A titanium-extracting slag-based cementitious material for full tailings cementation filling in mines and its preparation method

Abstract

The present invention relates to the technical field of underground filling in metal mines, and in particular to a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines, and a preparation method thereof. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines comprises the following components in parts by weight: 300-400 parts of titanium-extracting slag, 450-500 parts of vanadium-titanium tailings powder, 100-120 parts of glauberite tailings, 10-20 parts of carbide slag, 13-15 parts of inorganic grinding aids, 4-6 parts of organic grinding aids, and 1-3 parts of silane coupling agent modifier. The rheological properties, mechanical properties, and durability of the whole tailings cementitious filling material prepared using the titanium-extracting slag-based cementitious material of the present invention can meet the requirements of mine filling. Using the titanium-extracting slag-based cementitious material in whole tailings filling greatly reduces the consumption of materials such as cement, lowers filling costs, reduces carbon emissions, and increases tailings utilization, thereby achieving low-carbon, safe, and efficient production goals.

Description

Technical Field

[0001] The present invention relates to the technical field of underground filling of metal mines, and in particular to a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines and a preparation method thereof. Background Art

[0002] After smelting Panzhihua Iron and Steel's vanadium-titanium magnetite ore in a blast furnace, it produces granular or lumpy blast furnace slag. This slag is then treated using the chloride process to extract titanium resources, yielding a new type of industrial titanium-extracting slag. Panzhihua Iron and Steel produces over 2 million tons of high-titanium blast furnace slag as a byproduct annually, with approximately 50 million tons currently stockpiled. Using this titanium-extracting slag in the mine's full tailings cementation backfill would not only reduce backfill costs but also minimize the surface area occupied by the slag, significantly impacting regional environmental protection.

[0003] Currently, one of the main methods for disposing of the above-mentioned tailings is to mix these tailings with a certain proportion of cement or cement powder to prepare a cementitious filling material for filling mine goafs. In traditional cementitious filling materials, the aggregate of the full-tailings cementitious filling body is the full-size tailings from the concentrator without desliming, and the cementitious material is usually ordinary Portland cement. The two are evenly mixed with water in a certain proportion to form a filling slurry, which is then transported to the underground goaf via pipelines. Although my country's total cement production is relatively high, the cement manufacturing process is a high-carbon emission process. The use of cement not only increases the cost of tailings treatment, but also increases carbon emissions.

[0004] Therefore, there is an urgent need to provide a technical solution to the above-mentioned deficiencies in the existing technology. Summary of the Invention

[0005] To address the above technical issues, the present invention provides a titanium-extracting slag-based cementitious material for use in full-tailings cementitious backfilling in mines, and its preparation method. The titanium-extracting slag-based cementitious material provided by the present invention can completely replace ordinary Portland cement in full-tailings backfilling and achieve superior consolidation performance compared to cement, thereby reducing cement consumption, lowering costs, and reducing carbon emissions.

[0006] To achieve the above-mentioned purpose, the present invention provides a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines, which adopts the following technical solutions:

[0007] A titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines comprises the following components in parts by mass: 300-400 parts of titanium-extracting slag, 450-500 parts of vanadium-titanium tailings powder, 100-120 parts of glauberite tailings, 10-20 parts of carbide slag, 13-15 parts of inorganic grinding aids, 4-6 parts of organic grinding aids, and 1-3 parts of a silane coupling agent modifier.

[0008] Preferably, the mineral composition of the titanium-extracting slag includes β-C2S, γ-C2S, calcite, calcium titanate, and a large amount of glass. The glass is derived from the decomposition and melting of minerals at high temperatures, and forms an amorphous substance due to the inability of atoms to achieve the degree of order required for crystals. The titanium-extracting slag includes the following components by weight: 35-40% CaO, 15-20% SiO2, 10-15% Al2O3, 5-8% Fe2O3, 2-3% MgO, 2-3% TiO2, 5-7% Cl, 1-2% SO3, and the remainder is other chemical components. As can be seen from the above chemical composition, the calcium oxide content in the titanium-extracting slag reaches 35-40%, and therefore, the titanium-extracting slag is a high-calcium tailings.

[0009] Preferably, the vanadium-titanium tailings powder comprises the following components in percentage by mass: 20-22% Fe2O3, 11-13% CaO, 30-33% SiO2, 14-16% Al2O3, 8-10% TiO2, 10-12% MgO, and 0.5-1% of other chemical components.

