CN113060961B - Excitant for mine filling material and preparation method thereof - Google Patents
Excitant for mine filling material and preparation method thereof Download PDFInfo
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- CN113060961B CN113060961B CN202110275780.0A CN202110275780A CN113060961B CN 113060961 B CN113060961 B CN 113060961B CN 202110275780 A CN202110275780 A CN 202110275780A CN 113060961 B CN113060961 B CN 113060961B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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Abstract
The invention discloses an excitant for a mine filling material and a preparation method thereof. The activator comprises 76-78 parts of steel slag, 14-16 parts of sodium silicate, 2-4 parts of aluminum sulfate and 4-6 parts of ammonium sulfate, and further comprises high-molecular water-absorbing resin, calcium oxide and microcrystalline cellulose subjected to alkali treatment. The preparation method of the excitant for the mine filling material comprises the steps of crushing materials, mixing powdery steel slag and powdery sodium silicate, adding powdery aluminum sulfate, adding powdery ammonium sulfate and the like, and also comprises the steps of adding high-molecular water-absorbing resin, adding calcium oxide, adding microcrystalline cellulose subjected to alkali treatment and the like. The excitant prepared by the preparation method for the mine filling material can improve the product percent of pass of the gelling agent, reduce the production cost, ensure that the excitant has better fluidity, provide stronger alkalinity and have better economic and social benefits.
Description
Technical Field
The invention relates to a mine filling material technology, in particular to an excitant for a mine filling material and a preparation method thereof.
Background
The mining industry forms more goafs, causes the problems of ground settlement, subsidence and the like, causes a plurality of adverse effects on the production and life of people, and influences the safety of the production and life. Meanwhile, the mining industry and the metallurgical industry generate a large amount of solid wastes such as tailings and steel slag, and the storage of the solid wastes occupies a large amount of land, thereby causing resource waste.
The method has the advantages that solid waste such as tailings, steel slag and the like is backfilled into the goaf to form filling mining, so that the solid waste can be consumed, and meanwhile, the problems of ground settlement, collapse and the like of the goaf can be relieved to a great extent, so that the method achieves two purposes.
The gelling agent is a solid substance which needs to be added in the filling and mining process, and can play a role in accelerating the consolidation of the filling material and increasing the compressive strength of the filling and consolidating material. The activator is an indispensable component of the gelling agent. The excitant in the prior art has the problems of substandard performance, poor fluidity, insufficient alkalinity, low qualification rate of the produced gelatinizer and high use cost. Therefore, it is required to provide an activator for mine filling materials and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide an excitant for a mine filling material and a preparation method thereof, and the excitant for the mine filling material and the preparation method thereof can improve the product yield of a gelling agent, reduce the production cost, enable the excitant to have better fluidity and provide stronger alkalinity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an activator for a mine filling material, the activator comprising steel slag, sodium silicate, aluminium sulphate and ammonium sulphate;
the exciting agent for the mine filling material is prepared from the following raw materials in parts by weight: 76-78 parts of steel slag, 14-16 parts of sodium silicate, 2-4 parts of aluminum sulfate and 4-6 parts of ammonium sulfate;
the steel slag comprises electric furnace steel slag, the steel slag is obtained by naturally cooling under a drying condition, and the drying condition means that the environmental humidity is below 5%;
the sodium silicate comprises solid sodium silicate which is prepared by dry-method casting molding;
the aluminum sulfate comprises anhydrous aluminum sulfate;
the ammonium sulfate includes anhydrous ammonium sulfate.
Preferably, the exciting agent comprises steel slag, sodium silicate, aluminum sulfate and ammonium sulfate;
the exciting agent for the mine filling material is prepared from the following raw materials in parts by weight: 77 parts of steel slag, 15 parts of sodium silicate, 3 parts of aluminum sulfate and 5 parts of ammonium sulfate;
the steel slag comprises electric furnace steel slag, the steel slag is obtained by naturally cooling under a drying condition, and the drying condition refers to that the environmental humidity is 5%;
the sodium silicate comprises solid sodium silicate which is prepared by dry-method casting molding;
the aluminum sulfate comprises anhydrous aluminum sulfate;
the ammonium sulfate includes anhydrous ammonium sulfate.
Preferably, the steel slag comprises 4-6% of metallic iron, 4-5% of magnesium oxide and 1.1-2.3% of manganese oxide by mass.
