A green and environment-friendly fly ash multi-effect activator and its preparation and usage methods

Abstract

The present invention belongs to the field of comprehensive utilization of industrial waste resources, and specifically relates to a green environmental protection type fly ash multi-effect activator and its preparation and use methods. The fly ash multi-effect activator prepared by the present invention is obtained by fully mixing a composite active activator, a rapid setting and early strength agent, a modifier, and a composite high-efficiency ammonia-fixing agent. By weight, its raw material composition includes: 60%-90% of the composite active activator, 1%-12% of the rapid setting and early strength agent, 1%-5% of the modifier, and 5%-30% of the composite high-efficiency ammonia-fixing agent; this fly ash multi-effect activator can specifically be used in mine filling mining and concrete admixtures, can effectively activate the latent activity of fly ash, significantly improve the utilization rate of fly ash, and this multi-effect activator can solidify ammonia in fly ash, effectively solve the pungent odor problem generated during fly ash filling, and has broad application prospects.

Description

Technical Field

[0001] The present invention belongs to the field of comprehensive utilization of industrial waste resources, and particularly relates to a green environmental protection type fly ash multi-effect activator and its preparation and use methods. Background Art

[0002] Disclosing the information of this background art section is only intended to enhance the overall understanding of the present invention, and it is not necessarily regarded as an admission or an indication in any form that this information constitutes the prior art already known to those of ordinary skill in the art.

[0003] Fly ash is the fine ash captured from the flue gas after coal combustion and is the main solid waste discharged from coal-fired power plants. The impacts of fly ash from power plants on the environment are mainly manifested in: ① Storing fly ash requires a large amount of land or farmland, wasting land resources and polluting the soil; ② Dust pollution of the air; ③ Wet ash discharge will waste water resources and cause pollution of surface water bodies. When fly ash enters the water body, the turbidity of the water increases greatly, and the formed sediment will block the riverbed and make the lake shallower. Suspended substances and soluble substances will deteriorate the water quality; ④ Fly ash stored in the ash yard and fly ash floating in the atmosphere falling to the ground will pollute the soil, causing soil alkalization and other impacts, affecting the growth of crops, plants, and the production of aquaculture and animal husbandry.

[0004] Currently, the comprehensive utilization of fly ash mainly focuses on aspects such as making bricks, building roads, serving as admixtures for cement and concrete, extracting cenospheres, and improving the soil. Only a small part is used in the chemical industry and wastewater treatment. In recent years, the application of fly ash in coal mine backfill mining has been promoted, and relevant industries have utilized the following effective ways to activate the activity of fly ash for coal mine backfill. Currently, the activation of fly ash activity mainly includes: (1) Physical methods: grinding, sorting of fly ash, and control of curing temperature; (2) Chemical methods: various acidic activations, alkaline activations, sulfate activations, chloride salt additives; among them, chemical activation is a relatively simple and effective activation method, and only a small amount of additives need to be directly added to achieve the activation purpose.

[0005] The problems existing in current fly ash activators are as follows: The additives are mainly prepared by simply compounding inorganic materials or a combination of organic materials and inorganic materials, and both the applicability and stability are poor; secondly, when using fly ash for high-water cemented backfill in mines, pungent odors will appear in the backfill area to varying degrees.

[0006] The inventor comprehensively analyzed the reasons for the above phenomena as follows: At the present stage, coal-fired power plants generally adopt a denitrification process to reduce nitrogen oxides in the exhaust gas. The main process is selective catalytic reduction denitrification (SCR), but there will be some ammonia escape during the SCR denitrification process, and a small amount of SO 2 is oxidized to SO 3 , and ammonia in the flue gas reacts with SO3 The reaction generates ammonium salts such as ammonium sulfate and ammonium bisulfate, and the ammonium salts and ammonia gas are solidified into fly ash. Therefore, when fly ash is applied in filling mining, the ammonia gas adsorbed in the pores of fly ash, as well as the ammonium salts solidified in fly ash and the OH - generated by the reaction of the ammonium salts solidified in fly ash with the hydration of the activation material react to generate ammonia gas, which emits a pungent odor.

