CN114455866B - CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and preparation method thereof - Google Patents
CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and preparation method thereof Download PDFInfo
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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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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- 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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/02—Phosphate cements
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The invention relates to CaO-MgO-SiO for mine filling 2 ‑H 2 O-shaped cementing material and a preparation method thereof. The technical scheme is as follows: mixing 60-80 wt% of the pretreated iron tailing micro powder and 20-40 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture; adding silicon micropowder accounting for 5-10 wt% of the first mixture, 1-5 wt% of sodium hydroxide and 100-200 wt% of water into the first mixture, and mixing to obtain a second mixture; adjusting the pH value of the second mixture to 11-13, and magnetically stirring to obtain slurry; solid-liquid separation of the slurry, freezing and drying the separated solid, keeping the temperature at 800-1000 ℃ for 1-3 h, cooling along with the furnace, grinding to obtain CaO-MgO-SiO for mine filling 2 ‑H 2 And (3) O cementing material. The invention has the characteristics of high resource utilization rate, low production cost and simple process, the strength of the prepared product meets the specification of nonferrous metal mining design specification (GB 50771-2012), the bleeding rate of the filling slurry is low, and the additional value is high.
Description
Technical Field
The invention belongs to the technical field of cementing materials for mine filling. In particular to CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and a preparation method thereof.
Background
The iron tailings are solid or powder waste which is discharged after the ore dressing and cannot be temporarily utilized, are main components of industrial solid waste, and mainly comprise oxides of iron, silicon, magnesium, calcium and aluminum; the phosphate tailings are low-grade phosphate ores and are subjected to beneficiation and enrichment P 2 O 5 Solid waste is generated. At present, the stockpiling amount of the iron tailings and the phosphorus tailings is gradually changedThe land occupation is large, serious environmental problems such as vegetation damage, water source pollution and the like are brought, and even the risk of dam break exists. Therefore, the resource utilization of iron tailings and phosphorus tailings has attracted attention of those skilled in the art.
At present, the resource utilization of iron tailings mainly comprises the following aspects: (1) recleaning iron tailings; (2) filling the iron tailings underground; (3) use as a building material; (4) the fertilizer is used as a soil conditioner and a trace element fertilizer; and (5) reclaiming the vegetation by using the iron tailings and the like. The resource utilization of the phosphate tailings mainly comprises the following aspects: (1) recleaning phosphorus tailings; (2) filling the underground of the phospho-tailing mine; (3) use as a building material; (4) the fertilizer is used as a soil conditioner and a trace element fertilizer; and (5) reclaiming vegetation and the like by utilizing phosphorus tailings.
The two tailings are subjected to resource utilization, so that mine enterprises adopt a mine underground filling mode to greatly consume the tailings due to high production cost and low tailing resource utilization rate. The mine underground filling material comprises a cementing agent and filling aggregate, wherein the cementing agent is generally cement; the filling cost of the cement accounts for 70% of the total filling cost, so that the mine filling cost is too high, and the economic benefit of an enterprise is seriously influenced; the filling aggregate is generally classified tailings or full tailings, the average particle size of the full tailings is 52 mu m, and the particle size of the classified tailings is generally coarse fraction tailings larger than 75 mu m, so that a large amount of screened micro powder is accumulated and is difficult to use; when the whole tailing is filled, a large amount of cement needs to be consumed to ensure certain filling strength due to too much micro powder, poor grain size distribution and increase of cement cost, so that the reduction process of tailings is greatly limited, and a large amount of micro powder is accumulated.
Therefore, in order to solve the problem of tailing micro powder accumulation and reduce the filling cost of a mine, technical personnel carry out deep research and technical development:
for example, in the patent technology of 'an iron tailing cemented filling method' (CN 102562148 a), iron tailings, a consolidation agent and water are mixed and uniformly stirred to form slurry, namely, the mine cemented filling material, although the strength meets the specification in the nonferrous metal mining design specification (GB 50771-2012), the filling cost is not significantly reduced, the bleeding rate is high, the tailings serve as filling aggregates and are not converted into high value-added materials, so that the recycling utilization rate of tailing sand is not high.
