Mine filling material and preparation method thereof
By mixing waste such as red mud with other materials in solid and liquid phases, high-performance mine filling materials are prepared, which solves the problems of waste treatment and resource utilization, and achieves the reduction of environmental pollution and efficient utilization of resources.
Patent Information
- Application Number
- CN202510054121.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-13
- Publication Date
- 2025-03-14
AI Technical Summary
The prior art is difficult to effectively treat and refine the use of waste such as red mud, electrolytic manganese slag and phosphogypsum slag produced in the alumina production process, resulting in environmental pollution and waste of resources.
A mine filling material preparation method is adopted to prepare a mine filling material by mixing red mud, acidic wastewater, cement, construction waste, cellulose ether, sodium silicate and modified straw and mixing materials with solid phase and liquid phase, and prepare a mine filling material with high strength and durability.
It has realized the conversion of red mud and other waste into high-performance mine filling materials, solved the problems of waste treatment and resource utilization, reduced the risk of environmental pollution, and had good mechanical properties and erosion resistance.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of waste resources, and in particular to a mine filling material and a preparation method thereof. Background Art
[0002] Red mud is a highly alkaline solid waste produced during the production of alumina. Its harmless treatment and comprehensive resource utilization are currently global problems that restrict the green and healthy development of the alumina industry. The most common method of treating red mud is to stockpile it, but this method not only occupies a large amount of land, but also pollutes the soil, water sources, and the atmosphere. The environmental pollution and safety hazards it causes cannot be ignored.
[0003] Other products that are also in storage include electrolytic manganese slag and phosphogypsum slag. During the storage process, these two types of waste materials will be soaked by rainwater and other factors, which will produce a large amount of wastewater. There is no corresponding sewage treatment plant to treat them. The wastewater will seep into the soil or be discharged into rivers, causing irreversible damage to the ecological environment.
[0004] How to dispose of the above-mentioned waste in large quantities without using additional resources has become an urgent problem that needs to be solved at the current stage. Summary of the invention
[0005] The purpose of the present invention is to overcome the defects in the prior art and provide a mine filling material and a preparation method thereof.
[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0007] The invention provides a mine filling material, comprising the following raw materials in parts by mass: 100-130 parts of red mud, 20-30 parts of acidic waste water, 10-15 parts of cement, 20-40 parts of construction waste, 2-5 parts of cellulose ether, 1-3 parts of sodium silicate, 20-25 parts of modified straw and 70-80 parts of water.
[0008] Preferably, the acidic wastewater comprises leachate from an electrolytic manganese slag reservoir and / or leachate from a phosphogypsum slag reservoir; the pH of the acidic wastewater is 2-4.
[0009] Preferably, the particle size of the construction waste is 50-120 μm.
[0010] Preferably, the method for preparing the modified straw comprises the following steps:
[0011] The modified straw is obtained by mixing the heat-treated straw with a silane coupling agent solution for modification.
[0012] Preferably, the length of the straw is 0.5 to 1 cm;
[0013] The water temperature of the heat treatment is 80-90° C. and the time is 1-2 hours.
[0014] Preferably, the mass volume ratio of the straw and the silane coupling agent solution is 1 g: 10-20 mL;
[0015] The concentration of the silane coupling agent solution is 5-10%.
[0016] Preferably, the modification time is 1 to 2 hours and the temperature is 50 to 60°C.
[0017] The present invention also provides a method for preparing the mine filling material, comprising the following steps:
[0018] (1) solid-phase mixing red mud, cement, construction waste, cellulose ether, and sodium silicate to obtain a mixture;
[0019] (2) Mixing the mixed material, acidic wastewater, modified straw and water to obtain the mine filling material.
[0020] Preferably, the mixing speed in step (1) is 100-150 rpm and the mixing time is 0.5-1 h.
[0021] Preferably, the stirring speed of the mixing in step (2) is 100-150 rpm, and the stirring time is 0.5-1 h; the frequency of the vibration stirring is 100-150 Hz, and the vibration stirring time is 5-10 min.