[0007] Therefore, developing a green and environment-friendly multi-effect activator for fly ash is a technical problem that needs to be urgently solved by those skilled in the art. Summary of the Invention

[0008] Aiming at the problems existing in the prior art, the present invention provides a green and environment-friendly multi-effect activator for fly ash and its preparation and use methods. This activator can effectively stimulate the latent activity of fly ash, significantly improve the utilization rate of fly ash when used in mine filling mining, and this multi-effect activator can solidify ammonia in fly ash, effectively solving the problem of pungent odor generated during fly ash filling.

[0009] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0010] In the first aspect of the present invention, a green and environment-friendly multi-effect activator for fly ash is provided. Calculated by weight, its raw material composition includes: 60%-90% of a composite active activator, 1%-12% of a quick-setting and early-strength agent, 1%-5% of a modifier, and 5%-30% of a composite high-efficiency ammonia-fixing agent.

[0011] Preferably, calculated by weight, the raw material composition of the green and environment-friendly multi-effect activator for fly ash includes: 70%-85% of a composite active activator, 1%-10% of a quick-setting and early-strength agent, 1%-5% of a modifier, and 5%-20% of a composite high-efficiency ammonia-fixing agent.

[0012] Among them, the weight ratio of carbide slag, salt gypsum, blast furnace granulated slag, red mud, and spodumene slag in the composite active activator is 5:1:2:1:1; the weight ratio of aluminous cement clinker, sodium carbonate, quicklime, potassium alum, and silica fume in the quick-setting and early-strength agent is 2:2:1:3:2; the modifier generally consists of an expansive agent, a water reducing agent, and an antifoaming agent, and different modifiers are selected according to different construction environments. Among them, the expansive agent is selected from one or more of aluminum powder, sodium percarbonate, and aluminum sulfate; the water reducing agent is selected from one or more of naphthalene-based water reducing agents, polycarboxylate water reducing agents, aliphatic water reducing agents, and lignosulfonate water reducing agents; the antifoaming agent is an organosilicon antifoaming agent; the weight ratio of styrene-acrylic emulsion (solid content ≥ 45%), copper nitrate (purity ≥ 99%), glycerol (purity ≥ 90%), and triethanolamine in the composite high-efficiency ammonia-fixing agent is (1-5):6:1:1;

[0013] The second aspect of the present invention provides a preparation method of the above-mentioned green environmental protection type fly ash multi-effect activator, which includes the following steps:

[0014] S1. Mix carbide slag, salt gypsum, blast furnace granulated slag, red mud, and spodumene slag, and then conduct a calcination reaction to obtain a composite active activator;

[0015] S2. Mix bauxite clinker, sodium carbonate, quicklime, potassium alum, and silica fume to obtain a rapid setting and early strength agent;

[0016] S3. Mix the composite active activator, the rapid setting and early strength agent, and a modifier to obtain a component A composite high-efficiency active activator;

[0017] S4. Mix styrene-acrylic emulsion, copper nitrate, glycerol, and triethanolamine to obtain a component B composite high-efficiency ammonia-fixing agent;

[0018] S5. Mix the component A composite high-efficiency active activator and the component B composite high-efficiency ammonia-fixing agent evenly to obtain a fly ash multi-effect activator.

[0019] Preferably, in step S1, the temperature of the calcination reaction is 800-1000°C, and the time of the calcination reaction is 1.5-2.5 h; more preferably, the temperature of the calcination reaction is 950°C, and the time of the calcination reaction is 2 h.

[0020] Preferably, in step S1, the reactants after the calcination reaction are crushed and ground in sequence; the specific surface area of the ground composite active activator is not less than 500 m 2 / kg.

[0021] The third aspect of the present invention provides a method for using the green environmental protection type fly ash multi-effect activator in mine filling described in the first aspect, specifically: first mix fly ash with the fly ash multi-effect activator, and then add water to make a slurry, and the slurry is self-flowed or pumped through a pipeline to the filling area for filling.

[0022] Preferably, the fly ash and the fly ash multi-effect activator are mixed according to a weight ratio of (1-15):1; the solid-water weight ratio of the slurry is 1:(1.0-1.5).

[0023] The fourth aspect of the present invention provides a method for using the green environmental protection type fly ash multi-effect activator as a concrete admixture described in the first aspect, specifically: when in use, fly ash equivalently replaces 10%-20% of the cement dosage in concrete, and the green environmental protection type fly ash multi-effect activator is added according to 5%-20% of the total amount of fly ash after replacement.