Also, as a patent technology of 'a paste filling system and method for grading and partitioning of full tailings of metal ores' (CN 105317458A), the full tailings are graded into coarse-grade tailings and fine-grade tailings, and the coarse-grade tailings are filled to a stope with a large goaf and high strength requirement in a non-cemented manner; and (5) performing cemented filling on the fine-fraction tailings to a stope with a small goaf and low strength requirement. Although the utilization of fine-grained tailings is improved, a small amount of cement is still needed to provide early strength, and meanwhile, the fine-grained tailings only fill small goafs, so that the application of the fine-grained tailings to all goafs is limited; namely, although the filling cost is reduced, the production process is complex, and the consumption of fine-grade tailings cannot be greatly increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide CaO-MgO-SiO for mine filling, which has the advantages of high resource utilization rate of iron tailing micro powder and phosphorus tailing micro powder, low production cost and simple process 2 -H 2 Preparation method of O-type cementing material, and CaO-MgO-SiO prepared by method and used for mine filling 2 -H 2 The strength of the O-shaped cementing material meets the specification of nonferrous metal mining design specification (GB 50771-2012), the bleeding rate of the filling slurry is low, the mine filling cost can be effectively reduced, and the additional value is high.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
firstly, ball-milling the iron tailing micro powder and the phosphorus tailing micro powder for 2-3 min by using a ball mill respectively, then heating to 800-1000 ℃ at the speed of 0.5-5 ℃/min respectively, and preserving heat for 90-120 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
Mixing 60-80 wt% of the pretreated iron tailing micro powder and 20-40 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
And step two, adding 5-10 wt% of silica powder, 1-5 wt% of sodium hydroxide and 100-200 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11-13, and magnetically stirring for 4-10 hours at 40-100 ℃ to obtain the slurry.
Thirdly, solid-liquid separation is carried out on the slurry, the separated solid is frozen for 1 to 2 hours at the temperature of between 60 ℃ below zero and 30 ℃ below zero, and then the solid is dried for 12 to 24 hours under the conditions of room temperature and vacuum degree of 2 to 5Pa, thus obtaining the CaO-MgO-SiO for filling the mine 2 -H 2 And O, a cementing material precursor.
Step four, filling the mine with CaO-MgO-SiO 2 -H 2 Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 800-1000 ℃ at the speed of 0.5-5 ℃/min, preserving the heat for 1-3 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine 2 -H 2 And (3) O cementing material.
The average particle size of the iron tailing micro powder is less than or equal to 75 mu m; siO of iron tailing micro powder 2 The content is 30-40 wt%.
The average particle size of the phosphate tailing micro powder is less than or equal to 75 mu m; in the phosphate tailing micro powder: caO content is 30-40 wt%, mgO content is 20-30 wt%.
The average particle size of the silicon micro powder is less than or equal to 1 mu m; siO of silicon micropowder 2 The content is more than or equal to 98wt percent.
The rotating speed of the magnetic stirring is 400-500 r/min.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
the invention takes the iron tailing micro powder and the phosphorus tailing micro powder as main raw materials to prepare CaO-MgO-SiO for filling mines 2 -H 2 The O-shaped cementing material has high resource utilization rate. In the preparation process, the iron tailing micro powder and the phosphorus tailing micro powder are respectively ground and calcined and are uniformly mixed to obtain a first mixture; mixing and stirring the first mixture, the silicon micropowder, the sodium hydroxide and the water to obtain a second mixture; adjusting the pH value of the second mixture, and magnetically stirring to obtain slurry; filtering, freezing, drying, calcining at 800-1000 deg.C, grinding to obtain CaO-MgO-SiO powder for filling mine 2 -H 2 The O-type cementing material has simple process and low preparation cost, and is suitable for batch productionAnd (4) producing.
