Solid-waste-based cementing material modifier, cementing material and preparation method of solid-waste-based cementing material modifier

Abstract

The invention relates to the field of solid waste cementing materials, in particular to a solid waste-based cementing material modifier, a cementing material and a preparation method of the cementing material. The solid waste-based cementing material modifier comprises the following raw materials in parts by weight: 1-5 parts of a water-reducing dispersion component, 1-5 parts of a setting time adjusting component, 5-20 parts of a pH value adjusting component, 10-40 parts of a reinforcing component and 30-85 parts of an auxiliary component, and the auxiliary component is prepared by fly ash surface modification, nano-silica modification and mineral powder composite activation treatment. The modifier can significantly improve the strength, durability and workability of the cementing material and reduce the setting time. The cementing material is prepared by mixing activated gold tailings, steel slag, mineral slag, industrial byproduct gypsum and a modifier, is suitable for constructional engineering and has a wide prospect.

Description

Technical Field

[0001] The present invention relates to the field of solid waste cementitious materials, and particularly to a modifier for solid waste-based cementitious materials, a cementitious material and a preparation method thereof. Background Art

[0002] A cementitious material modifier is a chemical additive that can adjust the setting time of the cementitious material, improve the workability and mechanical properties, and is widely used in the production of mortar and concrete. Existing all-solid waste cementitious materials are usually composed of activated gold tailings, steel slag, slag and industrial by-product gypsum. Although they have environmental protection advantages, they have significant defects such as a large water demand for standard consistency and poor workability of the prepared concrete, which seriously restricts the popularization and application of solid waste-based cementitious materials.

[0003] Chinese Patent with application number CN202110692019.7 discloses a cementitious material and its preparation method and application. The invention provides a cementitious material and its preparation method and application, with the main components being coal gangue, carbide slag and an alkali activator (a mixed solution of sodium hydroxide aqueous solution and water glass). By combining carbide slag with coal gangue, the alkaline condition of the alkali activator is improved, the usage amount of sodium hydroxide is reduced, and at the same time, abundant calcium ions are provided for the polymerization reaction, enhancing the compressive strength. Thus, a high-strength coal gangue-carbide slag geopolymer cementitious material is successfully prepared under relatively low alkaline conditions. This cementitious material not only has good compressive strength and is suitable for rapid repair of tunnels and road surfaces, plugging of foundation leakage and solidification of soft soil masses, but also achieves the goals of green low-carbon and solid waste resource utilization. However, the above cementitious material is only composed of coal gangue, carbide slag and an alkali activator, and its performance adjustment mainly depends on the ratio of coal gangue to carbide slag and the dosage of the alkali activator. The adjustment means are relatively single and it is difficult to meet the diverse performance requirements of different projects for the cementitious material. Chinese Patent with application number CN201210596493.0 discloses a metakaolin-based inorganic composite cementitious material and its toughening modifier. The invention discloses a metakaolin-based inorganic composite cementitious material and its toughening modifier, which is composed of 60 - 80 parts by weight of fibers and 20 - 40 parts by weight of a fiber suspending agent. This toughening modifier can effectively improve the toughness and load-bearing capacity of the metakaolin-based inorganic composite cementitious material, and the preparation process is simple and the production cost is low. However, the polypropylene fiber mentioned in this technical solution is an organic substance, and there will be problems with the interfacial bonding between the inorganic metakaolin and slag, affecting the improvement of subsequent performance.

[0004] Therefore, developing a modifier for solid waste-based cementitious materials to improve the construction performance, mechanical properties and durability of the cementitious material is the key to realizing the wide application of solid waste-based cementitious materials. Summary of the Invention

[0005] To solve the above problems, the present invention provides a solid waste-based cementitious material modifier, a cementitious material and a preparation method thereof. By using specific modifier components and a preparation method, a modifier capable of significantly improving the performance of the cementitious material is obtained. By applying this modifier to the cementitious material, a cementitious material with high strength, high durability and good workability is obtained.

[0006] The technical solution adopted by the present invention to achieve the above object is as follows: A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 1-5 parts of a water-reducing and dispersing component, 1-5 parts of a setting time adjusting component, 5-20 parts of a pH value adjusting component, 10-40 parts of a strengthening component, and 30-85 parts of an auxiliary component; The preparation method of the auxiliary component is as follows: Step S1: Disperse fly ash in deionized water to form a dispersion liquid, heat the dispersion liquid to 60-70 °C, then add fatty alcohol polyoxyethylene ether and zirconia, stir for 3-4 h, and obtain preliminarily modified fly ash through post-treatment; Step S2: Under room temperature conditions, mix the preliminarily modified fly ash with a silane coupling agent, stir for 1-2 h, then add nano-silica, and stir at 55-65 °C for 2-3 h to obtain modified fly ash through post-treatment; Step S3: Mix the mineral powder with the modified fly ash obtained in Step S2 evenly to obtain a mixed material, dissolve sodium silicate, sodium hydroxide, and nano-aluminum oxide in deionized water to form a composite activation liquid, and add the composite activation liquid to the mixed material to obtain the auxiliary component through post-treatment.