Preferably, the activator further comprises a high-molecular water-absorbing resin, wherein the addition amount of the high-molecular water-absorbing resin is 0.1-0.3 part by weight, and the effect of the high-molecular water-absorbing resin is to avoid the reduction of the excitation performance caused by water vapor in the storage environment of the activator.
Preferably, the excitant further comprises calcium oxide, and the addition amount of the calcium oxide is 1-2 parts by weight, so that the reduction of the excitation performance caused by carbon dioxide existing in the storage environment of the excitant is avoided.
In a second aspect, the invention provides a method for preparing an activator for a mine filling material, the method comprising the steps of:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers respectively to obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate respectively, wherein the crushed environmental humidity is below 5%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 76-78 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 15-20 r/min, mixing for 5-7 min, adding 14-16 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 24-26 r/min, and mixing for 20-30 min to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 2-4 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 22-24 revolutions per minute, and mixing for 10-18 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: adding 4-6 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of powdery steel slag, powdery sodium silicate and powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 12-16 rpm, and mixing for 30-48 minutes to obtain the excitant.
Preferably, the material container of the V-shaped mixer is a sealed container.
Preferably, in the material mixing process of the step 2) to the step 4), dry nitrogen is filled into a material container of the V-shaped blender mixer for protection, so that water and carbon dioxide are prevented from reducing the performance of the excitant.
Preferably, the step 4) is followed by a step of adding a high molecular water-absorbent resin, wherein 0.1-0.3 part by weight of the high molecular water-absorbent resin is added into the activator, the rotating speed of the V-shaped mixer is set at 8-13 rpm, and the mixture is mixed for 30-36 minutes.
Preferably, the step 4) is followed by a step of adding calcium oxide, wherein 1-2 parts by weight of calcium oxide with the particle size of 30-60 micrometers is added into the exciting agent, and the rotating speed of the V-shaped mixer is set at 18-24 revolutions per minute and the mixture is mixed for 20-25 minutes.
Compared with the prior art, the invention has the following beneficial effects: (1) the problem of unstable performance of the prior exciting agent is solved, the product percent of pass of the exciting agent for producing the gelatinizing agent is improved, and the product percent of pass is improved to more than 90 percent from less than 90 percent; (2) the activator has better fluidity and can provide stronger alkalinity, thereby reducing the production cost of the gelling agent and reducing the production cost per ton by over 58 yuan; (3) the development of the product is based on solid wastes generated in steel making, iron making and pellet production, reduces the pollution of the solid wastes to the environment, fully utilizes effective elements in the solid wastes, and reduces the waste of resources; (4) has better economic and social benefits, can create 3700 ten thousand yuan of sales income every year, 1350 ten thousand yuan of net profit and 370 ten thousand yuan of tax payment all year round according to the calculation of the productivity of 10 ten thousand tons of gelling agents produced every year, and can also create nearly 40 employment posts.
Detailed Description
The invention provides an excitant for mine filling materials and a preparation method thereof, and the excitant for mine filling materials and the preparation method thereof can improve the product percent of pass of gelling agents and reduce the production cost.
The invention provides an exciting agent for a mine filling material, which comprises steel slag, sodium silicate, aluminum sulfate and ammonium sulfate;
the exciting agent for the mine filling material is prepared from the following raw materials in parts by weight: 76-78 parts of steel slag, 14-16 parts of sodium silicate, 2-4 parts of aluminum sulfate and 4-6 parts of ammonium sulfate;
the steel slag comprises electric furnace steel slag which is obtained by naturally cooling the steel slag under the drying condition, wherein the drying condition means that the environmental humidity is below 5 percent;
the sodium silicate comprises solid sodium silicate which is prepared by dry-method casting molding;
the aluminum sulfate includes anhydrous aluminum sulfate;
the ammonium sulfate includes anhydrous ammonium sulfate.
Preferably, the exciting agent comprises steel slag, sodium silicate, aluminum sulfate and ammonium sulfate;
the exciting agent for the mine filling material is prepared from the following raw materials in parts by weight: 77 parts of steel slag, 15 parts of sodium silicate, 3 parts of aluminum sulfate and 5 parts of ammonium sulfate;
the steel slag comprises electric furnace steel slag which is obtained by naturally cooling the steel slag under the drying condition, wherein the drying condition refers to that the environmental humidity is 5 percent;
the sodium silicate comprises solid sodium silicate which is prepared by dry-method casting molding;
the aluminum sulfate includes anhydrous aluminum sulfate;
the ammonium sulfate includes anhydrous ammonium sulfate.