CaO-MgO-SiO for mine filling prepared by the invention 2 -H 2 The O-type cementing material has high resource utilization rate, simple process and low preparation cost, the compressive strength of the O-type cementing material meets the regulations of nonferrous metal mining design Specifications (GB 50771-2012) and the bleeding rate of filling slurry is low, and the reasons are as follows:
on one hand, the invention adopts the iron tailing micro powder and the phosphorus tailing micro powder as raw materials, the iron tailing micro powder and the phosphorus tailing micro powder are subjected to mechanical and high-temperature heat treatment, caO and MgO with high activity exist in the phosphorus tailing micro powder after mechanical grinding and high-temperature treatment, and the CaO and the MgO with high activity exist in the phosphorus tailing micro powder after mechanical grinding and high-temperature treatment, and the high-activity SiO in the iron tailing micro powder and the silicon micro powder 2 And the calcium silicate hydrate and the magnesium silicate hydrate gel form a crystalline state with a compact network structure, and substances without gelling activity are cemented together, so that the compressive strength is improved.
On the other hand, the iron tailing micro powder is ground and calcined to lead SiO to be treated 2 The Si-O chemical bond is broken and recombined to improve SiO 2 The reactivity of (a); the addition of silicon micropowder can improve the high-activity SiO in the solution 2 Adding sodium hydroxide as an alkali activator to improve the alkalinity of the solution; OH in alkaline environment - Can lead SiO in the iron tailing micro powder 2 Dissolving; the hydration temperature of 40-100 ℃ can accelerate the SiO 2 With Ca in solution 2+ And Mg 2+ Improving CaO-SiO reaction 2 -H 2 O and MgO-SiO 2 -H 2 The reaction rate of the O system is high, so that hydrated calcium silicate and hydrated magnesium silicate gel are generated; simultaneously, the hydration temperature is increased to enable the gelled substance to have a higher crystalline state, the generated gel material is dried and then calcined at the temperature of 800-1000 ℃, the crystalline state of hydrated calcium silicate and hydrated magnesium silicate is removed of structural water to generate calcium silicate and magnesium silicate phases, the calcium silicate and the magnesium silicate phases are ground again until the granularity is less than or equal to 75 mu m, and the CaO-MgO-SiO for filling mines is prepared 2 -H 2 And O, cementing materials. The grinding can increase the specific surface area and the reaction activity of the cementing material, and is beneficial to forming high-density C-H-S (hydrated calcium silicate) after the calcium silicate and the magnesium silicate are rehydratedAnd M-H-S (hydrated magnesium silicate), and water is taken as a reactant and is greatly involved in the product, so that the bleeding rate of the slurry is greatly reduced. CaO-MgO-SiO for mine filling 2 -H 2 The O-gelled material can regenerate hydrated calcium silicate and hydrated magnesium silicate after being rehydrated, and the regenerated hydrated calcium silicate and hydrated magnesium silicate still present compact network structures. Can improve the compressive strength and has safe and reliable quality.
CaO-MgO-SiO for mine filling prepared according to the invention 2 -H 2 Preparing a material with the mass ratio of the O cementing material to the coarse fraction tailings to the water of 1: 2.5-8: 0.87-6.67, preparing a sample according to the building mortar basic performance test method standard (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring: the compressive strength is 6.77-15.04 MPa; the bleeding rate of the sample is 2.5-4.2%.
Therefore, the invention has the characteristics of high resource utilization rate of the iron tailing micro powder and the phosphorus tailing micro powder, low production cost and simple process, and the prepared CaO-MgO-SiO for mine filling 2 -H 2 The strength of the O-type cementing material meets the specification of non-ferrous metal mining design Specifications (GB 50771-2012), the bleeding rate of the filling slurry is low, the mine filling cost can be effectively reduced, and the additional value is high.
Detailed Description
The invention is further described with reference to specific embodiments, without limiting its scope.
In this embodiment:
the average particle size of the iron tailing micro powder is less than or equal to 75 mu m; siO of iron tailing micro powder 2 The content is 30-40 wt%.
The average particle size of the phosphate tailing micro powder is less than or equal to 75 mu m; in the phosphate tailing micro powder: 30 to 40 weight percent of CaO and 20 to 30 weight percent of MgO.