[0024] Preferably, the fly ash and the fly ash multi-effect activator are mixed according to a weight ratio of 100:(5-15).

[0025] The fifth aspect of the present invention provides an application of the green and environmentally friendly fly ash multi-effect stimulant described in the first aspect in the field of construction engineering.

[0026] The beneficial effects achieved by one or more technical solutions of the present invention are as follows:

[0027] (1) The present invention utilizes industrial wastes such as carbide slag, salt gypsum, blast furnace water-quenched slag, red mud, and spodumene slag to realize resource utilization of solid wastes with low cost and good economic and environmental benefits.

[0028] (2) The multi-effect stimulant prepared by the present invention can solidify the ammonia in the fly ash, effectively solving the problem of pungent odor generated during fly ash filling.

[0029] (3) When the fly ash multi-effect stimulant is used in the present invention, the fly ash multi-effect stimulant can be added to concrete to reduce the amount of cement in the concrete without affecting the overall performance of the concrete. The compressive strength of the 1d and 3d concrete is increased by 3-5MPa; the compressive strength of the 28-day concrete is increased by 5-10MPa.

[0030] (4) When the fly ash multi-effect stimulant of the present invention is used for mine filling and mining, the fly ash multi-effect stimulant and water in a certain proportion are gravity-flowed or pumped to the filling area through a pipeline for filling. No special equipment is required for preparation and dilution, and the construction process is simple. DETAILED DESCRIPTION

[0031] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0032] As mentioned above, when fly ash is used in filling mining and other fields, ammonia adsorbed into the pores of fly ash, and ammonium salt solidified in fly ash reacts with OH generated by hydration of the stimulating material. - The ammonia generated by the reaction emits a pungent odor. Therefore, it is a technical problem that those skilled in the art need to solve urgently to develop a green and environmentally friendly fly ash multi-effect stimulator that can effectively stimulate the potential activity of fly ash, significantly improve the utilization rate of fly ash when used for mining such as mine filling, and solidify the ammonia in fly ash, effectively solving the problem of pungent odor generated during fly ash filling.

[0033] In a specific embodiment of the present invention, a green and environmentally friendly fly ash multi-effect activator is provided, and its raw material composition includes, by weight: 70%-90% of a composite high-efficiency active activator, 1%-12% of a quick-setting early strength agent, 1%-5% of a modifier, and 5%-30% of a composite high-efficiency ammonia-fixing agent.

[0034] In another specific embodiment of the present invention, by weight, the raw material composition of the green environmental protection type fly ash multi-effect activator includes: 70%-85% of a composite active activator, 1%-10% of a quick-setting and early-strength agent, 1%-5% of a modifier, and 5%-20% of a composite high-efficiency ammonia-fixing agent.

[0035] Among them, the weight ratio of carbide slag, salt gypsum, blast furnace granulated slag, red mud, and spodumene slag in the composite active activator is 5:1:2:1:1; the weight ratio of alumina clinker, sodium carbonate, quicklime, potassium alum, and silica fume in the quick-setting and early-strength agent is 2:2:1:3:2; the modifier is generally composed of an expansive agent, a water reducing agent, and an antifoaming agent, and different modifiers are selected according to different construction environments, wherein the expansive agent is selected from one or more of aluminum powder, sodium percarbonate, and aluminum sulfate; the water reducing agent is selected from one or more of naphthalene-based water reducing agents, polycarboxylate water reducing agents, aliphatic water reducing agents, and lignosulfonate water reducing agents; the antifoaming agent is an organosilicon antifoaming agent; the weight ratio of styrene-acrylic emulsion (solid content ≥ 45%), copper nitrate (purity ≥ 99%), glycerol (purity ≥ 90%), and triethanolamine in the composite high-efficiency ammonia-fixing agent is (1-5):6:1:1.

[0036] In another specific embodiment of the present invention, a preparation method of the above green environmental protection type fly ash multi-effect activator is provided, including the following steps:

[0037] S1. Mix carbide slag, salt gypsum, blast furnace granulated slag, red mud, and spodumene slag and then carry out a calcination reaction to obtain a composite active activator;

[0038] S2. Mix alumina clinker, sodium carbonate, quicklime, potassium alum, and silica fume to obtain a quick-setting and early-strength agent;

[0039] S3. Mix the composite active activator, the quick-setting and early-strength agent, and the modifier to obtain component A composite high-efficiency active activator;

[0040] S4. Mix styrene-acrylic emulsion, copper nitrate, glycerol, and triethanolamine to obtain component B composite high-efficiency ammonia-fixing agent;

[0041] S5. Mix component A composite high-efficiency active activator and component B composite high-efficiency ammonia-fixing agent evenly to obtain a fly ash multi-effect activator.

