through π-π stacking, hydrogen bonding, or van der Waals forces to form a three-dimensional network structure. This improves the suspension stability of the slurry, preventing bleeding or stratification caused by solid-liquid separation during construction. Simultaneously, it fills the pores of hydration products in cementitious materials, reducing defects and improving 28-day compressive strength. The hydrophilicity / hydrophobicity of the substituents can be adjusted, enhancing interfacial compatibility with different solid waste particles (slag / fly ash). The stabilizing and reinforcing agent can reduce the surface energy of materials, reduce particle agglomeration, and synergistically improve initial flowability with dispersants. The molecules can capture free ions, inhibiting harmful crystallization.

[0030] The active activator of the present invention releases OH - And / or silicate ions activate aluminosilicates in industrial solid waste, promoting hydration to form CSH gel, laying the foundation for strength; dispersants disperse particles through electrostatic repulsion, while stabilizers form a three-dimensional network through intermolecular forces (hydrogen bonds, π-π stacking), both maintaining slurry fluidity and suspension stability in stages; retarder chelates Ca... 2+By delaying the hydration induction period, it complements the later cross-linking enhancement mechanism of the stabilizing agent, ensuring the construction window and improving the 28-day compressive strength through pore filling and interface strengthening, ultimately achieving performance balance under high industrial solid waste dosage.

[0031] Compared with the prior art, the beneficial effects of the present invention are:

[0032] 1. Significantly improved environmental performance: By replacing traditional cement base materials with high amounts of industrial solid waste, resource consumption and carbon emissions are greatly reduced, solid waste is utilized as a resource, and the environmental burden is reduced.

[0033] 2. Comprehensive performance optimization: While ensuring high fluidity and low flow loss rate, the material's long-term compressive strength and early strength show a significant improvement trend, meeting the requirements of high-strength engineering.

[0034] 3. Enhanced construction adaptability: Through the synergistic effect of the stabilizing agent and the mixing ratio, the initial setting time can be reasonably controlled, which not only extends the construction window but also maintains the stability of the slurry, effectively avoiding segregation or bleeding problems. Attached Figure Description

[0035] Figure 1 This is a method for synthesizing the stabilizing and reinforcing agent described in this invention. Detailed Implementation

[0036] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] Synthesis example 1

[0038] Synthesis of Stabilizing Reinforcing Agent 1:

[0039]

[0040] Step 1: Under a nitrogen atmosphere, 25 g of starting material 1, 20.19 g of starting material 2, 26.56 g of anhydrous potassium carbonate, 3.33 g of tetrakis(triphenylphosphine)palladium, and 250 g of a mixed solution of toluene, ethanol, and water (volume ratio 2:1:1) were added sequentially to the reaction system. The mixture was heated to 95°C and refluxed for 10 hours. The heating was then turned off, and the mixture was cooled to room temperature. After standing, the phases were separated. The aqueous phase was extracted twice with toluene. The organic phases were combined, washed three times with water, evaporated to dryness, and subjected to column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent to give 24.74 g of intermediate 1. MS: 346 (MS+H) + .

[0041] Step 2: Under a nitrogen atmosphere, 24.74 g of intermediate 1, 26.34 g of starting material 3, 19.80 g of anhydrous potassium carbonate, 1.97 g of tri-tert-butylphosphine, 0.7 g of tris(dibenzylacetone)dipalladium, and 250 g of toluene were added sequentially to the reaction system. The mixture was heated to 105 °C and refluxed for 10 hours. The heating was then turned off, the temperature was slightly lowered, and the mixture was filtered using silica gel. After the filtrate cooled to room temperature, it was washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried over anhydrous magnesium sulfate, evaporated to dryness, and subjected to column chromatography using a mixture of petroleum ether and ethyl acetate as the eluent to obtain 34.81 g of stabilizing agent 1. MS: 677 (MS+H) + .

[0042] Stabilizer 1 1 ¹H NMR (deuterated chloroform) values ​​are: δ 8.61 (s, 1H), 8.55 (d, 1H), 8.45 (d, 1H), 8.11 (dd, 1H), 8.03–7.98 (m, 1H), 7.85–7.69 (m, 4H), 7.65–7.58 (m, 1H), 7.46 (t, 2H), 7.32–7.19 (m, 2H), 7.10–7.00 (m, 2H), 6.35–6.28 (m, 1H), 6.17 (m, 1H), 5.48–5.40 (m, 2H), 4.66–4.58 (m, 1H), 3.73 (m, 1H), 3.22 (m, 2H), 2.49 (d, 3H), 1.42 (s, 6H), 1.10 (t, 3H).

[0043] Synthesis Example 2-Synthesis Example 5

[0044] The stabilizing agents synthesized in Synthetic Examples 2-5 were synthesized using the same method as in Example 1, except that raw material 1 was replaced. The specific structures of raw material 1, the stabilizing agents, and their MS data are shown in the table below.

[0045]

[0046]

[0047] Example 1

[0048] A green grouting material based on industrial solid waste has the following raw material composition by mass: 65 parts of industrial solid waste-based cementitious material (fly ash), 10 parts of active activator (sodium silicate), 2 parts of dispersant (sodium lignosulfonate), 0.8 parts of retarder (sodium gluconate), 40 parts of water, and 8 parts of stabilizing and reinforcing agent (stabilizing and reinforcing agent 1 synthesized in Synthesis Example 1).