[0010] Preferably, the mass percentage of Na2SO4 in the glauberite tailings is 17-25%, and the mass percentage of CaSO4 is 41-46%. The glauberite tailings used in the present invention are tailings produced after glauberite ore is used to produce sodium sulfate (Na2SO4), which contains a large amount of CaSO4 associated with Na2SO4.

[0011] Preferably, the main components of the carbide slag are Ca(OH)2 and CaCO3, wherein the mass percentage of Ca(OH)2 is greater than or equal to 80%, and the specific surface area is 423m 2 / kg.

[0012] Preferably, the inorganic grinding aid is ultrafine magnesium oxide, and the specific surface area of ​​the ultrafine magnesium oxide is 610-630m 2 / kg; the organic grinding aid is triethanolamine; the silane coupling agent modifier is a silane coupling agent alcohol solution, and the silane coupling agent is γ-aminopropyltriethoxysilane. The organic grinding aid is industrial-grade triethanolamine. (It can improve the early strength of the grouting material)

[0013] To achieve the above-mentioned purpose, the present invention provides a method for preparing a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines, which adopts the following technical scheme:

[0014] A method for preparing a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines comprises the following steps:

[0015] (1) spraying a silane coupling agent modifier evenly on the surface of an inorganic grinding aid, stirring and then drying to obtain a silane coupling agent-modified inorganic grinding aid; the mass ratio of the silane coupling agent modifier to the inorganic grinding aid is 1:60-70, the stirring rate is 1300-1400 r / min, the stirring time is 20-30 min, the drying temperature is 90-100° C., and the drying time is 4-5 h;

[0016] (2) Dry the titanium slag at 100-110°C, evenly spray the organic grinding aid on the surface of the titanium slag, and place it in a test mill for grinding for 15-20 minutes. Add the inorganic grinding aid modified by silane coupling agent and continue grinding for 20-30 minutes to obtain modified titanium slag powder;

[0017] (3) Grinding the vanadium-titanium tailings powder to obtain vanadium-titanium tailings fine powder; mixing the glauberite tailings with carbide slag and grinding them to obtain a mixture of carbide slag and glauberite tailings;

[0018] (4) The modified titanium-extracting slag powder, vanadium-titanium tailings powder, carbide slag and glauberite tailings mixture are mixed evenly to obtain a titanium-extracting slag-based cementitious material with full tailings cementation and filling.

[0019] By modifying the surface of magnesium oxide with a silane coupling modifier, an organic molecular layer can be generated on the surface of the inorganic powder, changing the inorganic powder from hydrophilic to organophilic, making the filler dispersed evenly, and improving the water repellency of the material.

[0020] Since the titanium-extracting slag is the main volcanic ash active substance in the filling material of the present invention, the fine volcanic ash activity of the titanium-extracting slag directly determines the performance of the filling cementitious material, so the titanium-extracting slag is ground and activated separately from other tailings (vanadium-titanium tailings, carbide slag and glauberite tailings).

[0021] At 100-110°C, the moisture in the titanium extraction slag is dried after 5 hours of drying. If the drying time is too short, the titanium extraction slag will contain residual moisture.

[0022] Inorganic grinding aids (ultrafine magnesium oxide) can penetrate the cracks created during the grinding process of titanium slag, improving grinding efficiency. They can also hydrate in the grouting slurry to form magnesium hydroxide, which expands and offsets the volume shrinkage of the grouting cementitious material caused by hydration, temperature changes, and water loss. They also offer excellent temperature stability and are inexpensive.

[0023] Preferably, in step (2), the test mill is a 5kg cement test mill with a model of Ø500×500, a ball-to-material ratio of 3:1, a rotation speed of the test mill of 45-55 r / min, and a specific surface area of ​​the modified titanium slag powder of 485 m 2 / kg,d 50 =18~20μm.

[0024] Preferably, in step (3), the vanadium-titanium tailings powder is ground using a 5kg cement test mill with a ball-to-material ratio of 3:1 and a grinding time of 10 to 15 minutes; the specific surface areas of the vanadium-titanium tailings powder before and after grinding are 420 to 450 m 2 / kg and 650~700m 2 / kg, its d before and after grinding 50 They are 16-18 μm and 7-8 μm respectively;

[0025] The mixed grinding of glauberite tailings and carbide slag adopts 5kg cement test mill, the ball-to-material ratio is 3:1, the grinding time is 10-20min, and the specific surface area of ​​the mixed material of carbide slag and glauberite tailings is 350-400m 2 / kg,d 50 =25~28μm.