[0042] In another specific embodiment of the present invention, in step S1, the temperature of the calcination reaction is 800-1000°C, and the time of the calcination reaction is 1.5-2.5 h.

[0043] In another specific embodiment of the present invention, the temperature of the calcination reaction is 950°C, and the time of the calcination reaction is 2 h.

[0044] In yet another specific embodiment of the present invention, in step S1, the reactants after the calcination reaction are sequentially crushed and ground; the specific surface area of the ground composite activity activator is not less than 500 m2 / kg.

[0045] In yet another specific embodiment of the present invention, a method for using the above-mentioned green and environment-friendly fly ash multi-effect activator in mine filling is provided, specifically: first, mix fly ash with the fly ash multi-effect activator, and then add water to make a slurry, and the slurry is self-flowed or pumped through a pipeline to the filling area for filling.

[0046] In yet another specific embodiment of the present invention, the fly ash and the fly ash multi-effect activator are mixed in a weight ratio of (1-15):1; the solid-water weight ratio of the slurry is 1:(1.0-1.5).

[0047] In yet another specific embodiment of the present invention, a method for using the above-mentioned green and environment-friendly fly ash multi-effect activator as a concrete admixture (in the construction field) is provided, specifically: during use, fly ash equivalently replaces 10%-20% of the cement dosage in the concrete, and the green and environment-friendly fly ash multi-effect activator is added in an amount of 5%-20% based on the total amount of fly ash after replacement.

[0048] In yet another specific embodiment of the present invention, the fly ash and the fly ash multi-effect activator are mixed in a weight ratio of 100:(5-15).

[0049] In yet another specific embodiment of the present invention, an application of the above-mentioned green and environment-friendly fly ash multi-effect activator in the field of construction engineering is provided.

[0050] Each raw material and its function:

[0051] Composite activity activator: The composite activity activator makes full use of industrial solid wastes such as carbide slag, salt gypsum, blast furnace granulated slag, red mud, and spodumene slag. Among them, carbide slag is the waste residue mainly composed of calcium hydroxide after the hydrolysis of carbide to obtain acetylene gas; salt gypsum is the industrial waste residue for preparing sea salt, and its main component is calcium sulfate dihydrate; blast furnace granulated slag is the solid waste generated during the blast furnace ironmaking process; red mud, also known as red mud, is the industrial solid waste discharged after extracting alumina from bauxite; spodumene slag is the industrial solid waste of lithium carbonate, which is a micron-scale inorganic substance with a complex mineral composition composed of a variety of inorganic substances and has extremely high potential activity.

[0052] The main function of the composite activity activator is to effectively activate the latent activity of fly ash by making full use of the alkaline substances, sulfates, silicates and other components in industrial waste. Combining the use of rapid setting and early strength agents and modifiers can significantly improve the compressive strength of fly ash at various ages; it can significantly increase the dosage of fly ash in cement or cement concrete, as well as the performance of cement concrete, improve the overall dosage of fly ash, save cement, reduce the cost of concrete and its products, and has significant economic and social benefits.

[0053] Rapid setting and early strength agent: The rapid setting and early strength agent is composed of aluminous cement clinker, sodium carbonate, quicklime, potassium alum and silica fume. Its mechanism of action is that its effective components can cause the rapid hydration of calcium aluminate minerals and precipitate their hydration product crystals in the solution; components such as aluminous cement clinker, quicklime and potassium alum in it also provide effective components for the formation of hydrated calcium sulfoaluminate and secondary gypsum crystals with very low solubility, which promotes the increase of compressive strength and flexural strength at 1-3d; at the same time, the addition of silica fume can improve the size and quantity of pores in the solidified body, making the microstructure of concrete more uniform and dense. Secondly, silica fume can reduce the segregation and bleeding of concrete, increase the cohesion inside the concrete, and the reactive silica in silica fume can react with calcium ions in the concrete to generate high-strength hydration products. The addition of silica fume mainly improves the compressive and flexural strength of concrete in the later stage (28d and later).