[0049] The preparation method includes the following steps:

[0050] S1. Pretreatment: Dry the fly ash at 75℃ for 1.5 hours, then coarsely crush it using a jaw crusher, and finally grind it in a ball mill for 50 minutes to control the specific surface area of ​​the material to reach 550-650 m². 2 / kg;

[0051] S2. Mixing: Add the pretreated slag, active activator, dispersant, retarder, and stabilizer to a twin-helix mixer and dry mix at 45 r / min for 4 min;

[0052] S3. Pulping: Inject water into the mixed dry material and stir for 8 minutes at 800 r / min using a high-speed mixer to obtain a green grouting material based on industrial solid waste.

[0053] Examples 2-5

[0054] Referring to the preparation method in Example 1, the stabilizing and reinforcing agents were sequentially replaced with the stabilizing and reinforcing agents synthesized in Synthesis Examples 2-5, while the rest remained unchanged.

[0055] Comparative Example 1

[0056] Following the preparation method in Example 1, the stabilizing agent was replaced with comparative compound 1, while the rest remained unchanged.

[0057] Comparative compound 1:

[0058] Comparative Example 2

[0059] Following the preparation method in Example 1, without adding any stabilizing and reinforcing agents, the rest remained unchanged.

[0060] Comparative Example 3

[0061] Referring to the preparation method in Example 1, the raw material composition by mass was changed to: 90 parts of industrial solid waste-based cementitious material (fly ash), 20 parts of active activator (sodium silicate), 2 parts of dispersant (sodium lignosulfonate), 0.8 parts of retarder (sodium gluconate), 40 parts of water, and 8 parts of stabilizing agent (stabilizing agent 1 synthesized in Synthesis Example 1), with the rest remaining unchanged.

[0062] Performance testing:

[0063] The setting times of the test examples and comparative examples were determined according to the national standard GB / T 1346-2011 "Standard Consistency Water Requirement, Setting Time and Soundness Test Methods for Cement". The compressive strength of each mortar at different ages was tested according to the national standard GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)". The results are shown in the table below.

[0064]

[0065] Compared to the comparative examples that did not use a specific stabilizing agent or had an unbalanced ratio, the examples using the stabilizing agent of this invention showed a significant improvement in both long-term compressive strength and early strength, while maintaining a reasonable initial setting time within a suitable construction window. The introduction of the stabilizing agent significantly optimized the mechanical properties and construction adaptability of the material. Although the comparative examples, lacking the stabilizing agent or having an excessive ratio, may have prolonged the initial setting time, their overall strength was still lower than that of the examples. This indicates that the synergistic effect of the stabilizing agent and the raw material ratio in this invention has a crucial impact on improving material performance.

[0066] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A green grouting material based on industrial solid waste, characterized in that, It is composed of the following raw materials in parts by weight: 50-80 parts of industrial solid waste-based cementitious material, 5-15 parts of active activator, 0.5-3 parts of dispersant, 0.1-1.5 parts of retarder, 30-50 parts of water, and 5-10 parts of stabilizer and reinforcing agent. The industrial solid waste-based cementitious material is at least one of slag, fly ash, and steel slag. The stabilizing agent is selected from any one of the compounds shown in the following structures: ； ； 。 2. The green grouting material based on industrial solid waste as described in claim 1, characterized in that, The specific surface area of ​​the industrial solid waste-based cementitious material is 400-600 m². 2 / kg.

3. The green grouting material based on industrial solid waste as described in claim 1, characterized in that, The active activator is selected from sodium hydroxide and / or sodium silicate.

4. The green grouting material based on industrial solid waste as described in claim 1, characterized in that, The dispersant is sodium lignosulfonate.

5. The green grouting material based on industrial solid waste as described in claim 1, characterized in that, The retarder is one of sodium gluconate, citric acid, or borax.

6. The green grouting material based on industrial solid waste as described in claim 1, characterized in that, The green grouting material based on industrial solid waste has an initial flowability ≥260mm, a flowability loss rate ≤10% in 30min, an initial setting time ≥2h, and a compressive strength ≥30MPa in 28d.

7. A method for preparing a green grouting material based on industrial solid waste as described in any one of claims 1-6, characterized in that, Includes the following steps: S1. Pretreatment: The industrial solid waste-based cementitious material is dried, crushed, and then ground to a specific surface area ≥ 400 m². 2 / kg; S2. Mixing: Dry mix the pretreated industrial solid waste-based cementitious material with the active activator, dispersant, retarder, and stabilizer according to the specified ratio for 3-5 minutes to obtain a mixed dry material; S3. Pulping: Add water to the mixed dry material and mix at a stirring speed of 600-1000 r / min for 5-10 min to obtain a green grouting material based on industrial solid waste.

8. The method for preparing a green grouting material based on industrial solid waste according to claim 7, characterized in that, The grinding time is 30-60 minutes.

9. The method for preparing a green grouting material based on industrial solid waste according to claim 7, characterized in that, The drying process is carried out at 70-80℃ for 1-2 hours.

Images