The main function of adding the steel slag into the exciting agent is to increase the contents of tricalcium silicate and dicalcium silicate in the gelling agent and improve the activity of the prepared gelling agent.
The addition of sodium silicate in the excitant of the invention has the functions of increasing the caking property of the gelling agent and improving the compressive strength of the gelling agent.
The activator of the invention is added with aluminum sulfate to improve the coagulation speed of the gelling agent, so that the activator meets the requirement of quick coagulation.
The exciting agent of the invention is added with ammonium sulfate to play the roles of catalysis and hardening.
The electric furnace steel slag naturally cooled under the dry condition contains a small amount of free calcium and magnesium oxides, and when the electric furnace steel slag is used as an exciting agent added into a gelling agent, the electric furnace steel slag chemically reacts with added water, more alkaline substances can be generated, the consolidation strength of filling materials can be improved, and the consolidation time can be shortened. In addition, the electric furnace steel slag obtained under the condition contains more gamma-type dicalcium silicate, so that the steel slag is easier to crush, and the preparation cost of the exciting agent is favorably reduced.
Preferably, the mass content of each substance in the steel slag is 4-6% of metallic iron, 4-5% of magnesium oxide and 1.1-2.3% of manganese oxide.
Preferably, the activator also comprises a high-molecular water-absorbing resin, and the addition amount of the high-molecular water-absorbing resin is 0.1-0.3 part by weight, and the function of the activator is to avoid the reduction of the excitation performance caused by water vapor existing in the storage environment of the activator. Is favorable for prolonging the shelf life of the excitant and better preserving the alkalinity providing capability of the excitant, thereby being favorable for shortening the consolidation time of the gelling agent and the filling material.
Preferably, the activator also comprises calcium oxide, the addition amount of the calcium oxide is 1-2 parts by weight, the effect is to avoid the reduction of the excitation performance by carbon dioxide existing in the storage environment of the activator, and the capability of the activator for providing alkalinity can be improved. Carbon dioxide in the air can react with various forms of alkaline substances present in the excitant, reducing its excitability. After a small amount of calcium oxide is added, carbon dioxide and water in the storage environment preferentially react with the calcium oxide to produce calcium carbonate, so that the performance of the excitant is maintained.
More preferably, the activator also comprises microcrystalline cellulose treated by alkali, the addition amount is 0.05-0.15 part by weight, the polymerization degree of the added microcrystalline cellulose is 100-200, and the particle size is 20-30 microns.
The alkali treatment method of the microcrystalline cellulose comprises the following steps: soaking microcrystalline cellulose in 1-2 mol/L sodium hydroxide solution for 20-40 minutes, then washing with water to be neutral, and drying with hot air at 70-80 ℃ to constant weight to obtain the alkali-treated microcrystalline cellulose.
The alkali-treated microcrystalline cellulose has alkaline groups in molecules, so that alkaline substances of the activator can be increased, the activity of the activator is enhanced, and meanwhile, a three-dimensional net structure taking the micro-cellulose as a skeleton is formed, so that the filling material forms a microstructure similar to reinforced concrete, and the compressive strength of the filling material can be enhanced.
The invention provides a preparation method of an exciting agent for a mine filling material, which comprises the following steps:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers respectively to obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate respectively, wherein the crushing environment humidity is below 5%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 76-78 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 15-20 r/min, mixing for 5-7 min, adding 14-16 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 24-26 r/min, and mixing for 20-30 min to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 2-4 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 22-24 revolutions per minute, and mixing for 10-18 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: adding 4-6 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of powdery steel slag, powdery sodium silicate and powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 12-16 rpm, and mixing for 30-48 minutes to obtain the excitant.
The invention adopts the substances such as powdery steel slag, powdery sodium silicate, powdery aluminum sulfate, powdery ammonium sulfate and the like to prepare the excitant, so that the excitant has better fluidity.
Preferably, the material container of the V-shaped mixer is a sealed container.
Preferably, in the material mixing process of the steps 2) to 4), dry nitrogen is filled into a material container of the V-shaped mixer for protection, so that the performance of the excitant is prevented from being reduced by water and carbon dioxide.
Preferably, the step 4) is followed by a step of adding a high molecular water-absorbing resin, wherein 0.1-0.3 part by weight of the high molecular water-absorbing resin is added into the activator, the rotating speed of the V-shaped mixer is set at 8-13 rpm, and the mixture is mixed for 30-36 minutes.