[0054] Modifier (expansive agent, water reducing agent, defoaming agent): The modifier is generally composed of an expansive agent, a water reducing agent, a defoaming agent, etc. Different modifiers are selected according to different construction environments to modify the slurry transportation performance and the mechanical properties of the filled body after curing.

[0055] Composite high-efficiency ammonia-fixing agent: The composite high-efficiency ammonia-fixing agent is composed of styrene-acrylic emulsion (solid content ≥ 45%), copper nitrate (purity ≥ 99%), glycerol (purity ≥ 90%) and triethanolamine. Glycerol and triethanolamine effectively disperse copper ions to fix ammonia in all directions. The styrene-acrylic emulsion has good film-forming properties, and after the emulsion forms a film, it can effectively prevent ammonia from overflowing.

[0056] Through the coordinated cooperation of each component, the ammonia in fly ash is fixed, effectively solving the problem of pungent odor caused by ammonia overflow during the large-volume filling of fly ash.

[0057] The mechanism of action of this fly ash multi-effect activator is:

[0058] Activation mechanism: The main mechanism of activation is to activate the latent activity of fly ash by relying on the effective components of the composite high-efficiency activator. The composite activator supplements the calcium content in the fly ash system. Because the amount of hydrated cementitious products formed after the activation of fly ash significantly affects the later strength of the fly ash-containing system, only with sufficient calcium can more hydrated cementitious products be formed after activation, and the later strength of the fly ash-containing system can be effectively improved. Using calcium hydroxide in the activator and sodium aluminate, the effective component in the early-strength agent, to directly destroy the acidic fly ash system, mainly reflected in OH - can break the Si-O bond and Al-O bond, thereby destroying the Si-O tetrahedron and Al-O octahedron network structures in the vitreous body, increasing the dissolution amount of active substances inside the fly ash particles, and accelerating Al 2 O 3 、SiO 2 react with Ca(OH) 2 to promote the generation of cementitious substances. Strong alkalis have an obvious effect on improving the early strength of the system. Potassium alum in the quick-setting and early-strength agent ionizes SO 4 2- in the aqueous solution. SO 4 2- under the action of Ca 2+ reacts with active Al 2 O 3 in the vitreous body to form ettringite, which fills the cement stone structure, greatly improving the compactness of the system and thus enhancing its early strength. At the same time, the large generation of ettringite can increase the solid volume, and the volume of the filling body increases after solidification. Combining with the use of the expansive agent in the modifier can effectively improve the expansion performance of the filling material. In addition, the tightness of the ettringite coating layer is smaller than that of the hydrated calcium silicate layer, which is beneficial to the diffusion of Ca 2+ to the inside of the fly ash particles and continue to react with the internal active substances, further promoting the generation of cementitious substances. After fly ash is compound-activated by strong alkalis, sulfates, etc., the vast majority of fly ash particles participate in the reaction, forming many flocculent hydrated calcium silicate, hydrated calcium aluminate and other products, making the whole system more compact. The present invention effectively activates the chemical activity of fly ash through the composite high-efficiency activator, which is beneficial to the dissolution of active substances. The main activation reactions are as follows:

[0059] SiO 2 (active) + m 1 Ca(OH) 2 + xH 2 O → m 1 CaO·SiO 2 ·xH 2 O

[0060] Al 2 O 3 (active) + m2 Ca(OH) 2 + yH2O → m 2 CaO·Al 2 O 3 ·yH 2 O

[0061] 2NaAlO 2 + 3CaO + 7H 2 O → 3CaO·Al 2 O 3 ·6H 2 O + 2NaOH

[0062] 3CaO·Al 2 O 3 ·6H 2 O + 3(CaSO 4 ·2H 2 O) + 20H 2 O → 3CaO·Al 2 O 3 ·3CaSO 4 ·32H 2 O (ettringite)

[0063] Ammonia fixation mechanism: Based on the theory of copper ion complexing ammonia, combined with a large number of experiments by the applicant of the present invention, it is found that the combined use of styrene-acrylic emulsion, glycerol, and triethanolamine can better carry copper ions and disperse them in water. The same amount of copper ions can bind more ammonia monohydrate, and the product can stably exist in an alkaline environment. For the above reasons, the present invention uses copper ions as a complexing agent, and styrene-acrylic emulsion, glycerol, and triethanolamine cooperate synergistically to solidify ammonia in fly ash. The specific reaction is as follows:

[0064] Cu 2+ + 4NH 3 ·H 2 O = [Cu(NH 3 ) 4 2+ + 4H 2 O

[0065] The following combines specific embodiments to further elaborate on the present invention. It should be noted that the specific embodiments are explanations rather than limitations of the present invention.

