Green and environment-friendly fly ash multi-effect exciting agent and preparation and use methods thereof

Abstract

The invention belongs to the field of industrial waste resource comprehensive utilization, and particularly relates to a green environment-friendly fly ash multi-effect exciting agent and a preparation and use method thereof. The fly ash multi-effect exciting agent prepared by the invention is prepared by fully and uniformly mixing a composite active exciting agent, a quick-setting early strength agent, a modifier and a composite efficient ammonia fixing agent, and the fly ash multi-effect exciting agent is prepared from the following raw materials in parts by weight: 60-90% of the composite active exciting agent, 1-12% of the quick-setting early strength agent, 1-5% of the modifier and 5-30% of the composite efficient ammonia fixing agent, the fly ash multi-effect exciting agent can be specifically used in mine filling mining and concrete admixtures, can effectively excite the potential activity of fly ash and remarkably improve the utilization rate of fly ash, can solidify ammonia in fly ash, effectively solves the problem of pungent smell generated during fly ash filling, and has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the field of comprehensive resource utilization of industrial waste, and specifically relates to a green and environment-friendly fly ash multi-effect stimulant and a preparation and use method thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Fly ash is the fine ash collected from the flue gas after coal combustion, and is the main solid waste discharged by coal-fired power plants. The impact of fly ash from power plants on the environment is mainly manifested in the following aspects: ① Ash storage requires a large amount of land or farmland, which wastes land resources and pollutes the soil; ② Dust pollutes the air; ③ Wet ash discharge will waste water resources and cause surface water pollution. Fly ash entering the water body will greatly increase the turbidity of the water, and the formed sediments will block the riverbed and make the lake shallower. Suspended matter and soluble matter will deteriorate the water quality; ④ Fly ash stored in the ash field will float in the atmosphere and fall to the ground, which will pollute the soil, cause soil alkalization and other effects, and affect the growth of crops and plants, as well as the production of breeding and animal husbandry.

[0004] At present, the comprehensive utilization of fly ash is mainly concentrated in the use for brick burning, road construction, cement and concrete admixture, selection of floating beads, soil improvement, etc., and only a small part is used in the chemical industry and wastewater treatment. In recent years, fly ash has been promoted and applied in coal mine filling mining. Relevant industries have used the following effective ways to stimulate the activity of fly ash for coal mine filling. At present, the main methods for stimulating the activity of fly ash are: (1) physical methods: grinding, sorting and curing temperature control of fly ash; (2) chemical methods: various acidic stimulations, alkaline stimulations, sulfate stimulations, chloride salt admixtures; among them, chemical stimulation is a relatively simple and effective stimulation method. It only needs to directly add a small amount of admixtures to achieve the purpose of stimulation.

[0005] The current problems with fly ash activators are that the admixtures are mainly made of inorganic materials or organic and inorganic materials through simple compounding, and have poor applicability and stability. Secondly, some mines have reported that when fly ash is used for high-water cementation filling, a pungent odor will appear in the filling area to varying degrees.

[0006] The inventors have comprehensively analyzed the reasons for the above phenomenon as follows: At present, coal-fired power plants generally use denitration technology to reduce nitrogen oxides in exhaust gas. The main process is selective catalytic reduction denitration (SCR). However, during the SCR denitration process, some ammonia will escape, and a small amount of SO2 in the flue gas will be oxidized to SO3. The ammonia in the flue gas reacts with SO3 to generate ammonium salts such as ammonium sulfate and ammonium bisulfate. The ammonium salts and ammonia are solidified in the fly ash. Therefore, when fly ash is used in backfill mining, the ammonia adsorbed into the pores of the fly ash, and the ammonium salts solidified in the fly ash react with the OH generated by the hydration of the exciting material. - The ammonia produced by the reaction emits a pungent odor.

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

[0008] In view of the problems existing in the prior art, the present invention provides a green and environmentally friendly fly ash multi-effect stimulant and a preparation and use method thereof. The stimulant can effectively stimulate the potential activity of fly ash and can significantly improve the utilization rate of fly ash when used for mine filling and mining. The multi-effect stimulant can solidify the ammonia in the fly ash and effectively solve the problem of pungent odor generated during fly ash filling.