The average particle size of the silicon micro powder is less than or equal to 1 mu m; siO of fine silica powder 2 The content is more than or equal to 98wt percent.
The detailed description is omitted in the embodiments.
Example 1
CaO-MgO-SiO for mine filling 2 -H 2 O-type cementing material and preparation method thereofThe method is carried out. The preparation method of the embodiment comprises the following steps:
firstly, ball-milling the iron tailing micro powder and the phosphorus tailing micro powder for 2-2.5 min by using a ball mill respectively, then heating to 800-850 ℃ at the speed of 0.5-2 ℃/min respectively, and keeping the temperature for 90-100 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
Mixing 60-65 wt% of the pretreated iron tailing micro powder and 35-40 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
And step two, adding silicon micropowder accounting for 5-6.25 wt% of the first mixture, 1-2 wt% of sodium hydroxide and 100-125 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11-11.5, and magnetically stirring for 4-5.5 hours at 40-55 ℃ to obtain slurry.
Thirdly, solid-liquid separation is carried out on the slurry, the separated solid is frozen for 1 to 1.25 hours at the temperature of between 60 ℃ below zero and 50 ℃ below zero, and then the solid is dried for 12 to 15 hours under the conditions of room temperature and vacuum degree of 2 to 3Pa, thus obtaining the CaO-MgO-SiO for filling the mine 2 -H 2 And O, a cementing material precursor.
Step four, filling the mine with CaO-MgO-SiO 2 -H 2 Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 800-850 ℃ at the speed of 0.5-2 ℃/min, preserving the heat for 1-1.5 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine 2 -H 2 And (3) O cementing material.
The rotating speed of the magnetic stirring is 400-430 r/min.
CaO-MgO-SiO for mine filling produced according to this example 2 -H 2 Preparing materials of an O cementing material, coarse fraction tailings and water according to the mass ratio of 1: 0.125-0.200: 2.5-6.7, preparing samples according to the standard of basic performance test method standards of building mortar (JGJ/T70-2009), curing the prepared samples for 28 days, and measuring: the compressive strength is 6.77-11.70 MPa; the bleeding rate of the sample is 2.50-3.52%.
Example 2
CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, ball milling the iron tailing micro powder and the phosphorus tailing micro powder for 2-2.5 min by using a ball mill respectively, then heating to 850-900 ℃ at the speed of 2-3 ℃/min respectively, and preserving the heat for 100-110 min to obtain the pretreated iron tailing micro powder and the pretreated phosphorus tailing micro powder respectively.
Mixing 65-70 wt% of the pretreated iron tailing micro powder and 30-35 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
And step two, adding silicon micropowder accounting for 6.25 to 7.50 weight percent of the first mixture, 2 to 3 weight percent of sodium hydroxide and 125 to 150 weight percent of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11.5 to 12, and magnetically stirring for 5.5 to 7 hours at the temperature of 55 to 70 ℃ to obtain slurry.
Thirdly, solid-liquid separation is carried out on the slurry, the separated solid is frozen for 1.25 to 1.5 hours at the temperature of between 50 ℃ below zero and 40 ℃ below zero, and then the solid is dried for 15 to 18 hours under the conditions of room temperature and vacuum degree of 3 to 4Pa, thus obtaining the CaO-MgO-SiO for filling the mine 2 -H 2 O a cementitious material precursor.
Step four, filling the mine with CaO-MgO-SiO 2 -H 2 Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 850-900 ℃ at the speed of 2-3 ℃/min, preserving the heat for 1.5-2 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine 2 -H 2 And O, cementing materials.
The rotating speed of the magnetic stirring is 430-450 r/min.
CaO-MgO-SiO for mine filling produced in this example 2 -H 2 Preparing materials of an O cementing material, coarse fraction tailings and water according to the mass ratio of 1: 3.85-5: 1.54-2.5, preparing a sample according to the standard of basic performance test method of building mortar (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring: the compressive strength is 7.91-12.95 MPa; the bleeding rate of the sample is 2.70-3.79%.