[0066] Embodiment 1: This embodiment provides a green and environment-friendly fly ash multi-effect activator and its preparation method.

[0067] By weight, the raw material composition of the green and environment-friendly fly ash multi-effect activator includes: 70% of a composite high-efficiency active activator, 10% of a rapid-setting and early-strength agent, 5% of a modifier, and 15% of a composite high-efficiency ammonia-fixing agent.​

[0068] The preparation method of the green environmental protection type fly ash multi-effect activator comprises the following steps:

[0069] S1. Mix carbide slag, salt gypsum, blast furnace granulated slag, red mud, and spodumene slag according to a weight ratio of 5:1:2:1:1, then calcine at 950 °C for 2 h, and after calcination, crush and grind to a specific surface area of 500 m2 / kg to obtain a composite active activator;

[0070] S2. Mix bauxite clinker, sodium carbonate, quicklime, potassium alum, and silica fume according to a weight ratio of 2:2:1:3:2 to obtain a rapid setting and early strength agent;

[0071] S3. Mix the composite active activator, the rapid setting and early strength agent, and a modifier (wherein, the expansive agent is aluminum sulfate, the water reducing agent is polycarboxylate water reducing agent, and the defoaming agent is silicone defoaming agent) to obtain a component A composite high-efficiency active activator;

[0072] S4. Mix styrene-acrylic emulsion, copper nitrate, glycerol, and triethanolamine according to a weight ratio of 1:6:1:1 to obtain a component B composite high-efficiency ammonia-fixing agent;

[0073] S5. Mix the component A composite high-efficiency active activator and the component B composite high-efficiency ammonia-fixing agent evenly to obtain the fly ash multi-effect activator.

[0074] Example 2: This example provides a green environmental protection type fly ash multi-effect activator and its preparation method.

[0075] By weight, the raw material composition of the green environmental protection type fly ash multi-effect activator includes: 68% of the composite high-efficiency active activator, 12% of the rapid setting and early strength agent, 5% of the modifier, and 15% of the composite high-efficiency ammonia-fixing agent; the preparation steps are the same as those in Example 1.

[0076] Comparative Example 1: Different from the components in Example 1, the rapid setting and early strength agent is not added, and other components are the same as those in Example 1; the preparation steps are the same as those in Example 1.

[0077] The specific raw material composition of the multi-effect activator includes: 79.3% of the composite high-efficiency active activator, 0% of the rapid setting and early strength agent, 5.7% of the modifier, and 15.1% of the composite high-efficiency ammonia-fixing agent.

[0078] Comparative Example 2: Different from the components in Example 1, silica fume is not added to the rapid setting and early strength agent, and other components are the same as those in Example 1; the preparation steps are the same as those in Example 1.

[0079] Comparative Example 3: Different from the components of Example 1, the weight ratio of styrene-acrylic emulsion (solid content ≥ 45%) to copper nitrate (purity ≥ 99%) in the composite high-efficiency nitrogen-fixing agent is 1:4, and other components are the same as those in Example 1; the preparation steps are the same as those in Example 1.

[0080] The raw material composition of the specific multi-effect activator includes: 70% of the composite high-efficiency active activator, 10% of the quick-setting and early-strength agent, 5% of the modifier, and 15% of the composite high-efficiency nitrogen-fixing agent.

[0081] Comparative Example 4: Different from the components of Example 1, the weight ratio of styrene-acrylic emulsion (solid content ≥ 45%) to glycerol (purity ≥ 90%) to triethanolamine in the composite high-efficiency nitrogen-fixing agent is 1:2:1, and other components are the same as those in Example 1; the preparation steps are the same as those in Example 1.

[0082] The raw material composition of the specific multi-effect activator includes: 70% of the composite high-efficiency active activator, 10% of the quick-setting and early-strength agent, 5% of the modifier, and 15% of the composite high-efficiency nitrogen-fixing agent.