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

[0010] The first aspect of the present invention provides a green and environmentally friendly fly ash multi-effect activator, which comprises, 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.

[0011] Preferably, the raw material composition of the green and environmentally friendly fly ash multi-effect activator includes, by weight: 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.

[0012] 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 modifier is generally composed of an expander, a water reducer and a defoamer, and different modifiers are selected according to different construction environments, wherein the expander 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; the defoamer is an organosilicon defoamer; 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 solidifying agent is (1-5):6:1:1;

[0013] The second aspect of the present invention provides a method for preparing the above-mentioned green and environmentally friendly fly ash multi-effect stimulant, comprising the following steps:

[0014] 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;

[0015] S2, mixing alumina clinker, sodium carbonate, quicklime, potassium aluminum sulfate and silica fume to prepare a rapid setting and early strength agent;

[0016] 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;

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

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

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

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

[0021] The third aspect of the present invention provides a method for using the green and environmentally friendly fly ash multi-effect stimulant for mine filling as described in the first aspect, specifically: firstly mix the fly ash and the fly ash multi-effect stimulant, and then add water to form a slurry, and the slurry is gravity-flowed or pumped to the filling area through a pipeline for filling.

[0022] Preferably, 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).

[0023] The fourth aspect of the present invention provides a method for using the green and environmentally friendly fly ash multi-effect stimulant as a concrete admixture as described in the first aspect, specifically: when using, the fly ash replaces 10%-20% of the cement in the concrete in an equal amount, and the green and environmentally friendly fly ash multi-effect stimulant is added at 5%-20% of the total amount of fly ash after replacement.

[0024] Preferably, the fly ash and the fly ash multi-effect stimulator are mixed in 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, the raw material composition of the green and environmentally friendly fly ash multi-effect activator includes, by weight: 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] The weight ratio of carbide slag, salt gypsum, blast furnace water-quenched 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 modifier is generally composed of an expander, a water reducer and a defoamer, and different modifiers are selected according to different construction environments, wherein the expander 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-based water reducer, polycarboxylic acid water reducer, aliphatic water reducer and lignin sulfonate water reducer; the defoamer is an organosilicon defoamer; 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 solidifying agent is (1-5):6:1:1.

[0036] In another specific embodiment of the present invention, a method for preparing the above-mentioned green and environmentally friendly fly ash multi-effect stimulant is provided, comprising the following steps:

[0037] 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;

[0038] S2, mixing alumina clinker, sodium carbonate, quicklime, potassium aluminum sulfate and silica fume to prepare a rapid setting and early strength agent;

[0039] 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;

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

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

[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 hours.

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

[0044] In another specific embodiment of the present invention, 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 500m2 / kg.

[0045] In another specific embodiment of the present invention, a method for using the above-mentioned green and environmentally friendly fly ash multi-effect stimulant for mine filling is provided, specifically: fly ash and fly ash multi-effect stimulant are first mixed, and then water is added to form slurry, and the slurry is gravity-flowed or pumped to the filling area through a pipeline for filling.

[0046] In another specific embodiment of the present invention, 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).

[0047] In another specific embodiment of the present invention, a method for using the above-mentioned green and environmentally friendly fly ash multi-effect stimulant as a concrete admixture (in the construction field) is provided, specifically: when using, the fly ash replaces 10%-20% of the cement in the concrete in an equal amount, and the green and environmentally friendly fly ash multi-effect stimulant is added at 5%-20% of the total amount of fly ash after replacement.

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

[0049] In another specific embodiment of the present invention, there is provided an application of the green and environmentally friendly fly ash multi-effect stimulant in the field of construction engineering.