[0026] To achieve the above-mentioned purpose, the present invention provides a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines, which adopts the following technical solutions:

[0027] The invention discloses an application of a titanium-extracting slag-based cementitious material for cementing and filling the whole tailings of a mine. The titanium-extracting slag-based cementitious material is used for cementing and filling the whole tailings of a mine. The whole tailings cementitious filling material for a mine comprises the following components in parts by mass: 180 to 200 parts of the titanium-extracting slag-based cementitious material, 630 to 660 parts of water, and 1200 to 1300 parts of tailings.

[0028] Beneficial effects

[0029] The titanium-extracting slag-based cementitious material provided by the present invention mainly uses solid waste (titanium-extracting slag, vanadium-titanium tailings powder and calcium glauberite tailings) as raw materials, supplemented by inorganic grinding aids, organic grinding aids, carbide slag and silane coupling agent modifiers to prepare titanium-extracting slag-based cementitious materials. Compared with the traditional full-tailings cementitious filling body that uses cement materials as a binder, the rheological properties, mechanical properties and durability of the full-tailings cementitious filling material prepared using the titanium-extracting slag-based cementitious material of the present invention can meet the requirements of mine filling. The titanium-extracting slag-based cementitious material is used to completely replace ordinary silicate cement in full tailings filling and can achieve an effect that is better than cement consolidation, greatly reducing the consumption of materials such as cement, reducing filling costs, reducing carbon emissions, and increasing tailings utilization, which can achieve low-carbon, safe and efficient production goals. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The drawings and descriptions that constitute part of this application are intended to provide a further understanding of this application. The exemplary embodiments and descriptions of this application are intended to explain this application and do not constitute an improper limitation on this application. Among them:

[0031] Figure 1XRD spectrum for phase analysis of titanium slag;

[0032] Figure 2 This is a curve chart of grinding time and specific surface area of ​​titanium slag. DETAILED DESCRIPTION

[0033] The present application will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments. Each example is provided by way of explanation of the present application and does not limit the present application. In fact, it will be clear to those skilled in the art that modifications and variations can be made in the present application without departing from the scope or spirit of the present application. For example, a feature shown or described as part of one embodiment can be used in another embodiment to produce yet another embodiment. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention should fall within the scope of protection of the embodiments of the present invention.

[0034] Example 1

[0035] A method for preparing a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines comprises the following steps:

[0036] (1) Weigh 15 parts of ultrafine magnesium oxide and 3 parts of silane coupling agent modifier, respectively, spray the silane coupling agent alcohol solution evenly on the surface of the ultrafine magnesium oxide, stir at a rate of 1400 r / min for 30 minutes, and then dry for 4 hours to obtain silane coupling agent modified magnesium oxide. The mass ratio of silane coupling agent modifier to ultrafine magnesium oxide is 1:60. The preparation process of the silane coupling agent alcohol solution includes the following steps: ① Prepare an alcohol solvent, mix water and alcohol (isopropyl alcohol or ethanol) in a mass ratio of 1:8, and stir evenly; ② Prepare a silane coupling agent alcohol solution, mix silane and alcohol solvent in a mass ratio of 1:5, and stir evenly.

[0037] (2) Take 400 parts of titanium slag and place them in an oven at a drying temperature of 110°C for 4 hours. Take 6 parts of triethanolamine and spray them evenly on the surface of the titanium slag and place them in a test mill for 15 minutes. Then add the modified magnesium oxide into the test mill and continue to grind for 30 minutes to obtain modified titanium slag powder. The test mill is a 5kg cement test mill with a model of Ø500×500, a ball-to-material ratio of 3:1, a test mill speed of 50±5r / min, and a specific surface area of ​​the modified titanium slag powder of 485m 2 / kg,d 50 =18~20μm.