Preferably, the step 4) is followed by a step of adding calcium oxide, wherein 1-2 parts by weight of calcium oxide with the particle size of 30-60 micrometers is added into the exciting agent, and the rotating speed of the V-shaped mixer is set at 18-24 revolutions per minute and is mixed for 20-25 minutes.
Further preferably, the step 4) is followed by a step of adding alkali-treated microcrystalline cellulose, wherein 0.05-0.15 part by weight of alkali-treated microcrystalline cellulose with the particle size of 20-30 microns is added into the activator, the rotating speed of the V-shaped mixer is set at 11-15 revolutions per minute, and the mixture is mixed for 30-35 minutes.
The technical solutions of the present invention will be described clearly and completely by the following embodiments, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The composition of the activator used in this example was as follows: the steel slag is obtained by naturally cooling electric furnace steel slag under the drying condition that the environmental humidity is 5%, wherein the steel slag comprises 4% of iron, 5% of magnesium oxide and 1.1% of manganese oxide, the sodium silicate is solid sodium silicate prepared by dry casting and forming, the aluminum sulfate is anhydrous aluminum sulfate, and the ammonium sulfate is anhydrous ammonium sulfate.
The activator of this example was prepared as follows:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 20-25 micrometers, 40-50 micrometers, 15-20 micrometers and 110-120 micrometers to respectively obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate, wherein the crushed environment humidity is about 4%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 76 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 15 revolutions per minute, mixing for 7 minutes, adding 16 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 26 revolutions per minute, and mixing for 20 minutes to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 2 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 24 revolutions per minute, and mixing for 10 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: and (2) adding 6 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of powdery steel slag, powdery sodium silicate and powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 12 revolutions per minute, and mixing for 48 minutes to obtain the exciting agent.
The obtained activator has 18% higher fluidity than the activators of the prior art.
The exciting agent obtained in the embodiment is used for preparing a 1:8 magnetite gelling agent, and the formula (mass percentage) comprises 70% of granulated slag, 17% of desulfurized gypsum, 7% of steel slag and 6% of the exciting agent prepared in the embodiment. The qualification rate of the obtained gelling agent reaches more than 91 percent, and the production cost is reduced by 56 yuan/ton gelling agent. The filling is carried out by adopting an in-service filling mining method, the strength is more than 2.8Mpa in 28 days, and the consolidation time is shortened by 14 percent.
Example 2
The composition of the activator used in this example was as follows: 78 parts of steel slag, 14 parts of sodium silicate, 4 parts of aluminum sulfate and 4 parts of ammonium sulfate, wherein the steel slag is obtained by naturally cooling the electric furnace steel slag under the drying condition that the ambient humidity is 3%, the main substances of the steel slag comprise 6% of iron, 4% of magnesium oxide and 2.3% of manganese oxide, the sodium silicate is solid sodium silicate prepared by dry casting and forming, the aluminum sulfate is anhydrous aluminum sulfate, and the ammonium sulfate is anhydrous ammonium sulfate.
The activator of this example was prepared as follows:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 25-30 micrometers, 50-60 micrometers, 10-15 micrometers and 100-110 micrometers to respectively obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate, wherein the crushed environment humidity is about 5%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 78 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 20 revolutions per minute, mixing for 5 minutes, adding 14 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 24 revolutions per minute, and mixing for 30 minutes to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 4 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 22 revolutions per minute, and mixing for 18 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: and 4 parts by weight of the powdery ammonium sulfate obtained in the step 1) is added into the mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate obtained in the step 3), the rotating speed of the V-shaped mixer is set at 16 revolutions per minute, and the mixture is mixed for 30 minutes to obtain the exciting agent.
The obtained excitant has the fluidity improved by 19 percent compared with the excitant of the prior art.
The exciting agent obtained in the embodiment is used for preparing a 1:8 magnetite gelling agent, and the formula (mass percentage) comprises 70% of granulated slag, 17% of desulfurized gypsum, 7% of steel slag and 6% of the exciting agent prepared in the embodiment. The qualification rate of the obtained gelling agent reaches more than 90 percent, and the production cost is reduced by 55 yuan/ton gelling agent. The filling is carried out by adopting an in-service filling mining method, and the 28-day strength is more than 2.8 MPa.