[0007] Further, the addition amount of fly ash in the dispersion liquid in Step S1 is 0.1-0.15 g / mL, and the mass ratio of fatty alcohol polyoxyethylene ether, zirconia to fly ash is 0.5-1.5:0.2-0.8:10.

[0008] Further, the mass ratio of the preliminarily modified fly ash, the silane coupling agent to nano-silica in Step S2 is 1:0.01-0.05:0.01-0.04.

[0009] Further, the mass ratio of the mineral powder to the modified fly ash obtained in Step S2 in Step S3 is 0.6-2:1, the mass ratio of sodium silicate, sodium hydroxide, and nano-aluminum oxide is 6-7:2-3:1, the addition amount of nano-aluminum oxide in the composite activation liquid is 0.02-0.03 g / mL, and the mass-volume ratio of the mixed material to the composite activation liquid is 1:0.1-0.2 g / mL.

[0010] Furthermore, the preparation method of the water-reducing and dispersing component is as follows: preheat the polycarboxylate water reducer at 40 - 60 °C for 20 - 40 min, then add sodium lignosulfonate, stir for 40 - 50 min, then add an antifoaming agent, and continue to stir for 10 - 20 min. After cooling to room temperature, the water-reducing and dispersing component is obtained. Among them, the mass ratio of the polycarboxylate water reducer, sodium lignosulfonate, and the antifoaming agent is 2:0.8 - 1.2:0.002 - 0.005.

[0011] Furthermore, the setting time adjusting component is obtained by mixing sodium carbonate, bone glue protein, and sucrose.

[0012] Furthermore, the pH value adjusting component is slaked lime or sodium hydroxide.

[0013] Furthermore, the strengthening component is obtained by mixing sodium silicate, triethanolamine, triisopropanolamine, and an antifoaming agent.

[0014] A cementitious material comprises the following raw materials in parts by weight: 18 - 22 parts of activated gold tailings, 16 - 20 parts of steel slag, 48 - 52 parts of slag, 10 - 14 parts of industrial by - product gypsum, and 3 - 6 parts of the above - mentioned solid - waste - based cementitious material modifier.

[0015] A preparation method of a cementitious material comprises the following steps: mix the activated gold tailings, steel slag, slag, and industrial by - product gypsum evenly, and then add the solid - waste - based cementitious material modifier and mix evenly to obtain the product.

[0016] The present invention has the following beneficial effects: The present invention provides a solid waste-based cementitious material modifier composed of organic and inorganic functional materials. First, fly ash is modified by fatty alcohol polyoxyethylene ether and zirconia, then modified by nano-silica, and finally mixed with mineral powder and activated by a composite activator. The prepared auxiliary component synergistically acts with the water-reducing and dispersing component, setting time regulating component, pH value regulating component and strengthening component, which can significantly improve the performance of the cementitious material. Among them, the auxiliary component plays a crucial role in the solid waste-based cementitious material modifier. By combining physical modification and chemical activation, the compressive strength, flexural strength, fluidity and durability of the cementitious material can be significantly improved, and the water demand and setting time can be reduced; the water-reducing and dispersing component is prepared from polycarboxylate superplasticizer, sodium lignosulfonate and defoamer in a specific proportion, which can reduce the water demand for standard consistency and improve the fluidity of the paste; the setting time regulating component is composed of sodium carbonate, bone glue protein and sucrose, which can effectively reduce the setting time and meet the construction standard; the pH value regulating component selects slaked lime or sodium hydroxide, which can increase the pH value of the pore solution of the paste and provide an alkaline environment for the early reaction; the strengthening component is composed of water glass, triethanolamine, triisopropanolamine and defoamer. Among them, water glass activates the mineral activity to improve the early strength, triethanolamine and triisopropanolamine enhance the later strength, and the defoamer reduces the air content to improve the compactness. Through the synergy of each component, this modifier can reduce the water demand for standard consistency and setting time of the cementitious material, optimize the water-binder ratio, and at the same time significantly improve the fluidity, flexural strength and compressive strength, and improve the durability. The mortar concrete prepared with this modifier has excellent workability, and combines environmental protection and engineering practicability, and has broad application prospects. Specific embodiments

[0017] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.