[0022] The present invention provides a mine filling material, comprising the following raw materials in parts by mass: 100-130 parts of red mud, 20-30 parts of acidic wastewater, 10-15 parts of cement, 20-40 parts of construction waste, 2-5 parts of cellulose ether, 1-3 parts of sodium silicate, 20-25 parts of modified straw, and 70-80 parts of water. In the present invention, red mud is used as the main material, and acidic wastewater is used for excitation to improve the strength of the filling material. The present invention uses construction waste as aggregate, which can improve the mechanical properties of the filling material while reducing costs, and fully utilizes the waste materials. The cellulose ether added in the present invention can improve the initial fluidity of the filling material, which is convenient for the material to fully fill the target space. The use of sodium silicate in the present invention can improve the anti-scouring and durability of the filling material, thereby improving the compressive strength of the material. After the straw in the present invention is heat-treated and silane-modified, the ends of the straw fibers are divergent, which increases its own specific surface area, forms a debonding and pulling-out effect, and can fully combine different types of raw materials to improve the strength of the material.
[0023] The present invention also provides a method for preparing the mine filling material, comprising the following steps: (1) solid-phase mixing red mud, cement, construction waste, cellulose ether, and sodium silicate to obtain a mixture; (2) mixing the mixture, acidic wastewater, modified straw, and water to obtain the mine filling material. The preparation method provided by the present invention is simple, suitable for large-scale preparation, and convenient for on-site use and promotion. DETAILED DESCRIPTION
[0024] The invention provides a mine filling material, comprising the following raw materials in parts by mass: 100-130 parts of red mud, 20-30 parts of acidic waste water, 10-15 parts of cement, 20-40 parts of construction waste, 2-5 parts of cellulose ether, 1-3 parts of sodium silicate, 20-25 parts of modified straw and 70-80 parts of water.
[0025] In the present invention, the mass fraction of the red mud is preferably 105 to 125 parts, more preferably 110 to 120 parts, and even more preferably 114 to 116 parts.
[0026] In the present invention, the mass fraction of the acidic wastewater is preferably 21 to 29 parts, more preferably 22 to 28 parts, and even more preferably 24 to 26 parts.
[0027] In the present invention, the mass fraction of the cement is preferably 11 to 14 parts, more preferably 12 to 13 parts, and even more preferably 12.4 to 12.6 parts.
[0028] In the present invention, the cement used is P·C 42.5 cement.
[0029] In the present invention, the mass fraction of the construction waste is preferably 25 to 35 parts, more preferably 26 to 34 parts, and even more preferably 28 to 32 parts.
[0030] In the present invention, the weight percentage of the cellulose ether is preferably 2.5 to 4.5 parts, more preferably 3 to 4 parts, and even more preferably 3.4 to 3.6 parts.
[0031] In the present invention, the mass fraction of the sodium silicate is preferably 1.5 to 2.5 parts, more preferably 1.8 to 2.2 parts, and even more preferably 1.9 to 2.1 parts.
[0032] In the present invention, the mass fraction of the modified straw is preferably 21 to 24 parts, more preferably 22 to 23 parts, and even more preferably 22.4 to 22.6 parts.
[0033] In the present invention, the mass fraction of water is preferably 72 to 78 parts, more preferably 73 to 77 parts, and even more preferably 74 to 76 parts.
[0034] In the present invention, the acidic wastewater comprises electrolytic manganese slag reservoir leachate and / or phosphogypsum slag reservoir leachate; the pH of the acidic wastewater is preferably 2-4, more preferably 2.5-3.5, and more preferably 2.8-3.2.
[0035] In the present invention, construction waste is waste from the crushing of buildings, including bricks, cement precast panels, concrete parts, etc.; the particle size of the construction waste is preferably 50-120 μm, more preferably 60-100 μm, and more preferably 70-80 μm.
[0036] In the present invention, the preparation method of the modified straw comprises the following steps:
[0037] The modified straw is obtained by mixing the heat-treated straw with a silane coupling agent solution for modification.
[0038] In the present invention, the length of the straw is preferably 0.5 to 1 cm, more preferably 0.6 to 0.9 cm, and even more preferably 0.7 to 0.8 cm.
[0039] In the present invention, the straw is immersed in hot water for heat treatment, and the water temperature of the heat treatment is preferably 80-90°C, more preferably 82-88°C, and more preferably 84-86°C; the time is preferably 1-2h, more preferably 1.2-1.8h, and more preferably 1.4-1.6h.