[0038] (3) Take the specific surface area as 420~450m 2 / kg,d 50 = 450 parts of vanadium-titanium tailings powder with a particle size of 16-18 μm were ground into a specific surface area of ​​650 m2 using a 5 kg cement test mill with a ball-to-material ratio of 3:1. 2 / kg,d 50 =8μm, and vanadium titanium tailings powder was obtained. 20 parts of carbide slag and 100 parts of glauberite tailings were mixed and ground for 20 minutes using a 5kg cement test mill with a ball-to-material ratio of 3:1 to obtain a powder with a specific surface area of ​​400m 2 / kg,d 50 =25μm mixture of carbide slag and glauberite tailings.

[0039] (4) The modified titanium extraction slag powder, vanadium titanium tailings powder, carbide slag and glauberite tailings mixture are evenly mixed to obtain the titanium extraction slag-based cementitious material A1 with full tailings cementation filling.

[0040] Depend on Figure 1 It can be seen that the XRD spectrum of the titanium slag is normal, and most of the phase components are glass, containing some crystalline minerals such as β-C2S, γ-C2S, calcite and calcium titanate. After proper grinding, it has high potential activity. From the XRD spectrum, it can be seen that the main mineral components in the tailings are kaolinite, feldspar, calcite, brookite (TiO2) and magnesite (magnesium carbonate). The grinding specific surface area is from 450m 2 / kg increased to 670m 2 / kg, the diffraction intensity of the characteristic peaks of kaolinite and albite in XRD was significantly weakened, indicating that mechanical activation had a significant effect on these two minerals. No obvious quartz characteristic peaks were detected in the tailings, indicating that the quartz content was low. The SiO2 component in the raw materials mainly existed in the form of feldspar and kaolinite minerals, which was conducive to their activation by mechanical force.

[0041] Figure 2 To obtain the relationship between grinding time and specific surface area of ​​titanium slag, Figure 2 It can be seen that within 15 minutes of grinding, the specific surface area of ​​titanium slag is linearly related to the grinding time, and the first peak of 303m3 is reached after 15 minutes of grinding. 2 / kg; after that, the specific surface area showed a downward trend with the increase of grinding time, and reached the second peak of 393m at 25min of grinding. 2 / kg, and then it dropped again, indicating that reverse crushing phenomenon is easy to occur when grinding without adding grinding aids, the material agglomerates, and the specific surface area is difficult to increase further.

[0042] The above experiments found that the activity of titanium-extracting slag is proportional to the specific surface area of ​​the titanium-extracting slag after grinding. The activity index of the titanium-extracting slag after grinding and activation in the present invention can reach 92.3% 28 days later. The test was carried out according to the "Test Method for Strength of Cement Mortar (ISO Method)" (GB / T 17671-2020) to determine the compressive strength of titanium-extracting slag mortar and cement comparison mortar, and the activity index of titanium-extracting slag micropowder was determined by the ratio of the compressive strengths of the two.

[0043] Example 2

[0044] A method for preparing a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines comprises the following steps:

[0045] (1) Weigh 13 parts of ultrafine magnesium oxide and 1 part of silane coupling agent modifier, spray the silane modifier alcohol solution evenly on the surface of the ultrafine magnesium oxide, stir at a speed of 1300 r / min for 20 minutes, and then dry for 5 hours to obtain silane coupling agent modified magnesium oxide. The mass ratio of silane coupling agent modifier to ultrafine magnesium oxide is 1:60.

[0046] (2) Take 300 parts of titanium slag and place them in an oven at a drying temperature of 110°C for 5 hours. Take 4 parts of triethanolamine and spray them evenly on the surface of the titanium slag. Place it in a test mill and grind it for 15 minutes. Then place the modified magnesium oxide in the test mill and continue grinding for 30 minutes to obtain modified titanium slag powder. The test mill is a 5kg cement test mill with a model of Ø500×500, a ball-to-material ratio of 3:1, a test mill speed of 50±5r / min, and a specific surface area of ​​the modified titanium slag powder of 485m 2 / kg,d 50 =18~20μm.

[0047] (3) Take the specific surface area as 420~450m 2 / kg,d 50 = 500 parts of vanadium-titanium tailings powder with a particle size of 16-18 μm were ground to a specific surface area of ​​650 m2 using a test mill with a ball-to-material ratio of 3:1. 2 / kg,d 50 =8μm, and vanadium titanium tailings powder was obtained. 10 parts of carbide slag and 120 parts of glauberite tailings were mixed and ground for 10 minutes using a test mill with a ball-to-material ratio of 3:1 to obtain a specific surface area of ​​350m 2 / kg,d 50 =28μm carbide slag and glauberite tailings mixture.