[0018] The raw materials used in the following examples are all ordinary commercially available products. The fly ash has a mesh number of 325, a density of 2.6 g / cm³, and a melting point of 1200 °C, and is purchased from Hebei Leijiang New Material Technology Co., Ltd.; the fatty alcohol polyoxyethylene ether has an active ingredient content of 99% and an HLB value of 12.5, and is purchased from Shandong Yihui Chemical Co., Ltd.; the zirconia has a mesh number of 300 and an active ingredient content of 99%, and is purchased from Qinghe County Chaotai Metal Materials Co., Ltd.; the silane coupling agent is silane coupling agent KH-550; the nano-silica is TSP-H10 with a particle size of 20 nm and a silica content of 99%, and is purchased from Nanjing Tianxing New Material Co., Ltd.; the water glass has an active ingredient content of 40% and a model of ss-006, and is purchased from Jinan Songsheng New Material Co., Ltd.; the nano-alumina has a particle size of 50 nm and an active ingredient content of 99.99%, and is purchased from Hebei Wenlun Metal Materials Co., Ltd.; the polycarboxylate water reducing agent has an active ingredient content of 99% and a water reducing rate of 40%, and is purchased from Jinan Yanglan New Material Technology Co., Ltd.; the sodium lignosulfonate has an active ingredient content of 99%, and is purchased from Shandong Yihui Chemical Co., Ltd.; the defoaming agent has an active substance content of 90% and is an organosilicon defoaming agent with a model of AK-012, and is purchased from Shandong Aokai Chemical Co., Ltd.; the bone collagen protein has an active ingredient content of 99% and the main raw material is bone collagen, and is purchased from Henan Jiqian Biotechnology Co., Ltd.

[0019] Example 1 A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 1 part of water reducing and dispersing component, 1 part of setting time adjusting component, 5 parts of pH value adjusting component, 10 parts of strengthening component, and 30 parts of auxiliary component; Among them, the setting time adjusting component is obtained by mixing sodium carbonate, bone collagen protein, and sucrose in a mass ratio of 3:1:1; the pH value adjusting component is slaked lime; the strengthening component is obtained by mixing water glass, triethanolamine, triisopropanolamine, and defoaming agent in a mass ratio of 1000:40:20:1; The preparation method of the auxiliary component is as follows: Step S1: Disperse fly ash in deionized water to form a dispersion liquid, heat the dispersion liquid to 65 °C, then add fatty alcohol polyoxyethylene ether and zirconia, stir for 3.5 h, and then spray dry under the conditions of an inlet air temperature of 180 °C and an outlet air temperature of 100 °C to obtain preliminarily modified fly ash, wherein the addition amount of fly ash in the dispersion liquid is 0.12 g / mL, and the mass ratio of fatty alcohol polyoxyethylene ether, zirconia, and fly ash is 1:0.6:10; Step S2: Under room temperature conditions, mix the preliminarily modified fly ash with the silane coupling agent and stir for 1.5 h. Then add nano-silica and stir at 60°C for 2.5 h. Subsequently, conduct vacuum drying at 100°C until constant weight. Select zirconia balls, with the grinding ball size ratio of 10 mm:5 mm:3 mm = 3:5:2, the ball-to-material ratio of 8:1, the rotation speed of 400 rpm, and ball mill for 3 h to obtain the modified fly ash, where the mass ratio of the preliminarily modified fly ash, the silane coupling agent, and nano-silica is 1:0.03:0.02; Step S3: Mix the mineral powder and the modified fly ash evenly. Dissolve sodium silicate, sodium hydroxide, and nano-aluminum oxide in deionized water to form a composite activator solution. Spray the composite activator solution into the mixed materials at a spraying speed of 0.5 L / min. Then select zirconia balls, with the grinding ball size ratio of 10 mm:5 mm:3 mm = 3:5:2, the ball-to-material ratio of 8:1, the rotation speed of 350 rpm, and ball mill for 2 h. Then cure in an incubator at 60°C for 3 h, and then conduct vacuum drying at 100°C until constant weight to obtain the auxiliary component, where the mass ratio of the mineral powder to the modified fly ash is 1:1, the mass ratio of sodium silicate, sodium hydroxide, and nano-aluminum oxide is 6.5:2.5:1, the addition amount of nano-aluminum oxide in the composite activator solution is 0.025 g / mL, and the mass-volume ratio of the mixed materials to the composite activator solution is 1:0.15 g / mL.