Example 3
The composition of the activator used in this example was as follows: 77 parts of steel slag, 15 parts of sodium silicate, 3 parts of aluminum sulfate and 5 parts of ammonium sulfate, wherein the steel slag is obtained by naturally cooling the electric furnace steel slag under the drying condition that the ambient humidity is 4%, the main substance content is 5% of iron, 4.5% of magnesium oxide and 1.7% of manganese oxide, the sodium silicate is solid sodium silicate prepared by dry casting and molding, the aluminum sulfate is anhydrous aluminum sulfate, and the ammonium sulfate is anhydrous ammonium sulfate.
The activator of this example was prepared as follows:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers to respectively obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate, wherein the crushed environment humidity is about 3%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 77 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 18 revolutions per minute, mixing for 6 minutes, adding 15 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 25 revolutions per minute, and mixing for 25 minutes to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 3 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 23 revolutions per minute, and mixing for 14 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: and (2) adding 5 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 14 revolutions per minute, and mixing for 39 minutes to obtain the exciting agent.
The obtained excitant has 17% higher fluidity than the excitant of the prior art.
The exciting agent obtained in the embodiment is used for preparing a 1:8 magnetite gelling agent, and the formula (mass percentage) comprises 70% of granulated slag, 17% of desulfurized gypsum, 7% of steel slag and 6% of the exciting agent prepared in the embodiment. The qualification rate of the obtained gelling agent reaches more than 92 percent, and the production cost is reduced by 58 yuan/ton gelling agent. The filling is carried out by adopting an in-service filling mining method, and the 28-day strength is more than 2.8 MPa.
Example 4
The composition of the activator used in this example was as follows: 77 parts of steel slag, 15 parts of sodium silicate, 3 parts of aluminum sulfate, 5 parts of ammonium sulfate and 0.2 part of macromolecular water-absorbing resin, wherein the steel slag is obtained by naturally cooling electric furnace steel slag under the drying condition of the environmental humidity of 4%, the main substance content is 5% of iron, 4.5% of magnesium oxide and 1.7% of manganese oxide, the sodium silicate is solid sodium silicate prepared by dry casting molding, the aluminum sulfate is anhydrous aluminum sulfate, and the ammonium sulfate is anhydrous ammonium sulfate.
The activator of this example was prepared as follows:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers to respectively obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate, wherein the crushed environment humidity is about 3%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 77 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 18 revolutions per minute, mixing for 6 minutes, adding 15 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 25 revolutions per minute, and mixing for 25 minutes to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 3 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 23 revolutions per minute, and mixing for 14 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: adding 5 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 14 revolutions per minute, and mixing for 39 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate and the ammonium sulfate;
adding a high-molecular water-absorbent resin: 0.2 weight part of high molecular water-absorbing resin is taken, and the mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate and the ammonium sulfate obtained in the step 4) is added to be uniformly mixed, so that the excitant is obtained.
The storage life of the activator obtained in this example was extended by 8% or more due to the addition of the water-absorbent polymer resin.
The exciting agent obtained in the embodiment is used for preparing a 1:8 magnetite gelling agent, and the formula (mass percentage) comprises 70% of granulated slag, 17% of desulfurized gypsum, 7% of steel slag and 6% of the exciting agent prepared in the embodiment. The qualification rate of the obtained gelling agent reaches more than 93 percent, and the production cost is reduced by 53 yuan/ton gelling agent. The filling is carried out by adopting an in-situ filling mining method, the strength is more than 2.8Mpa in 28 days, and the consolidation time is shortened by 16 percent.
Example 5
The composition of the activator used in this example was as follows: 77 parts of steel slag, 15 parts of sodium silicate, 3 parts of aluminum sulfate, 5 parts of ammonium sulfate, 0.1 part of macromolecular water-absorbing resin and 1.5 parts of calcium oxide, wherein the steel slag is obtained by naturally cooling the electric furnace steel slag under the drying condition of the environmental humidity of 4 percent, the main substance content of the steel slag is 5 percent of iron, 4.5 percent of magnesium oxide and 1.7 percent of manganese oxide, the sodium silicate is solid sodium silicate prepared by dry casting and molding, the aluminum sulfate is anhydrous aluminum sulfate, and the ammonium sulfate is anhydrous ammonium sulfate.