[0083] Comparative Example 5:

[0084] Different from the components of Example 1, PO425 ordinary Portland cement was used to replace the composite multi-effect activator for the test.

[0085] Example 3: This example provides the specific weight percentages of the components of the multi-effect activator involved in Examples 1-2 and Comparative Examples 1-5, as shown in Table 1:

[0086] Table 1 Component contents of the green environmental protection type mine multi-effect functional additive

[0087]

[0088] Test Example 1:

[0089] In this test example, the performances of the multi-effect activators prepared in Examples 1-2 and Comparative Examples 1-5 in the application of fly ash high-water cemented filling were compared respectively. The specific fly ash high-water filling ratio values are shown in Table 2; the comparison of the performance test data is shown in Table 3:

[0090] Table 2 Fly ash high-water filling ratio

[0091] Fly ash Multi-effect activator (PO425 ordinary Portland cement) Water 1000 200 1200

[0092] Table 3 Comparison of test data

[0093]

[0094] As shown in Table 3, the performance of the multi-effect activator obtained in Examples 1-2 is superior to that of Comparative Examples 1-5. Compared with Comparative Example 1, the rapid-setting early-strength agent is beneficial to enhancing the compressive and flexural strengths of the multi-effect activator in the application of high-water cementitious filling of fly ash, and can effectively solidify ammonia in fly ash; compared with Comparative Example 2, it can be seen that the addition of silica fume in the rapid-setting early-strength agent mainly improves the compressive and flexural strengths of the high-water cementitious filling of fly ash in the later stage (28 days and later); compared with Comparative Examples 3-4, it can be seen that the composite high-efficiency ammonia-fixing agent component of the multi-effect activator is more beneficial to synergistically enhancing the compressive and flexural strengths of the multi-effect activator in the application of high-water cementitious filling of fly ash and can effectively solidify ammonia in fly ash when all components are added in proportion compared with only using a single component; compared with Comparative Example 5, it can be seen that the compressive and flexural strengths and ammonia-fixing amount of PO425 ordinary Portland cement are lower than those of the composite multi-effect activator.

[0095] Test Example 2:

[0096] In this experimental example, the performances of the multi-effect activators prepared in Examples 1-2 and Comparative Examples 1-5 were compared when used as concrete admixtures (in the construction field). The specific concrete mix ratios are shown in Table 4; the comparison of performance test data is shown in Table 5:

[0097] Table 4 Concrete Mix Ratio

[0098] Example Cement Fly ash Multi-effect activator Sand Gravel Water Example 1 250 113 7 606 1230 185 Example 2 250 113 7 606 1230 185 Comparative example 1 250 113 7 606 1230 185 Comparative example 2 250 113 7 606 1230 185 Comparative example 3 250 113 7 606 1230 185 Comparative example 4 250 113 7 606 1230 185 Comparative example 5 300 70 0 606 1230 185

[0099] Table 5 Comparison of Concrete Test Data

[0100]

[0101]

[0102] As shown in Table 5, the performance of the multi-effect activator obtained in Examples 1-2 is superior to that of Comparative Examples 1-5. Compared with Comparative Example 1, the rapid-setting early-strength agent is beneficial to enhancing the compressive and flexural strengths of the concrete and can reduce the initial slump and effectively solidify ammonia in fly ash; compared with Comparative Example 2, it can be seen that the addition of silica fume in the rapid-setting early-strength agent mainly improves the compressive and flexural strengths of the concrete in the later stage (28 days and later); compared with Comparative Examples 3-4, it can be seen that the composite high-efficiency ammonia-fixing agent component of the multi-effect activator is more beneficial to synergistically improving the compressive and flexural strengths of the concrete, reducing the initial slump and effectively solidifying ammonia in fly ash when all components are added in proportion compared with only using a single component; compared with Comparative Example 5, although the initial slump value of PO425 ordinary Portland cement is lower, its compressive and flexural strengths and ammonia-fixing amount are lower than those of the composite multi-effect activator.