[0020] The preparation method of the water-reducing and dispersing component is as follows: Preheat the polycarboxylate water reducer at 50°C for 30 min, then add sodium lignosulfonate and stir for 45 min. Then add the defoaming agent and continue to stir for 15 min. After cooling to room temperature, the water-reducing and dispersing component is obtained, and the mass ratio of the polycarboxylate water reducer, sodium lignosulfonate, and the defoaming agent is 2:1:0.004.

[0021] A cementitious material, comprising the following raw materials in parts by weight: 18 parts of activated gold tailings, 16 parts of steel slag, 48 parts of slag, 10 parts of industrial by-product gypsum, and 3 parts of the above solid waste-based cementitious material modifier.

[0022] A preparation method of a cementitious material, comprising the following steps: Mix the activated gold tailings, steel slag, slag, and industrial by-product gypsum evenly, and then add the solid waste-based cementitious material modifier and mix for 15 min to obtain it.

[0023] Example 2 A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 5 parts of water-reducing and dispersing component, 5 parts of setting time regulating component, 20 parts of pH value regulating component, 40 parts of strengthening component, and 85 parts of auxiliary component; Among them, the setting time regulating component and the strengthening component are the same as those in Example 1; the pH value regulating component is sodium hydroxide; The preparation method of the auxiliary component and the preparation method of the water-reducing and dispersing component are the same as those in Example 1.

[0024] A cementitious material, comprising the following raw materials in parts by weight: 22 parts of activated gold tailings, 20 parts of steel slag, 52 parts of slag, 14 parts of industrial by-product gypsum, and 6 parts of the above-mentioned solid waste-based cementitious material modifier.

[0025] A preparation method of a cementitious material, comprising the following steps: mixing the activated gold tailings, steel slag, slag, and industrial by-product gypsum evenly, and then adding the solid waste-based cementitious material modifier and mixing for 20 min to obtain.

[0026] Example 3 A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 3 parts of water-reducing and dispersing component, 2 parts of setting time regulating component, 10 parts of pH value regulating component, 30 parts of strengthening component, and 50 parts of auxiliary component; Among them, the setting time regulating component, pH value regulating component, and strengthening component are the same as those in Example 1; The preparation method of the auxiliary component and the preparation method of the water-reducing and dispersing component are the same as those in Example 1.

[0027] A cementitious material, comprising the following raw materials in parts by weight: 20 parts of activated gold tailings, 18 parts of steel slag, 50 parts of slag, 12 parts of industrial by-product gypsum, and 4 parts of the above-mentioned solid waste-based cementitious material modifier.

[0028] A preparation method of a cementitious material, comprising the following steps: mixing the activated gold tailings, steel slag, slag, and industrial by-product gypsum evenly, and then adding the solid waste-based cementitious material modifier and mixing for 18 min to obtain.

[0029] Example 4 A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 3 parts of water-reducing and dispersing component, 2 parts of setting time regulating component, 10 parts of pH value regulating component, 30 parts of strengthening component, and 50 parts of auxiliary component; Among them, the setting time regulating component, pH value regulating component, and strengthening component are the same as those in Example 1; The preparation method of the auxiliary component is as follows: Step S1: Disperse fly ash in deionized water to form a dispersion liquid, heat the dispersion liquid to 70 °C, then add fatty alcohol polyoxyethylene ether and zirconia, stir for 4 h, and then spray dry at an inlet air temperature of 180 °C and an outlet air temperature of 100 °C to obtain preliminarily modified fly ash, wherein the addition amount of fly ash in the dispersion liquid is 0.15 g / mL, and the mass ratio of fatty alcohol polyoxyethylene ether, zirconia to fly ash is 1.5:0.8:10; Step S2: Under room temperature conditions, mix the preliminarily modified fly ash with the silane coupling agent and stir for 2 h. Then add nano-silica and stir at 65 °C for 3 h. Subsequently, conduct vacuum drying at 100 °C until constant weight. Select zirconia balls, with the size ratio of grinding balls being 10 mm:5 mm:3 mm = 3:5:2, the ball-to-material ratio being 8:1, the rotation speed being 400 rpm, and mill for 3 h to obtain the modified fly ash. The mass ratio of the preliminarily modified fly ash, the silane coupling agent, and nano-silica is 1:0.05:0.04; Step S3: Mix the mineral powder and the modified fly ash evenly. Dissolve sodium silicate, sodium hydroxide, and nano-aluminum oxide in deionized water to form a composite activator solution. Spray the composite activator solution into the mixed materials at a spraying speed of 0.5 L / min. Then select zirconia balls, with the size ratio of grinding balls being 10 mm:5 mm:3 mm = 3:5:2, the ball-to-material ratio being 8:1, the rotation speed being 350 rpm, and mill for 2 h. Then cure in a constant temperature oven at 60 °C for 3 h, and then conduct vacuum drying at 100 °C until constant weight to obtain the auxiliary component. The mass ratio of the mineral powder to the modified fly ash is 2:1, the mass ratio of sodium silicate, sodium hydroxide, and nano-aluminum oxide is 7:3:1, the addition amount of nano-aluminum oxide in the composite activator solution is 0.03 g / mL, and the mass-to-volume ratio of the mixed materials to the composite activator solution is 1:0.2 g / mL.