The activator of this example was prepared as follows:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers to respectively obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate, wherein the crushed environment humidity is about 3%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 77 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 18 revolutions per minute, mixing for 6 minutes, adding 15 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 25 revolutions per minute, and mixing for 25 minutes to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 3 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 23 revolutions per minute, and mixing for 14 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: adding 5 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 14 revolutions per minute, and mixing for 39 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate and the ammonium sulfate;
adding a high-molecular water-absorbent resin: and (3) adding 0.1 part by weight of high molecular water-absorbent resin into the mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate and the ammonium sulfate obtained in the step 4), and uniformly mixing to obtain a mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate, the ammonium sulfate and the high molecular water-absorbent resin.
Adding calcium oxide: 1.5 parts by weight of powdery calcium oxide is taken, and a mixture of powdery steel slag, powdery sodium silicate, powdery aluminum sulfate, ammonium sulfate and high-molecular water-absorbent resin is added to be uniformly mixed, so that the excitant is obtained.
The storage life of the activator obtained in this example was extended by 13% or more by the addition of the high molecular water-absorbent resin and calcium oxide.
The exciting agent obtained in the embodiment is used for preparing a 1:8 magnetite gelling agent, and the formula (mass percentage) comprises 70% of granulated slag, 17% of desulfurized gypsum, 7% of steel slag and 6% of the exciting agent prepared in the embodiment. The qualification rate of the obtained gelling agent reaches more than 94 percent, and the production cost is reduced by 51 yuan/ton of gelling agent. The filling is carried out by adopting an in-situ filling mining method, the strength is more than 2.8Mpa in 28 days, and the consolidation time is shortened by 18 percent.
Example 6
The composition of the activator used in this example was as follows: 77 parts of steel slag, 15 parts of sodium silicate, 3 parts of aluminum sulfate, 5 parts of ammonium sulfate, 0.2 part of high-molecular water-absorbing resin, 2 parts of calcium oxide and 0.1 part of microcrystalline cellulose subjected to alkali treatment, wherein the steel slag is obtained by naturally cooling electric furnace steel slag under the drying condition that the ambient humidity is 4%, the main substance content is 5% of iron, 4.5% of magnesium oxide and 1.7% of manganese oxide, the sodium silicate is solid sodium silicate prepared by dry casting molding, the aluminum sulfate is anhydrous aluminum sulfate, and the ammonium sulfate is anhydrous ammonium sulfate. The polymerization degree of the added microcrystalline cellulose is about 150, the particle size is about 25 microns, the microcrystalline cellulose is soaked in 1.5mol/L sodium hydroxide solution for 30 minutes, then is washed to be neutral by water, and is dried to constant weight by using hot air at 75 ℃, so that the microcrystalline cellulose treated by alkali is obtained.
The activator of this example was prepared as follows:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, and crushing the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers to respectively obtain powdery steel slag, powdery sodium silicate, powdery aluminum sulfate and powdery ammonium sulfate, wherein the crushed environment humidity is about 3%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 77 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 18 revolutions per minute, mixing for 6 minutes, adding 15 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 25 revolutions per minute, and mixing for 25 minutes to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 3 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 23 revolutions per minute, and mixing for 14 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: adding 5 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 14 revolutions per minute, and mixing for 39 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate and the ammonium sulfate;
adding a high-molecular water-absorbent resin: taking 0.1 part by weight of high molecular water-absorbing resin, adding the mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate and the ammonium sulfate obtained in the step 4), and uniformly mixing to obtain a mixture of the powdery steel slag, the powdery sodium silicate, the powdery aluminum sulfate, the ammonium sulfate and the high molecular water-absorbing resin;
adding calcium oxide: taking 1.5 weight parts of powdery calcium oxide, adding a mixture of powdery steel slag, powdery sodium silicate, powdery aluminum sulfate, ammonium sulfate and high-molecular water-absorbing resin, and uniformly mixing to obtain the calcium oxide-calcium composite material
Adding alkali-treated microcrystalline cellulose: 0.1 weight part of microcrystalline cellulose subjected to alkali treatment is taken, and a mixture of powdery steel slag, powdery sodium silicate, powdery aluminum sulfate, ammonium sulfate, high-molecular water-absorbing resin and calcium oxide is added and uniformly mixed to obtain the excitant.
The storage life of the activator obtained in this example was extended by 13% or more by the addition of the high molecular water-absorbent resin and calcium oxide.
The exciting agent obtained in the embodiment is used for preparing a 1:8 magnetite gelling agent, and the formula (mass percentage) comprises 70% of granulated slag, 17% of desulfurized gypsum, 7% of steel slag and 6% of the exciting agent prepared in the embodiment. The qualification rate of the obtained gelling agent reaches more than 94 percent, and the production cost is reduced by 46 yuan/ton gelling agent. The filling is carried out by adopting an in-process filling mining method, the strength can reach 2.6Mpa in 24 days and can be more than 3.0 Mpa in 28 days due to the addition of the microcrystalline cellulose, and the consolidation time is shortened by 19 percent.