[0048] (4) The modified titanium extraction slag powder, vanadium titanium tailings powder, carbide slag and glauberite tailings mixture are evenly mixed to obtain the titanium extraction slag-based cementitious material A2 with full tailings cementation and filling.

[0049] Example 3

[0050] A method for preparing a titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines comprises the following steps:

[0051] (1) Weigh 14 parts of ultrafine magnesium oxide and 2 parts of silane coupling agent modifier. Spray the alcohol solution of silane modifier evenly on the surface of ultrafine magnesium oxide, stir at 1300 r / min for 15 minutes, and then dry for 5 hours to obtain silane coupling agent-modified magnesium oxide. The mass ratio of silane coupling agent modifier to ultrafine magnesium oxide is 1:70.

[0052] (2) Take 350 parts of titanium slag and place them in an oven at a drying temperature of 110°C for 4 hours. Take 5 parts of triethanolamine and spray them evenly on the surface of the titanium slag and place them in a test mill for 20 minutes. Then place the modified magnesium oxide in the test mill and continue to grind for 30 minutes to obtain modified titanium slag powder. The test mill is a 5kg cement test mill with a model of Ø500×500, a ball-to-material ratio of 3:1, a test mill speed of 50±5r / min, and a specific surface area of ​​the modified titanium slag powder of 485m 2 / kg,d 50 =18~20μm.

[0053] (3) Take the specific surface area as 420~450m 2 / kg,d 50 = 550 parts of vanadium-titanium tailings powder with a particle size of 16-18 μm were ground to a specific surface area of ​​700 m2 using a test mill with a ball-to-material ratio of 3:1. 2 / kg,d 50 =7μm, and vanadium titanium tailings powder was obtained. 10 parts of carbide slag and 120 parts of glauberite tailings were mixed and ground for 15 minutes using a test mill with a ball-to-material ratio of 3:1 to obtain a specific surface area of ​​380m 2 / kg,d 50 =26μm carbide slag and glauberite tailings mixture.

[0054] (4) The modified titanium extraction slag powder, vanadium titanium tailings powder, carbide slag and glauberite tailings mixture are evenly mixed to obtain the titanium extraction slag-based cementitious material A3 with full tailings cementation and filling.

[0055] Example 4

[0056] A method for preparing a full tailings cemented filling material using titanium-extracting slag-based cementitious material comprises the following steps:

[0057] (1) Prepare the materials: weigh 200 parts of titanium slag-based cementitious material (A1), 660 parts of water, and 1200 parts of tailings according to their mass.

[0058] (2) Put the above prepared materials into a concrete mixer and mix them evenly to obtain a mixture of all-tailings cemented filling materials;

[0059] (3) The above-mentioned full tailings cemented filling material mixture was filled into a mold, demolded and formed after 48 hours, and cured under standard curing conditions (20±2°C, 95±5% relative humidity) to obtain full tailings cemented filling material specimen B1.

[0060] Example 5

[0061] A method for preparing a full tailings cemented filling material using titanium-extracting slag-based cementitious material comprises the following steps:

[0062] (1) Prepare the materials. Weigh 190 parts of titanium slag-based cementitious material (A2), 630 parts of water, and 1,300 parts of tailings according to their mass.

[0063] (2) Put the above prepared materials into a concrete mixer and mix them evenly to obtain a mixture of all-tailings cemented filling materials;

[0064] (3) The above-mentioned full tailings cemented filling material mixture was filled into a mold, demolded and formed after 48 hours, and cured under standard curing conditions (20±2°C, 95±5% relative humidity) to obtain full tailings cemented filling material specimen B2.

[0065] Example 6

[0066] A method for preparing a full tailings cemented filling material using titanium-extracting slag-based cementitious material comprises the following steps:

[0067] (1) Prepare the materials. Weigh 180 parts of titanium slag-based cementitious material (A3), 640 parts of water, and 1,300 parts of tailings according to their mass.

[0068] (2) Put the above prepared materials into a concrete mixer and mix them evenly to obtain a mixture of all-tailings cemented filling materials.