[0103] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A green and environmentally friendly fly ash multi-effect stimulator, characterized in that: The raw material composition includes, by weight: 60%-90% of a composite active activator, 1%-12% of a quick-setting early strength agent, 1%-5% of a modifier, and 5%-30% of a composite high-efficiency ammonia-fixing agent; The weight ratio of carbide slag, salt gypsum, blast furnace water quenching slag, red mud and spodumene slag in the composite active activator is 5:1:2:1:1; the weight ratio of alumina clinker, sodium carbonate, quicklime, potassium aluminum sulfate and silica fume in the quick-setting early strength agent is 2:2:1:3:2; the weight ratio of styrene acrylic emulsion, copper nitrate, glycerol and triethanolamine in the composite high-efficiency ammonia solidifying agent is (1-5):6:1:1; The styrene acrylic emulsion has good film-forming properties, and after the emulsion forms a film, it can effectively prevent ammonia from overflowing; The modifier is composed of an expansion agent, a water reducing agent, and a defoaming agent, and different modifiers are selected according to different construction environments; The composite active activator is obtained by mixing carbide slag, salt gypsum, blast furnace water-quenched slag, red mud and spodumene slag and then calcining the mixture.

2. The green and environmentally friendly fly ash multi-effect stimulator according to claim 1, characterized in that: By weight, the raw material composition of the green and environmentally friendly fly ash multi-effect activator includes: 70%-85% of a composite active activator, 1%-10% of a quick-setting early strength agent, 1%-5% of a modifier, and 5%-20% of a composite high-efficiency ammonia-fixing agent.

3. The green and environmentally friendly fly ash multi-effect stimulator according to any one of claims 1 to 2, characterized in that: The expansion agent is selected from one or more of aluminum powder, sodium percarbonate, and aluminum sulfate; the water reducer is selected from one or more of naphthalene water reducer, polycarboxylic acid water reducer, aliphatic water reducer, and lignin sulfonate water reducer; and the defoamer is an organosilicon defoamer.

4. A method for preparing the green and environmentally friendly fly ash multi-effect stimulant according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1, mixing carbide slag, salt gypsum, blast furnace water-quenched slag, red mud, and spodumene slag and calcining them to obtain a composite active activator; S2, mixing alumina clinker, sodium carbonate, quicklime, potassium aluminum sulfate and silica fume to prepare a rapid setting and early strength agent; S3, mixing a composite active activator, a quick-setting early strength agent, and a modifier to obtain a component A composite high-efficiency active activator; S4, mixing styrene-acrylic emulsion, copper nitrate, glycerol and triethanolamine to obtain a component B composite high-efficiency ammonia-fixing agent; S5. Mix the composite high-efficiency active stimulant of component A and the composite high-efficiency ammonia-fixing agent of component B to obtain a fly ash multi-effect stimulant.

5. The preparation method according to claim 4, characterized in that: In step S1, the calcination reaction temperature is 800-1000° C., and the calcination reaction time is 1.5-2.5 h.

6. The preparation method according to claim 5, characterized in that: The calcination reaction temperature is 950° C., and the calcination reaction time is 2 h.

7. The preparation method according to claim 5, characterized in that: In step S1, the reactants after the calcination reaction are crushed and ground in sequence; the specific surface area of ​​the composite active activator after grinding is not less than 500 m2 / kg.

8. A method for using the green and environmentally friendly fly ash multi-effect stimulant for mine filling as claimed in any one of claims 1 to 3, characterized in that: The method for using the mine filling is specifically as follows: firstly, the fly ash is mixed with the fly ash multi-effect stimulator, and then water is added to form a slurry, and the slurry is transported to the filling area through a pipeline by gravity or by pumping for filling.

9. The method for using the green and environmentally friendly fly ash multi-effect stimulant for mine filling as claimed in claim 8, characterized in that: The fly ash and the fly ash multi-effect stimulator are mixed in a weight ratio of (1-15):1; the solid-water weight ratio of the slurry is 1:(1.0-1.5).

10. A method for mixing concrete with the green and environmentally friendly fly ash multi-effect stimulator as claimed in any one of claims 1 to 3, characterized in that: The concrete admixture use method is specifically as follows: when using, the fly ash is used to replace 10%-20% of the cement in the concrete, and a green and environmentally friendly fly ash multi-effect activator is added according to 5%-20% of the total amount of fly ash after replacement.

11. The method for mixing concrete with the green and environmentally friendly fly ash multi-effect stimulator according to claim 10, characterized in that: The fly ash and the fly ash multi-effect stimulator are mixed in a weight ratio of 100:(5-15).

12. Application of the green and environment-friendly fly ash multi-effect stimulator according to any one of claims 1 to 3 in the field of construction engineering.

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