[0040] In the present invention, the mass volume ratio of the straw to the silane coupling agent solution is preferably 1 g: 10-20 mL, more preferably 1 g: 12-18 mL, and even more preferably 1 g: 14-16 mL.
[0041] In the present invention, the concentration of the silane coupling agent solution is preferably 5 to 10%, more preferably 6 to 9%, and even more preferably 7 to 8%.
[0042] In the present invention, the silane coupling agent is KH550 and / or KH560.
[0043] In the present invention, the modification time is preferably 1-2h, more preferably 1.2-1.8h, more preferably 1.4-1.6h; the temperature is preferably 50-60°C, more preferably 52-58°C, more preferably 54-56°C; after the modification, the modified straw is filtered and dried to obtain.
[0044] The present invention also provides a method for preparing the mine filling material, comprising the following steps:
[0045] (1) solid-phase mixing red mud, cement, construction waste, cellulose ether, and sodium silicate to obtain a mixture;
[0046] (2) Mixing the mixed material, acidic wastewater, modified straw and water to obtain the mine filling material.
[0047] In the present invention, the mixing speed in step (1) is preferably 100-150 rpm, more preferably 110-140 rpm, more preferably 120-130 rpm; the mixing time is preferably 0.5-1 h, more preferably 0.6-0.9 h, more preferably 0.7-0.8 h.
[0048] In the present invention, the stirring speed of the mixing in step (2) is preferably 100-150 rpm, more preferably 110-140 rpm, more preferably 120-130 rpm; the stirring time is preferably 0.5-1 h, more preferably 0.6-0.9 h, more preferably 0.7-0.8 h; after the stirring is completed, vibration stirring is performed, and the frequency of the vibration stirring is preferably 100-150 Hz, more preferably 110-140 Hz, more preferably 120-130 Hz; the vibration stirring time is preferably 5-10 min, more preferably 6-9 min, more preferably 7-8 min.
[0049] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0050] Example 1
[0051] 120 parts of red mud, 25 parts of acidic wastewater, 12 parts of cement, 34 parts of construction waste, 3 parts of cellulose ether, 2 parts of sodium silicate, 23 parts of modified straw, and 75 parts of water.
[0052] Among them, the acidic wastewater used was the leachate from the electrolytic manganese slag reservoir, with a pH of 2.78; the particle size of the construction waste was 80μm.
[0053] The preparation method of the modified straw is as follows: after processing the straw into small segments of 0.8 cm, soak it in 85°C hot water for 1.5 hours; then use KH550 to prepare a silane coupling agent solution with a concentration of 8%, mix the straw and the silane coupling agent solution in a ratio of 1g:15mL, and modify it at 55°C for 1.5 hours; after modification, filter and dry to obtain the modified straw.
[0054] Red mud, cement, construction waste, cellulose ether and sodium silicate were mixed and stirred at 140 rpm for 0.8 h; then acidic wastewater, modified straw and water were added and stirred at 130 rpm for 1 h, and then the frequency was controlled to be 100 Hz for vibration stirring for 10 min to obtain mine filling material.
[0055] Example 2
[0056] 109 parts of red mud, 27 parts of acidic wastewater, 11 parts of cement, 24 parts of construction waste, 3.4 parts of cellulose ether, 1.8 parts of sodium silicate, 24 parts of modified straw, and 76 parts of water.
[0057] Among them, the acidic wastewater used was the leachate from the phosphogypsum slag reservoir, with a pH of 3.2; the particle size of the construction waste was 110μm.
[0058] The preparation method of the modified straw is as follows: after processing the straw into small segments of 0.6 cm, soak it in 90°C hot water for 1 hour; then use KH560 to prepare a 5% silane coupling agent solution, mix the straw and the silane coupling agent solution in a ratio of 1g:12mL, and modify it at 60°C for 2 hours; after modification, filter and dry to obtain the modified straw.