[0069] (3) The above-mentioned full tailings cemented filling material mixture was filled into a mold, demolded and formed after 48 hours, and cured under standard curing conditions (20±2°C, 95±5% relative humidity) to obtain full tailings cemented filling material specimen B3.

[0070] Comparative Example 1

[0071] A method for preparing a cement-based cementitious filling material comprises the following steps:

[0072] (1) Prepare the materials by weighing 200 parts of 32.5 composite Portland cement, 660 parts of water, and 1200 parts of metal tailings according to their mass.

[0073] (2) Put the above-mentioned materials into a concrete mixer and mix them evenly to obtain cement-based bonding filling materials.

[0074] (3) The above-mentioned cement-based cementitious filling material was filled into a mold, demolded after 48 h, and cured under standard curing conditions (20 ± 2 °C, 95 ± 5% relative humidity) for 28 days to obtain the full tailings cementitious filling material specimen S1.

[0075] Comparative Example 2

[0076] A method for preparing a cement-based cementitious filling material comprises the following steps:

[0077] (1) Prepare the materials by weighing 600 parts of 42.5 ordinary Portland cement, 15 parts of water, and 1500 parts of metal tailings powder according to their mass.

[0078] (2) The prepared materials are placed in a concrete mixer and mixed evenly to obtain a cement-based cementitious filling material.

[0079] (3) The cement-based cementitious filling material was filled into a mold, demolded after 48 hours, and cured under standard curing conditions (20±2°C, 95±5% relative humidity) for 28 days to obtain a full tailings cementitious filling material specimen S2.

[0080] Characterization and analysis

[0081] 1. The mechanical properties of the filling materials of Examples 4-6 and Comparative Examples 1-6 were tested according to the cement mortar strength test method of GB / T17671-2021. The results are shown in Table 1.

[0082] Table 1 Mechanical properties test results

[0083] type 7d compressive strength / MPa 28d compressive strength / MPa Example 4 (B1) 5.21 11.45 Example 5 (B2) 4.92 11.96 Example 6 (B3) 5.13 12.11 Comparative Example 1 (S1) 3.38 6.21 Comparative Example 2 (S2) 3.14 6.10

[0084] 2. The expansion rates of the filling materials of Examples 4-6 and Comparative Examples 1-6 were tested according to the JC / T313-2009 expansion rate test method for expansive cement. The results are shown in Table 2.

[0085] Table 2 Expansion rate test results

[0086] type 7d expansion rate 28d expansion rate Example 4 (B1) 1.21% 1.71% Example 5 (B2) 1.32% 2.13% Example 6 (B3) 1.56% 1.93% Comparative Example 1 (S1) -0.29% -0.56% Comparative Example 2 (S2) -0.33% -0.52%

[0087] From the above results, it can be seen that the full tailings cementitious filling material prepared with the titanium slag-based cementitious material provided by the present invention has good mechanical properties. The 7d compressive strength can reach 5.21MPa, which is 54.1% higher than that of cement-based cementitious filling materials. The 28d strength can reach 12.115MPa, which is 95.0% higher than that of cement-based cementitious filling materials. In addition, the 7d expansion rate of the full tailings cementitious filling material prepared by the embodiment of the present invention is 1.21%~1.56%, and the 28d expansion rate does not change much compared with the 7d expansion rate, which can avoid the influence of late expansion on filling. The above results show that the full tailings cementitious filling material provided by the present invention has better expansion performance than cement without adding an expansion agent, can effectively avoid multiple grouting, and greatly saves manpower and material resources. The comprehensive experimental results of Examples 4~6 in terms of mechanical properties and expansion rate are all better than those of the comparative examples.