[0050] Raw materials and functions:

[0051] Composite active activator: The composite active activator makes full use of industrial solid wastes such as carbide slag, salt gypsum, blast furnace water-quenched slag, red mud and spodumene slag. Carbide slag is the waste slag with calcium hydroxide as the main component after acetylene gas is obtained by hydrolysis of calcium carbide; salt gypsum is the industrial waste slag for preparing sea salt, and its main component is calcium sulfate dihydrate; blast furnace water-quenched slag is the solid waste generated in the blast furnace ironmaking process; red mud, also known as red mud, is the industrial solid waste discharged after alumina is extracted from bauxite; spodumene slag is the industrial solid waste of lithium carbonate, which is a micron-sized inorganic substance with a complex mineral composition mixed with multiple inorganic substances, and has extremely high potential activity.

[0052] The main function of the composite active activator is to make full use of the alkaline substances, sulfates, silicates and other components in industrial waste to effectively stimulate the potential activity of fly ash. Combined with the use of quick-setting and early-strength agents and modifiers, it can significantly improve the compressive strength of fly ash at all ages; it can significantly increase the dosage of fly ash in cement or cement concrete, as well as the performance of cement concrete, increase the overall dosage of fly ash, save cement and reduce the cost of concrete and its products, and has significant economic and social benefits.

[0053] Quick-setting and early-strength agent: The quick-setting and early-strength agent is a mixture of alumina clinker, sodium carbonate, quicklime, potassium aluminum sulfate and silica fume. Its mechanism of action is that the effective components can cause the rapid hydration of calcium aluminate minerals and precipitate their hydration product crystals in the solution; the alumina clinker, quicklime, potassium aluminum sulfate and other components provide effective components for the formation of hydrated calcium sulfoaluminate and secondary gypsum crystals with very low solubility, which promotes the increase of 1-3d compressive strength and flexural strength; at the same time, the addition of silica fume can improve the size and number of pores in the solidified body, making the microstructure of the concrete more uniform and dense. Secondly, silica fume can reduce the segregation and bleeding of concrete, increase the cohesion inside the concrete, and the active silicon dioxide in silica fume can react with calcium ions in concrete to generate high-strength hydration products. The addition of silica fume mainly improves the later (28d and later) compressive and flexural strength of concrete.

[0054] Modifier (expansion agent, water reducer, defoamer): Modifiers are generally composed of expansion agent, water reducer, defoamer, etc. Different modifiers are selected according to different construction environments to modify the slurry transportation performance and the mechanical properties of the filling 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 solidify ammonia in all directions. Styrene-acrylic emulsion has good film-forming properties. After the emulsion forms a film, it can effectively prevent the overflow of ammonia.

[0056] The ammonia in the fly ash is solidified by the coordinated cooperation of various components, which effectively solves the problem of ammonia overflow and pungent odor when large-volume fly ash is filled.

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

[0058] Activity activation mechanism: The main mechanism of activity activation is to stimulate the potential activity of fly ash by the effective components of the composite high-efficiency activator. The composite active activator supplements the calcium content of the fly ash system. Because the amount of hydration and gelation products formed after fly ash activation has a significant impact on the later strength of the fly ash system, only with sufficient calcium can more hydration and gelation products be formed after activation, and the later strength of the fly ash system can be effectively improved; the calcium hydroxide in the activator and the effective component sodium aluminate in the alumina clinker in the early strength agent are used to directly destroy the acidic fly ash system, which is mainly reflected in OH - It can break Si-O bonds and Al-O bonds, thus destroying the Si-O tetrahedron and Al-O octahedron network structure in the glass, increasing the amount of active matter dissolved inside the fly ash particles, accelerating the reaction of Al2O3, SiO2 and Ca(OH)2, and promoting the formation of gel. Strong alkali has a significant effect on improving the early strength of the system; potassium aluminum sulfate in the quick-setting early strength agent ionizes SO4 in the aqueous solution 2- , SO4 2- In Ca 2+ Under the action of calcium sulfide, it reacts with the active Al2O3 in the glass to form calcium sulfide, which is filled in the cement stone structure, greatly improving the density of the system, thereby improving its early strength; at the same time, the large amount of calcium sulfide generated can increase the volume of the solid phase, and the volume of the filling body increases after solidification. Combined with the use of expansion agent in the modifier, it can effectively improve the expansion performance of the filling material. In addition, the compactness of the calcium sulfide coating layer is smaller than that of the hydrated calcium silicate layer, which is beneficial to the Ca 2+ Diffuse into the interior of the fly ash particles, continue to react with the internal active substances, and further promote the production of gel. After the fly ash is compositely stimulated by strong alkali, sulfate, etc., most of the fly ash particles participate in the reaction, forming many silky products such as hydrated calcium silicate and hydrated calcium aluminate, making the entire system more compact. The present invention effectively stimulates the chemical activity of fly ash through a composite high-efficiency stimulator, which is beneficial to the dissolution of active substances. The main excitation reactions are as follows:

[0059] SiO2(active)+m1Ca(OH)2+xH2O→m1CaO·SiO2·xH2O

[0060] Al2O3(active)+m2Ca(OH)2+yH2O→m2CaO·Al2O3·yH2O

[0061] 2NaAlO2+3CaO+7H2O→3CaO·Al2O3·6H2O+2NaOH

[0062] 3CaO·Al2O3·6H2O+3(CaSO4·2H2O)+20H2O→3CaO·Al2O3·3CaSO4·32H2O (ettringite)

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

[0064] Cu 2+ +4NH3·H2O=[Cu(NH3)4] 2+ +4H2O

[0065] The present invention will be further described in detail below in conjunction with specific embodiments. It should be noted that the specific embodiments are intended to explain the present invention rather than to limit it.

[0066] Example 1: This example provides a green and environmentally friendly fly ash multi-effect stimulator and a preparation method thereof.

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

[0068] The preparation method of the green and environmentally friendly fly ash multi-effect stimulator comprises the following steps:

[0069] S1, carbide slag, salt gypsum, blast furnace water quenching slag, red mud, spodumene slag in a weight ratio of 5:1:2:1:1, calcined at 950°C for 2 hours, crushed and ground to a specific surface area of ​​500m2 / kg to obtain a composite active activator;

[0070] S2. Alumina clinker, sodium carbonate, quicklime, potassium aluminum sulfate and silica fume are mixed in a weight ratio of 2:2:1:3:2 to prepare a quick-setting early strength agent;

[0071] S3, mixing a composite active activator, a quick-setting early strength agent, and a modifier (wherein the expansion agent is aluminum sulfate, the water reducer is a polycarboxylic acid water reducer, and the defoamer is an organic silicon defoamer) to obtain a composite high-efficiency active activator of component A;

[0072] S4, styrene acrylic emulsion, copper nitrate, glycerol, and triethanolamine are mixed in a weight ratio of 1:6:1:1 to obtain a component B composite high-efficiency ammonia fixer;

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

[0074] Example 2: This example provides a green and environmentally friendly fly ash multi-effect stimulator and a preparation method thereof.

[0075] By weight, the raw material composition of the green and environmentally friendly fly ash multi-effect activator includes: 68% of a composite high-efficiency active activator, 12% of a quick-setting early strength agent, 5% of a modifier, and 15% of a composite high-efficiency ammonia-fixing agent; the preparation steps are consistent with Example 1.

[0076] Comparative Example 1: The components of Comparative Example 1 are different from those of Example 1 in that no quick-setting and early-strength agent is added, and the other components are the same as those of Example 1; and the preparation steps are the same as those of Example 1.

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

[0078] Comparative Example 2: The difference between the components of Example 1 is that no silica fume is added to the quick-setting early strength agent, and the other components are the same as those of Example 1; the preparation steps are consistent with those of Example 1.

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

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

[0081] Comparative Example 4: The difference from the components in Example 1 is that the weight ratio of styrene acrylic emulsion (solid content ≥45%), glycerol (purity ≥90%), and triethanolamine in the composite high-efficiency ammonia solidifier is 1:2:1, and the other components are the same as those in Example 1; the preparation steps are consistent with those in Example 1.