[0030] The preparation method of the water-reducing and dispersing component is as follows: Preheat the polycarboxylate water reducer at 60 °C for 40 min, then add sodium lignosulfonate and stir for 50 min. Then add the defoaming agent and continue to stir for 20 min. After cooling to room temperature, the water-reducing and dispersing component is obtained. The mass ratio of the polycarboxylate water reducer, sodium lignosulfonate, and the defoaming agent is 2:1.2:0.005.

[0031] A cementitious material, comprising the following raw materials in parts by weight: 20 parts of activated gold tailings, 18 parts of steel slag, 50 parts of slag, 12 parts of industrial by-product gypsum, and 4 parts of the above solid waste-based cementitious material modifier.

[0032] A preparation method of a cementitious material, comprising the following steps: Mix the activated gold tailings, steel slag, slag, and industrial by-product gypsum evenly, and then add the solid waste-based cementitious material modifier and mix for 18 min to obtain it.

[0033] Comparative Example 1 A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 0.1 part of water-reducing and dispersing component, 2 parts of setting time adjusting component, 5 parts of pH value adjusting component, 30 parts of strengthening component, and 5 parts of auxiliary component; Among them, the setting time adjusting component, the pH value adjusting component, and the strengthening component are the same as those in Example 1; The preparation method of the auxiliary component and the preparation method of the water-reducing and dispersing component are the same as those in Example 1.

[0034] A cementitious material, comprising raw materials in the following parts by weight: 20 parts of activated gold tailings, 18 parts of steel slag, 50 parts of slag, 12 parts of industrial by-product gypsum, and 1 part of the above solid waste-based cementitious material modifier.

[0035] A preparation method of a cementitious material, comprising the following steps: uniformly mixing activated gold tailings, steel slag, slag, and industrial by-product gypsum, and then adding the solid waste-based cementitious material modifier and mixing for 10 min to obtain the product.

[0036] Comparative Example 2 A solid waste-based cementitious material modifier, comprising raw materials in the following parts by weight: 3 parts of water-reducing and dispersing component, 2 parts of setting time regulating component, 10 parts of pH value regulating component, 30 parts of strengthening component, and 50 parts of auxiliary component; wherein the setting time regulating component, pH value regulating component, and strengthening component are the same as those in Example 1; The preparation method of the auxiliary component is as follows: Step S1: Disperse fly ash in deionized water to form a dispersion liquid, heat the dispersion liquid to 65 °C, then add fatty alcohol polyoxyethylene ether and zirconia, stir for 3.5 h, and then spray dry at an inlet air temperature of 180 °C and an outlet air temperature of 100 °C to obtain preliminarily modified fly ash, wherein the addition amount of fly ash in the dispersion liquid is 0.12 g / mL, and the mass ratio of fatty alcohol polyoxyethylene ether, zirconia to fly ash is 1:0.6:10; Step S2: Under room temperature conditions, mix the preliminarily modified fly ash with a silane coupling agent, stir for 1.5 h, then add nano-silica, stir at 60 °C for 2.5 h, and then vacuum dry at 100 °C to constant weight. Select zirconia balls, the grinding ball size ratio is 10 mm:5 mm:3 mm = 3:5:2, the ball-to-material ratio is 8:1, the rotation speed is 400 rpm, and ball mill for 3 h to obtain the auxiliary component, wherein the mass ratio of the preliminarily modified fly ash, silane coupling agent to nano-silica is 1:0.03:0.02; The preparation method of the water-reducing and dispersing component is to preheat the polycarboxylate water reducer at 50 °C for 30 min, then add lignosulfonate, stir for 45 min, then add an antifoaming agent, and continue to stir for 15 min. After cooling to room temperature, the water-reducing and dispersing component is obtained, and the mass ratio of the polycarboxylate water reducer, lignosulfonate to the antifoaming agent is 2:1:0.004.

[0037] A cementitious material, comprising raw materials in the following parts by weight: 20 parts of activated gold tailings, 18 parts of steel slag, 50 parts of slag, 12 parts of industrial by-product gypsum, and 4 parts of the above solid waste-based cementitious material modifier.