Example 3
A kind ofCaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, ball milling the iron tailing micro powder and the phosphorus tailing micro powder for 2.5-3 min by using a ball mill respectively, then heating to 900-950 ℃ at the speed of 3-4 ℃/min respectively, and preserving the heat for 110-115 min to obtain the pretreated iron tailing micro powder and the pretreated phosphorus tailing micro powder respectively.
And mixing 70-75 wt% of the pretreated iron tailing micro powder and 25-30 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
And step two, adding silicon micropowder accounting for 7.50-8.75 wt% of the first mixture, 3-4 wt% of sodium hydroxide and 150-175 wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 12-12.5, and magnetically stirring for 7-8.5 hours at 70-85 ℃ to obtain slurry.
Thirdly, solid-liquid separation is carried out on the slurry, the separated solid is frozen for 1.5 to 1.75 hours at the temperature of between 40 ℃ below zero and 35 ℃ below zero, and then the solid is dried for 18 to 21 hours under the conditions of room temperature and vacuum degree of 4 to 5Pa, thus obtaining the CaO-MgO-SiO for filling the mine 2 -H 2 And O, a cementing material precursor.
Fourthly, filling the mine with CaO-MgO-SiO 2 -H 2 Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 900-950 ℃ at the speed of 3-4 ℃/min, preserving the heat for 2-2.5 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine 2 -H 2 And (3) O cementing material.
The rotating speed of the magnetic stirring is 450-480 r/min.
CaO-MgO-SiO for mine filling produced in this example 2 -H 2 Preparing materials of an O cementing material, coarse fraction tailings and water according to the mass ratio of 1: 3.03-3.85: 1.11-1.54, preparing samples according to the standard of basic performance test method standard of building mortar (JGJ/T70-2009), curing the prepared samples for 28 days, and measuring: the compressive strength is 9.12-14.01 MPa; the bleeding rate of the sample is 3.05-4.01%.
Example 4
CaO-MgO-SiO for mine filling 2 -H 2 O-shaped cementing material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
firstly, ball-milling the iron tailing micro powder and the phosphorus tailing micro powder for 2.5-3 min by using a ball mill respectively, then heating to 950-1000 ℃ at the speed of 4-5 ℃/min respectively, and preserving heat for 115-120 min to obtain pretreated iron tailing micro powder and pretreated phosphorus tailing micro powder respectively.
Mixing 75-80 wt% of the pretreated iron tailing micro powder and 20-25 wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture.
And step two, adding silicon micropowder accounting for 8.75-10 wt% of the first mixture, sodium hydroxide accounting for 4-5 wt% of the first mixture and water accounting for 175-200 wt% of the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 12.5-13, and magnetically stirring for 8.5-10 hours at 85-100 ℃ to obtain slurry.
Thirdly, solid-liquid separation is carried out on the slurry, the separated solid is frozen for 1.75 to 2 hours at the temperature of minus 35 to minus 30 ℃, and then the solid is dried for 21 to 24 hours under the conditions of room temperature and vacuum degree of 4 to 5Pa, thus obtaining the CaO-MgO-SiO for filling the mine 2 -H 2 And O, a cementing material precursor.
Step four, filling the mine with CaO-MgO-SiO 2 -H 2 Placing the precursor of the O-cementing material in a high-temperature furnace, heating to 950-1000 ℃ at the speed of 4-5 ℃/min, preserving the heat for 2.5-3 h, cooling to room temperature along with the furnace, grinding to the granularity of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for filling the mine 2 -H 2 And (3) O cementing material.
The rotating speed of the magnetic stirring is 480-500 r/min.
CaO-MgO-SiO for mine filling produced in this example 2 -H 2 Preparing the materials of the O cementing material, the coarse fraction tailings and the water according to the mass ratio of 1: 3.5-3.03: 0.87-1.11, preparing a sample according to the standard of basic performance test method of building mortar (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring: the compressive strength is 10.28-15.04 MPa; the bleeding rate of the sample is 3.23-4.20%.