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

[0083] Comparative Example 5:

[0084] The difference from the components of Example 1 is that PO425 ordinary Portland cement is used instead of 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 stimulants involved in Examples 1 to 2 and Comparative Examples 1 to 5, as shown in Table 1:

[0086] Table 1 Content of each component of green and environmentally friendly multi-functional additives for mining

[0087]

[0088] Test Example 1:

[0089] This experimental example compares the performance of the multi-effect activator prepared in Examples 1 to 2 and Comparative Examples 1 to 5 in the application of fly ash high-water cementing filling. The specific fly ash high-water filling ratio values ​​are shown in Table 2; the performance test data comparison 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 stimulator obtained in Examples 1 to 2 is better than that in Comparative Examples 1 to 5. Compared with Comparative Example 1, in Examples 1 to 2, the quick-setting early strength agent is beneficial to enhancing the compressive and flexural strength of the multi-effect stimulator in the application of fly ash high-water cementing filling, and can effectively solidify the ammonia in the fly ash; compared with Comparative Example 2, it can be seen that the addition of silica fume components in the quick-setting early strength agent mainly improves the compressive and flexural strength of the fly ash high-water cementing filling in the later period (28 days and later); compared with Comparative Examples 3 to 4, it can be seen that the composite high-efficiency ammonia-fixing agent component of the multi-effect stimulator is more conducive to synergistically enhancing the compressive and flexural strength of the multi-effect stimulator in the application of fly ash high-water cementing filling, and can effectively solidify the ammonia in the fly ash; compared with Comparative Example 5, it can be seen that the compressive, flexural strength and ammonia-fixing amount of PO425 ordinary silicate cement are lower than those of the composite multi-effect stimulator.

[0095] Test Example 2:

[0096] This experimental example compares the performance of the multi-effect stimulators prepared in Examples 1-2 and Comparative Examples 1-5 when used as concrete admixtures (construction field). The specific concrete mix ratio values ​​are shown in Table 4; the performance test data comparison is shown in Table 5:

[0097] Table 4 Concrete mix ratio

[0098] Examples cement Fly ash Multi-effect stimulant Sand Stone 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 Concrete test data comparison

[0100]

[0101]

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

[0103] The above description is only a preferred embodiment of the present invention and is 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 in 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.

2. The green and environmentally friendly fly ash multi-effect stimulator according to claim 1, characterized in that: The raw material composition of the green and environmentally friendly fly ash multi-effect activator includes, by weight: 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 weight ratio of carbide slag, salt gypsum, blast furnace water-quenched 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.

4. The green and environmentally friendly fly ash multi-effect stimulator according to any one of claims 1 to 2, characterized in that: The modifier is generally composed of an expander, a water reducer, and a defoamer. Different modifiers are selected according to different construction environments. The expander 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-based water reducers, polycarboxylic acid water reducers, aliphatic water reducers, and lignin sulfonate water reducers; and the defoamer is an organosilicon defoamer.

5. A method for preparing the green and environmentally friendly fly ash multi-effect stimulator according to any one of claims 1 to 4, 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 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.

6. The preparation method according to claim 5, characterized in that: In step S1, the calcination reaction temperature is 800-1000°C, and the calcination reaction time is 1.5-2.5h; preferably, the calcination reaction temperature is 950°C, and the calcination reaction time is 2h.

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 500m2 / kg.

8. A method for using a green and environmentally friendly fly ash multi-effect stimulant for mine filling, 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 activator, and then water is added to form a slurry, and the slurry is delivered to the filling area by gravity or pumping through a pipeline for filling; Preferably, 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).

9. A method for mixing concrete with a green and environmentally friendly fly ash multi-effect activator, characterized in that: The concrete blending method is specifically as follows: when using, the fly ash replaces 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; Preferably, the fly ash and the fly ash multi-effect stimulator are mixed in a weight ratio of 100:(5-15).

10. Application of the green and environment-friendly fly ash multi-effect stimulator according to any one of claims 1 to 4 in the field of construction engineering.

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