[0038] A preparation method of a cementitious material, comprising the following steps: uniformly mixing activated gold tailings, steel slag, slag, and industrial by-product gypsum, and then adding a solid waste-based cementitious material modifier, and mixing for 18 min to obtain the product.

[0039] Comparative Example 3 A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 3 parts of a water-reducing and dispersing component, 2 parts of a setting time adjusting component, 10 parts of a pH value adjusting component, 30 parts of a strengthening component, and 50 parts of an auxiliary component; Wherein the setting time adjusting component, the pH value adjusting component, and the strengthening component are the same as those in Example 1; The preparation method of the auxiliary component is to disperse fly ash in deionized water to form a dispersion liquid, heat the dispersion liquid to 65 °C, then add fatty alcohol polyoxyethylene ether and zirconia, stir for 3.5 h, and then spray dry under the conditions of an inlet air temperature of 180 °C and an outlet air temperature of 100 °C to obtain the auxiliary component, wherein the addition amount of fly ash in the dispersion liquid is 0.12 g / mL, and the mass ratio of fatty alcohol polyoxyethylene ether, zirconia to fly ash is 1:0.6:10; The preparation method of the water-reducing and dispersing component is to preheat the polycarboxylate water reducer at 50 °C for 30 min, then add sodium lignosulfonate, stir for 45 min, then add an antifoaming agent, and continue to stir for 15 min, and cool to room temperature to obtain the water-reducing and dispersing component, and the mass ratio of the polycarboxylate water reducer, sodium lignosulfonate to the antifoaming agent is 2:1:0.004.

[0040] A cementitious material, comprising the following raw materials in parts by weight: 20 parts of activated gold tailings, 18 parts of steel slag, 50 parts of slag, 12 parts of industrial by-product gypsum, and 4 parts of the above solid waste-based cementitious material modifier.

[0041] A preparation method of a cementitious material, comprising the following steps: uniformly mixing activated gold tailings, steel slag, slag, and industrial by-product gypsum, and then adding a solid waste-based cementitious material modifier, and mixing for 18 min to obtain the product.

[0042] Comparative Example 4 A solid waste-based cementitious material modifier, comprising the following raw materials in parts by weight: 3 parts of a water-reducing and dispersing component, 2 parts of a setting time adjusting component, 10 parts of a pH value adjusting component, 30 parts of a strengthening component, and 50 parts of an auxiliary component; Wherein the setting time adjusting component, the pH value adjusting component, and the strengthening component are the same as those in Example 1; The auxiliary component is fly ash; the water-reducing and dispersing component is a polycarboxylate water reducer.

[0043] A cementitious material, comprising the following raw materials in parts by weight: 20 parts of activated gold tailings, 18 parts of steel slag, 50 parts of slag, 12 parts of industrial by-product gypsum, and 4 parts of the above solid waste-based cementitious material modifier.

[0044] A preparation method of a cementitious material, comprising the following steps: uniformly mixing activated gold tailings, steel slag, slag, and industrial by-product gypsum, and then adding a solid waste-based cementitious material modifier, and mixing for 18 min to obtain the product.

[0045] Table 1 Main chemical components of raw materials (w%) Table 2 Physical properties of raw materials Table 1 and Table 2 are the main chemical components and physical properties of raw materials such as activated gold tailings, steel slag, slag, and industrial by-product gypsum for preparing the cementitious material.

[0046] Performance test: According to the standard GB / T 1346-2024 "Test Methods for Standard Consistency Water Requirement, Setting Time and Soundness of Cement", the standard consistency water requirement, setting time and soundness of each sample were measured. The results are shown in Table 3, where the reference all-solid waste sample refers to the cementitious material without adding the solid waste-based cementitious material modifier.

[0047] Taking GB / T 8077-2023 "Test Methods for Homogeneity of Concrete Admixtures" as the standard, W / B and fluidity were measured, and the water consumption was selected as 87 g; taking GB / T 17671-2021 "Test Methods for Cement Mortar Strength (ISO Method)" as the standard, samples were prepared and cured, and the flexural strength and compressive strength of each sample were measured. The results are shown in Table 4.

[0048] Taking GB / T 50080-2016 "Standard Test Methods for Properties of Ordinary Concrete Mixtures" as the standard, the slump of the concrete with the cementitious material prepared by this invention as one of the raw materials was measured; taking GB / T 50081-2019 "Standard Test Methods for Physical and Mechanical Properties of Concrete" as the standard, the compressive strength of the concrete was measured. The results are shown in Table 5.