Compared with the prior art, the specific implementation mode has the following positive effects:
the specific embodiment takes the iron tailing micro powder and the phosphorus tailing micro powder as main raw materials to prepare CaO-MgO-SiO for filling the mine 2 -H 2 The O cementing material has high recycling rate. In the process of the re-preparation, the iron tailing micro powder and the phosphorus tailing micro powder are respectively ground and calcined and are uniformly mixed to obtain a first mixture; mixing the first mixture, the silicon micropowder, the sodium hydroxide and the water, and stirring to obtain a second mixture; adjusting the pH value of the second mixture, and magnetically stirring to obtain slurry; filtering, freezing, drying, calcining at 800-1000 deg.C, grinding to obtain CaO-MgO-SiO powder for filling mine 2 -H 2 The O-type cementing material has simple process and low preparation cost, and is suitable for batch production.
CaO-MgO-SiO for mine filling prepared by the embodiment 2 -H 2 The O-type cementing material has high resource utilization rate, simple process and low preparation cost, the compressive strength of the O-type cementing material meets the regulations of nonferrous metal mining design Specifications (GB 50771-2012) and the bleeding rate of filling slurry is low, and the reasons are as follows:
on one hand, the specific embodiment adopts the iron tailing micro powder and the phosphorus tailing micro powder as raw materials, the iron tailing micro powder and the phosphorus tailing micro powder are subjected to mechanical and high-temperature heat treatment, caO and MgO with high activity exist in the phosphorus tailing micro powder after mechanical grinding and high-temperature treatment, and the CaO and the MgO with high activity exist in the phosphorus tailing micro powder after mechanical grinding and high-temperature treatment, and the high-activity SiO in the iron tailing micro powder and the silicon micro powder 2 And the calcium silicate hydrate and the magnesium silicate hydrate gel form a crystalline state with a compact network structure, and substances without gelling activity are bonded together, so that the compressive strength is improved.
On the other hand, the iron tailing micro powder is ground and calcined to lead SiO to be treated 2 The Si-O chemical bond of the silicon-oxygen is broken and recombined to improve SiO 2 The reactivity of (a); the addition of silicon micropowder can improve the high-activity SiO in the solution 2 Adding sodium hydroxide as an alkali activator to improve the alkalinity of the solution; OH in alkaline environment - Can lead SiO in the iron tailing micro powder 2 Dissolving; the hydration temperature of 40-100 ℃ can accelerate the SiO 2 With Ca in solution 2+ And Mg 2+ Improving CaO-SiO reaction 2 -H 2 O and MgO-SiO 2 -H 2 The reaction rate of the O system is high, so that hydrated calcium silicate and hydrated magnesium silicate gel are generated; simultaneously, the hydration temperature is increased to enable the gel substance to have higher crystalline state, the generated gel material is dried, then the material is calcined at the temperature of 800-1000 ℃, the crystalline state of hydrated calcium silicate and hydrated magnesium silicate is dehydrated to generate calcium silicate and magnesium silicate phases, the calcium silicate and the magnesium silicate phases are ground again until the granularity is less than or equal to 75 mu m, and the CaO-MgO-SiO for filling mines is prepared 2 -H 2 And (3) O cementing material. The grinding can increase the specific surface area and the reaction activity of the cementing material, is beneficial to forming high-density C-H-S (hydrated calcium silicate) and M-H-S (hydrated magnesium silicate) after the calcium silicate and the magnesium silicate are rehydrated, and water is used as a reactant to participate in the product in a large amount, thereby greatly reducing the bleeding rate of slurry. CaO-MgO-SiO for mine filling 2 -H 2 The O-gelled material can regenerate hydrated calcium silicate and hydrated magnesium silicate after being rehydrated, and the regenerated hydrated calcium silicate and hydrated magnesium silicate still present compact network structures. Can improve the compressive strength and has safe and reliable quality.