[0088] Throughout the present invention, terms such as "one embodiment," "some embodiments," "examples," "specific examples," or "some examples" mean that a specific feature, structure, material, or characteristic described in conjunction with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0089] The foregoing description is merely a preferred embodiment of the present application and is not intended to limit the present application. Various modifications and variations are readily apparent to those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A titanium-extracting slag-based cementitious material for cementing and filling full tailings in mines, characterized in that: The invention comprises the following components in parts by mass: 300-400 parts of titanium slag, 450-500 parts of vanadium-titanium tailings powder, 100-120 parts of calcium sulfate tailings, 10-20 parts of calcium carbide slag, 13-15 parts of inorganic grinding aids, 4-6 parts of organic grinding aids, and 1-3 parts of silane coupling agent modifier. The inorganic grinding aid is ultrafine magnesium oxide, and the specific surface area of ​​the ultrafine magnesium oxide is 610-630 m 2 / kg; The method for preparing the titanium-extracting slag-based gelled material comprises the following steps: (1) spraying a silane coupling agent modifier evenly on the surface of an inorganic grinding aid, stirring and then drying to obtain a silane coupling agent-modified inorganic grinding aid; the mass ratio of the silane coupling agent modifier to the inorganic grinding aid is 1:60-70, the stirring rate is 1300-1400 r / min, the stirring time is 20-30 min, the drying temperature is 90-100° C., and the drying time is 4-5 h; (2) Dry the titanium slag at 100-110°C, evenly spray the organic grinding aid on the surface of the titanium slag, and place it in a test mill for grinding for 15-20 minutes. Add the inorganic grinding aid modified by silane coupling agent and continue grinding for 20-30 minutes to obtain modified titanium slag powder; (3) Grinding the vanadium-titanium tailings powder to obtain vanadium-titanium tailings fine powder; mixing the glauberite tailings with carbide slag and grinding them to obtain a mixture of carbide slag and glauberite tailings; (4) The modified titanium-extracting slag powder, vanadium-titanium tailings powder, carbide slag and glauberite tailings mixture are mixed evenly to obtain a titanium-extracting slag-based cementitious material with full tailings cementation and filling.

2. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines according to claim 1, characterized in that: The mineral components of the titanium-extracting slag include β-C2S, γ-C2S, calcium aluminum feldspar, and calcium titanate; the titanium-extracting slag includes the following components in percentage by mass: 35-40% CaO, 15-20% SiO2, 10-15% Al2O3, 5-8% Fe2O3, 2-3% MgO, 2-3% TiO2, 5-7% Cl, and 1-2% SO3.

3. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines according to claim 1, characterized in that: The vanadium-titanium tailings powder includes the following components in percentage by mass: 20-22% Fe2O3, 11-13% CaO, 30-33% SiO2, 14-16% Al2O3, 8-10% TiO, and 10-12% MgO.

4. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines according to claim 1, characterized in that: In the glauberite tailings, the mass percentage of Na2SO4 is 17-25%, and the mass percentage of CaSO4 is 41-46%.

5. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines according to claim 1, characterized in that: The main components of the carbide slag are Ca(OH)2 and CaCO3, wherein the mass percentage of Ca(OH)2 is greater than or equal to 80%, and the specific surface area is 423m 2 / kg.

6. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines according to claim 1, characterized in that: The organic grinding aid is triethanolamine; the silane coupling agent modifier is a silane coupling agent alcohol solution; and the silane coupling agent is gamma-aminopropyltriethoxysilane.

7. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines according to claim 1, characterized in that: In step (2), the test mill is a 5kg cement test mill with a model of Ø500×500, a ball-to-material ratio of 3:1, a rotation speed of 45-55 r / min, and a specific surface area of ​​the modified titanium slag powder of 485 m 2 / kg,d 50 =18~20μm.

8. The titanium-extracting slag-based cementitious material for cementing and filling whole tailings in mines according to claim 1, characterized in that: In step (3), the vanadium titanium tailings powder is ground using a 5kg cement test mill with a ball-to-material ratio of 3:1 and a grinding time of 10 to 15 minutes; the specific surface areas of the vanadium titanium tailings powder before and after grinding are 420 to 450 m 2 / kg and 650~700m 2 / kg, its d before and after grinding 50 The mixed grinding of the glauberite tailings and carbide slag adopts a 5kg cement test mill with a ball-to-material ratio of 3:1 and a grinding time of 10 to 20 minutes. The specific surface area of ​​the mixture of the carbide slag and glauberite tailings is 350 to 400m 2 / kg,d 50 =25~28μm.

9. The use of the titanium-extracting slag-based cementitious material for cementing and filling the whole tailings of a mine as described in any one of claims 1 to 6, wherein the titanium-extracting slag-based cementitious material is used for cementing and filling the whole tailings of a mine, and the whole tailings cementing and filling material for a mine comprises the following components in parts by mass: 180 to 200 parts of titanium-extracting slag-based cementitious material, 630 to 660 parts of water, and 1200 to 1300 parts of tailings.

Images