[0049] Table 3 Standard consistency water requirement, setting time, soundness Table 4 Physical properties of the cementitious material As can be seen from Table 3 and Table 4, the water requirement for normal consistency, setting time, soundness, W / B water-binder ratio, fluidity, flexural strength, compressive strength and other properties of the cementitious materials prepared in Examples 1-4 are all better than those of Comparative Example 1, and are close to the performance parameters of P.O 42.5 cement. Therefore, it can be shown that the formulation proposed in the present invention for preparing the cementitious material is the best and meets the requirements of the general Portland cement standard. From the data in Table 3 and Table 4, it can be seen that the performance of the cementitious material prepared in Comparative Example 2 has decreased to varying degrees, indicating that the performance improvement effect of the solid waste-based cementitious material modifier prepared in Comparative Example 2 is not good. When preparing the solid waste-based cementitious material modifier in Comparative Example 2, the process of treating the composite of modified fly ash and mineral powder with a composite activator solution is missing. Spraying the composite activator solution in this process can effectively promote the hydration reaction of mineral powder, etc., accelerate the setting speed of the cementitious material, and shorten the setting time. Moreover, components such as sodium silicate and sodium hydroxide in the composite activator solution can affect the hydration behavior of the mixture, thereby regulating the water requirement of the cementitious material during the hydration process. The nano-aluminum oxide in the composite activator solution has good dispersibility and surface activity, and can react with components such as aluminum oxide and silicon dioxide in the mineral powder and modified fly ash to form a finer and more uniform crystal structure. This structure helps to improve the density and impermeability of the material, thereby enhancing the durability of the cementitious material. The introduction of nano-aluminum oxide can also reduce the porosity in the material and improve the flexural and compressive strength of the cementitious material; sodium hydroxide and sodium silicate in the composite activator solution can adjust the pH value of the material, so that the cementitious material maintains good workability and fluidity during construction.

[0050] From the data in Table 3 and Table 4, it can be seen that the water requirement for normal consistency, setting time, soundness and physical properties of the cementitious material prepared in Comparative Example 3 have decreased again, indicating that the performance improvement effect of the solid waste-based cementitious material modifier prepared in this comparative example has decreased again. When preparing the solid waste-based cementitious material modifier in Comparative Example 3, not only is the process of treating the composite of modified fly ash and mineral powder with a composite activator solution missing, but also the nano-silica modification process is missing. In the nano-silica modification process, the activity of fly ash is improved through the treatment with silane coupling agent and nano-silica, and the hydration reaction is promoted, shortening the setting time of the gel material; the introduction of the silane coupling agent can also reduce the surface energy of fly ash particles, reduce the agglomeration phenomenon, improve the dispersibility of fly ash in the cementitious material, thereby improving the fluidity of the paste and reducing the water requirement of the cementitious material. Nano-silica is grafted onto the surface of fly ash through the organic chain segment of the silane coupling agent to fill the surface microcracks and improve the density of the cementitious material. At the same time, the introduction of the silane coupling agent and nano-silica can promote the hydration reaction and generate more cementitious substances, thereby improving the compressive and flexural strength of the cementitious material.

[0051] As can be seen from the data in Tables 3 and 4, the standard consistency water requirement, setting time, soundness and physical property data of the cementitious material prepared in Comparative Example 4 are the lowest, indicating that the performance improvement effect of the solid waste-based cementitious material modifier prepared in this comparative example is the worst. The auxiliary component is fly ash and the water-reducing and dispersing component is polycarboxylate water reducer when preparing the solid waste-based cementitious material modifier in Comparative Example 3, and the modification part is missing. The introduction of fatty alcohol polyoxyethylene ether during the modification of the auxiliary component can improve the surface properties of fly ash and reduce the agglomeration phenomenon between particles. During the modification of the water-reducing and dispersing component, polycarboxylate water reducer and lignosulfonate can also reduce particle agglomeration through electrostatic repulsion and steric hindrance effects. The two work synergistically to jointly improve the fluidity and soundness of the cementitious material. Zirconia can be used as a nano-level filler during the modification of the auxiliary component to fill the micropores on the surface of fly ash, reduce the water absorption rate, and synergistically with the modified water-reducing and dispersing component to reduce the water requirement of the cementitious material. The addition of zirconia can also further improve the surface activity of fly ash, making it easier to chemically react with other components, enhancing its role in the cementitious material, enabling fly ash to more effectively participate in the reaction during the subsequent hydration reaction, generating more cementitious substances, thereby improving the strength of the cementitious material and reducing the setting time.