Comparative example
The activator is prepared by the method in the prior art, the qualification rate of the gelatinizer prepared by the activator is only about 88 percent, and the production cost is about 60 yuan/ton higher than that of the gelatinizer prepared by the activator.
In conclusion, the excitant and the preparation method thereof solve the problem of unstable performance of the current excitant, improve the product percent of pass of the excitant for producing the gelatinizer, and improve the product percent of pass from less than 90% to more than 90%; the compressive strength of the filling material is improved; the fluidity and the alkalinity providing capability of the excitant are improved, so that the consolidation capability of the excitant is improved; the activator of the invention is used for producing the gelling agent, so that the production cost of the gelling agent is reduced, and the production cost per ton is reduced by over 58 yuan; the development of the product is based on solid wastes generated in steel making, iron making and pellet production, reduces the pollution of the solid wastes to the environment, fully utilizes effective elements in the solid wastes, and reduces the waste of resources; has better economic and social benefits, can create 3700 ten thousand yuan of sales income every year, 1350 ten thousand yuan of net profit and 370 ten thousand yuan of tax payment all year round according to the calculation of the productivity of 10 ten thousand tons of gelling agents produced every year, and can also create nearly 40 employment posts.
Finally, it should be noted that: the above-mentioned embodiments are only specific embodiments of the present invention, which are used for illustrating the technical solutions of the present invention and not for limiting the same, and the protection scope of the present invention is not limited thereto, although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the present invention in its spirit and scope. Are intended to be covered by the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
The applicant declares that the technical solution of the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, the present invention is not meant to be implemented only by relying on the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. An activator for a mine fill material, comprising: steel slag, sodium silicate, aluminum sulfate and ammonium sulfate;
the exciting agent for the mine filling material is prepared from the following raw materials in parts by weight: 76-78 parts of steel slag, 14-16 parts of sodium silicate, 2-4 parts of aluminum sulfate and 4-6 parts of ammonium sulfate;
the steel slag comprises electric furnace steel slag, the steel slag is obtained by naturally cooling under a drying condition, and the drying condition means that the environmental humidity is below 5%;
the sodium silicate comprises solid sodium silicate which is prepared by dry-method casting molding;
the aluminum sulfate comprises anhydrous aluminum sulfate;
the ammonium sulfate comprises anhydrous ammonium sulfate;
the activator also comprises microcrystalline cellulose subjected to alkali treatment, the addition amount is 0.05-0.15 part by weight, the polymerization degree of the added microcrystalline cellulose is 100-200, and the granularity is 20-30 microns;
the alkali treatment method of the microcrystalline cellulose comprises the following steps: soaking microcrystalline cellulose in 1-2 mol/L sodium hydroxide solution for 20-40 minutes, washing with water to be neutral, and drying with hot air at 70-80 ℃ to constant weight to obtain alkali-treated microcrystalline cellulose;
the preparation method of the excitant comprises the following steps:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, so that the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate are respectively crushed into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers, and the powdered steel slag, the powdered sodium silicate, the powdered aluminum sulfate and the powdered ammonium sulfate are respectively obtained, wherein the crushed environment humidity is below 5%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 76-78 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 15-20 r/min, mixing for 5-7 min, adding 14-16 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 24-26 r/min, and mixing for 20-30 min to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 2-4 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 22-24 revolutions per minute, and mixing for 10-18 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: adding 4-6 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of powdery steel slag, powdery sodium silicate and powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 12-16 rpm, and mixing for 30-48 minutes to obtain an excitant;
and 4) adding alkali-treated microcrystalline cellulose, namely adding 0.05-0.15 part by weight of alkali-treated microcrystalline cellulose with the granularity of 20-30 micrometers into an exciting agent, setting the rotating speed of a V-shaped mixer at 11-15 revolutions per minute, and mixing for 30-35 minutes.