CaO-MgO-SiO prepared according to the embodiment for mine filling 2 -H 2 Preparing a material with the mass ratio of the O cementing material to the coarse fraction tailings to the water of 1: 2.5-8: 0.87-6.67, preparing a sample according to the building mortar basic performance test method standard (JGJ/T70-2009), curing the prepared sample for 28 days, and measuring: the compressive strength is 6.77-15.04 MPa; the bleeding rate of the sample is 2.5-4.2%.
Therefore, the concrete implementation has the characteristics of high resource utilization rate of the iron tailing micro powder and the phosphorus tailing micro powder, low production cost and simple process, and the prepared CaO-MgO-SiO for mine filling 2 -H 2 The strength of the O-type cementing material meets the specification of non-ferrous metal mining design Specifications (GB 50771-2012), the bleeding rate of the filling slurry is low, the mine filling cost can be effectively reduced, and the additional value is high.
Claims (6)
1. CaO-MgO-SiO for mine filling 2 -H 2 The preparation method of the O-shaped cementing material is characterized by comprising the following steps:
firstly, ball-milling iron tailing micropowder and phosphate tailing micropowder respectively for 2 to 3min by using a ball mill, heating to 800 to 1000 ℃ at the speed of 0.5 to 5 ℃/min, and keeping the temperature for 90 to 120min to obtain pretreated iron tailing micropowder and pretreated phosphate tailing micropowder respectively;
mixing 60 to 80wt% of the pretreated iron tailing micro powder and 20 to 40wt% of the pretreated phosphorus tailing micro powder to obtain a first mixture;
adding silicon micropowder accounting for 5 to 10wt% of the first mixture, 1 to 5wt% of sodium hydroxide and 100 to 200wt% of water into the first mixture, mixing to obtain a second mixture, adjusting the pH value of the second mixture to 11 to 13, and magnetically stirring for 4 to 10h at the temperature of 40 to 100 ℃ to obtain slurry;
and thirdly, carrying out solid-liquid separation on the slurry, freezing the separated solid for 1 to 2h under the conditions of-60 to-30 ℃, and then drying for 12 to 24h under the conditions of room temperature and vacuum degree of 2 to 5Pa to obtain CaO-MgO-SiO for filling the mine 2 -H 2 O a cementitious material precursor;
step four, filling the mine with CaO-MgO-SiO 2 -H 2 Placing the precursor of the O-type cementing material in a high-temperature furnace, heating to 800-1000 ℃ at the speed of 0.5-5 ℃/min, preserving heat for 1-3 h, cooling to room temperature along with the furnace, grinding to the particle size of less than or equal to 75 mu m, and preparing the CaO-MgO-SiO for mine filling 2 -H 2 And O, cementing materials.
2. The mine filling CaO-MgO-SiO according to claim 1 2 -H 2 The preparation method of the O-shaped cementing material is characterized in that the average particle size of the iron tailing micro powder is less than or equal to 75 mu m; siO of iron tailing micro powder 2 The content is 30 to 40wt%.
3. The mine filling CaO-MgO-SiO according to claim 1 2 -H 2 The preparation method of the O-shaped cementing material is characterized in that the average particle size of the phosphate tailing micro powder is less than or equal to 75 mu m; phosphorus tailIn ore micropowder: the CaO content is 30 to 40wt%, and the MgO content is 20 to 30wt%.
4. The mine filling CaO-MgO-SiO according to claim 1 2 -H 2 The preparation method of the O-shaped cementing material is characterized in that the average grain size of the silicon micro powder is less than or equal to 1 mu m; siO of fine silica powder 2 The content is more than or equal to 98wt percent.
5. The mine filling CaO-MgO-SiO according to claim 1 2 -H 2 The preparation method of the O-shaped cementing material is characterized in that the rotating speed of magnetic stirring is 400 to 500r/min.
6. CaO-MgO-SiO for mine filling 2 -H 2 O cementing material, which is characterized in that the CaO-MgO-SiO for filling mine 2 -H 2 The O-cement is CaO-MgO-SiO for mine filling according to any one of claims 1~5 2 -H 2 CaO-MgO-SiO for mine filling prepared by preparation method of O cementing material 2 -H 2 And O, cementing materials.
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