[0052] Table 5 Comparison of Concrete Properties For Sample 1 in Table 5, the concrete performance test was carried out using the reference all-solid waste, and for Sample 2, the cementitious material prepared in Example 4 was used for the concrete performance test. The water consumption, slump and mechanical properties of the two cementitious materials during application were compared. As can be seen from the data in Table 5, when the cementitious material prepared in Example 4 of the present invention is compared with cement, the same slump can be achieved under the same water consumption per cubic meter of concrete. Although the 7-day strength is slightly lower, the 28-day strength is better than that of cement. In addition, compared with Sample 1, the dosage of water reducer in Sample 2 was reduced by 25% and the water consumption was reduced by 10 kg. Introducing the solid waste-based cementitious material prepared in Example 4 not only improved the early strength of the concrete, with the 7-day strength increased by more than 40% and the 28-day strength also increased by 20%, but also effectively improved the slump performance. Generally speaking, the concrete prepared with the cementitious material introduced with the solid waste-based cementitious material modifier is comparable to P.O 42.5 cement in terms of physical and mechanical properties.

[0053] Although the embodiments of the present application have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present application. The scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A modifier for solid waste-based cementitious materials, characterized in that, It comprises raw materials in the following parts by weight: 1-5 parts of water-reducing and dispersing component, 1-5 parts of setting time regulating component, 5-20 parts of pH value regulating component, 10-40 parts of strengthening component, and 30-85 parts of auxiliary component; The preparation method of the auxiliary component is as follows: Step S1: Disperse fly ash in deionized water to form a dispersion liquid. Heat the dispersion liquid to 60-70 °C, then add fatty alcohol polyoxyethylene ether and zirconia, stir for 3-4 h, and obtain preliminarily modified fly ash through post-treatment; Step S2: Under room temperature conditions, mix the preliminarily modified fly ash with a silane coupling agent, stir for 1-2 h, then add nano-silica, and stir for 2-3 h under the condition of 55-65 °C, and obtain modified fly ash through post-treatment; Step S3: Mix the mineral powder with the modified fly ash obtained in Step S2 evenly to obtain a mixed material. Dissolve water glass, sodium hydroxide, and nano-aluminum oxide in deionized water to form a composite activator solution, add the composite activator solution to the mixed material, and obtain the auxiliary component through post-treatment.

2. The solid waste-based cementitious material modifier according to claim 1, characterized in that, In Step S1, the addition amount of fly ash in the dispersion liquid is 0.1-0.15 g / mL, and the mass ratio of fatty alcohol polyoxyethylene ether, zirconia to fly ash is 0.5-1.5:0.2-0.8:

10.

3. The solid waste-based cementitious material modifier according to claim 1, wherein In Step S2, the mass ratio of the preliminarily modified fly ash, silane coupling agent to nano-silica is 1:0.01-0.05:0.01-0.

04.

4. The solid waste-based cementitious material modifier according to claim 1, characterized in that, In Step S3, the mass ratio of the mineral powder to the modified fly ash obtained in Step S2 is 0.6-2:1, the mass ratio of water glass, sodium hydroxide, and nano-aluminum oxide is 6-7:2-3:1, the addition amount of nano-aluminum oxide in the composite activator solution is 0.02-0.03 g / mL, and the mass-volume ratio of the mixed material to the composite activator solution is 1:0.1-0.2 g / mL.

5. The solid waste-based cementitious material modifier according to claim 1, characterized in that, The preparation method of the water-reducing and dispersing component is: Preheat the polycarboxylate water reducer at 40-60 °C for 20-40 min, then add sodium lignosulfonate, stir for 40-50 min, then add an antifoaming agent, and continue to stir for 10-20 min. After cooling to room temperature, the water-reducing and dispersing component is obtained, wherein the mass ratio of the polycarboxylate water reducer, sodium lignosulfonate to the antifoaming agent is 2:0.8-1.2:0.002-0.

005.

6. The solid waste-based cementitious material modifier according to claim 1, wherein The setting time regulating component is obtained by mixing sodium carbonate, bone glue protein and sucrose.

7. The solid waste-based cementitious material modifier according to claim 1, wherein The pH value regulating component is slaked lime or sodium hydroxide.

8. The solid waste-based cementitious material modifier according to claim 1, characterized in that, The strengthening component is obtained by mixing water glass, triethanolamine, triisopropanolamine and an antifoaming agent.

9. A gelling material, characterized in that, It comprises raw materials in the following parts by weight: 18-22 parts of activated gold tailings, 16-20 parts of steel slag, 48-52 parts of slag, 10-14 parts of industrial by-product gypsum, and 3-6 parts of the solid waste-based cementitious material modifier according to any one of Claims 1-8.

10. The preparation method of the gelling material according to claim 9, wherein It comprises the following steps: Mix the activated gold tailings, steel slag, slag, and industrial by-product gypsum evenly, and then add the solid waste-based cementitious material modifier and mix evenly to obtain.

Images