2. The exciting agent for mine filling material according to claim 1, comprising: steel slag, sodium silicate, aluminum sulfate and ammonium sulfate;
the exciting agent for the mine filling material is prepared from the following raw materials in parts by weight: 77 parts of steel slag, 15 parts of sodium silicate, 3 parts of aluminum sulfate and 5 parts of ammonium sulfate;
the steel slag comprises electric furnace steel slag, the steel slag is obtained by naturally cooling under a drying condition, and the drying condition refers to that the environmental humidity is 5%;
the sodium silicate comprises solid sodium silicate which is prepared by dry-method casting molding;
the aluminum sulfate comprises anhydrous aluminum sulfate;
the ammonium sulfate includes anhydrous ammonium sulfate.
3. The exciting agent for mine filling material according to claim 1, wherein said steel slag contains the following substances by mass: 4-6% of metallic iron, 4-5% of magnesium oxide and 1.1-2.3% of manganese oxide.
4. The excitation agent for the mine filling material as recited in claim 1, wherein the excitation agent further comprises a high molecular water-absorbent resin, and the high molecular water-absorbent resin is added in an amount of 0.1 to 0.3 parts by weight, and has an effect of preventing the excitation performance from being reduced by water vapor existing in the storage environment of the excitation agent.
5. The exciting agent for the mine filling material according to claim 1, wherein the exciting agent further comprises calcium oxide, and the calcium oxide is added in an amount of 1-2 parts by weight, and has an effect of preventing the exciting performance from being reduced by carbon dioxide existing in a storage environment of the exciting agent.
6. The preparation method of the exciting agent for the mine filling material according to claim 1, characterized by comprising the following steps:
step 1) crushing materials: respectively putting the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate into a crusher, so that the steel slag, the sodium silicate, the aluminum sulfate and the ammonium sulfate are respectively crushed into powder with the particle sizes of 20-30 micrometers, 40-60 micrometers, 10-20 micrometers and 100-120 micrometers, and the powdered steel slag, the powdered sodium silicate, the powdered aluminum sulfate and the powdered ammonium sulfate are respectively obtained, wherein the crushed environment humidity is below 5%;
step 2) mixing powdery steel slag and powdery sodium silicate: taking 76-78 parts by weight of the powdery steel slag obtained in the step 1), conveying the powdery steel slag into a V-shaped mixer, setting the rotating speed of the V-shaped mixer at 15-20 r/min, mixing for 5-7 min, adding 14-16 parts by weight of the powdery sodium silicate obtained in the step 1), increasing the rotating speed of the V-shaped mixer to 24-26 r/min, and mixing for 20-30 min to obtain a mixture of the powdery steel slag and the powdery sodium silicate;
step 3), adding powdery aluminum sulfate: adding 2-4 parts by weight of the powdery aluminum sulfate obtained in the step 1) into the mixture of the powdery steel slag and the powdery sodium silicate obtained in the step 2), setting the rotating speed of a V-shaped mixer at 22-24 revolutions per minute, and mixing for 10-18 minutes to obtain a mixture of the powdery steel slag, the powdery sodium silicate and the powdery aluminum sulfate;
step 4), adding powdery ammonium sulfate: adding 4-6 parts by weight of powdery ammonium sulfate obtained in the step 1) into the mixture of powdery steel slag, powdery sodium silicate and powdery aluminum sulfate obtained in the step 3), setting the rotating speed of a V-shaped mixer at 12-16 rpm, and mixing for 30-48 minutes to obtain an excitant;
and 4) adding alkali-treated microcrystalline cellulose, namely adding 0.05-0.15 part by weight of alkali-treated microcrystalline cellulose with the granularity of 20-30 micrometers into an exciting agent, setting the rotating speed of a V-shaped mixer at 11-15 revolutions per minute, and mixing for 30-35 minutes.
7. The method according to claim 6, wherein the material container of the V-type blender is a sealed container.
8. The preparation method of claim 6, wherein during the material mixing process of the steps 2) to 4), the material container of the V-shaped blender is filled with dry nitrogen for protection, so as to prevent water and carbon dioxide from reducing the performance of the excitant.
9. The preparation method according to claim 6, further comprising a step of adding a polymeric water-absorbent resin after the step 4), wherein 0.1 to 0.3 part by weight of the polymeric water-absorbent resin is added to the activator, and the rotation speed of the V-type mixer is set to 8 to 13 rpm and the mixture is mixed for 30 to 36 minutes.
10. The preparation method of claim 6, further comprising a step of adding calcium oxide after the step 4), wherein 1-2 parts by weight of calcium oxide with a particle size of 30-60 microns is added into the activator, and the rotating speed of the V-shaped mixer is set at 18-24 rpm and the mixture is mixed for 20-25 minutes.
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