[0059] Red mud, cement, construction waste, cellulose ether and sodium silicate were mixed and stirred at 110 rpm for 0.7 h; then acidic wastewater, modified straw and water were added and stirred at 120 rpm for 0.5 h, and then the frequency was controlled to be 110 Hz and vibrated and stirred for 8 min to obtain mine filling material.
[0060] Example 3
[0061] 125 parts of red mud, 24 parts of acidic wastewater, 14 parts of cement, 37 parts of construction waste, 4.1 parts of cellulose ether, 2.6 parts of sodium silicate, 22 parts of modified straw, and 74 parts of water.
[0062] Among them, the acidic wastewater used was the leachate from the electrolytic manganese slag reservoir and the leachate from the phosphogypsum slag reservoir, with a volume ratio of 1:1 and a pH of 2.8; the particle size of the construction waste was 60μm.
[0063] The preparation method of the modified straw is as follows: after processing the straw into small segments of 1 cm, soak it in 82°C hot water for 1.8 hours; then use KH550 to prepare a 9% silane coupling agent solution, mix the straw and the silane coupling agent solution in a ratio of 1g:15mL, and modify it at 54°C for 1.5 hours; after modification and combination, filter and dry to obtain the modified straw.
[0064] Red mud, cement, construction waste, cellulose ether and sodium silicate were mixed and stirred at 130 rpm for 0.9 h; then acidic wastewater, modified straw and water were added and stirred at 100 rpm for 1 h, and then the frequency was controlled to be 150 Hz and vibrated and stirred for 9 min to obtain mine filling material.
[0065] Example 4
[0066] 106 parts of red mud, 21 parts of acidic waste, 12 parts of cement, 36 parts of construction waste, 3.5 parts of cellulose ether, 1.1 parts of sodium silicate, 24 parts of modified straw, and 78 parts of water.
[0067] Among them, the acidic wastewater used was the leachate from the electrolytic manganese slag reservoir and the leachate from the phosphogypsum slag reservoir, with a volume ratio of 1:3 and a pH of 3.4; the particle size of the construction waste was 110μm.
[0068] The preparation method of the modified straw is as follows: after processing the straw into small segments of 0.7 cm, soak it in 84°C hot water for 2 hours; then use KH560 to prepare a 7% silane coupling agent solution, mix the straw and the silane coupling agent solution in a ratio of 1g:11mL, and modify it at 58°C for 1.5 hours; after modification, filter and dry to obtain the modified straw.
[0069] Red mud, cement, construction waste, cellulose ether and sodium silicate were mixed and stirred at 150 rpm for 1 hour; then acidic wastewater, modified straw and water were added and stirred at 150 rpm for 0.8 hours, and then the frequency was controlled to be 120 Hz and vibrated and stirred for 5 minutes to obtain mine filling material.
[0070] The mine filling materials prepared in Examples 1 to 4 were cured for 28 days and then subjected to performance tests. The strength was tested according to the "Test Method for Cement Mortar Strength" (GB / T17671-2021); the initial and final setting times were tested according to the "Test Method for Cement Standard Consistency Water Consumption, Setting Time, and Stability" (GB / T1346-2011). The results are recorded in Table 1.
[0071] Table 1 Performance test results
[0072] Compressive strength(MPa) Initial setting time (h) Final setting time (h) Example 1 4.2 5.3 13.5 Example 2 4.6 6.1 13.2 Example 3 4.1 5.7 12.8 Example 4 4.3 5.5 13.3
[0073] As can be seen from the above embodiments, the present invention provides a mine filling material, wherein red mud, cement, construction waste, cellulose ether, and sodium silicate are solid-phase mixed to obtain a mixture; and the mixture, acidic wastewater, modified straw, and water are mixed to obtain the mine filling material. The filling material provided by the present invention has a compressive strength of 4.6MPa after 28 days of curing, an initial setting time of 5.3 to 6.1h, and a final setting time of 12.8 to 13.5h, and can be used for mine filling in goaf areas, fully turning waste into treasure and achieving the purpose of recycling waste resources.
[0074] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A mine filling material, characterized in that: The invention comprises the following raw materials in parts by weight: 100-130 parts of red mud, 20-30 parts of acidic waste water, 10-15 parts of cement, 20-40 parts of construction waste, 2-5 parts of cellulose ether, 1-3 parts of sodium silicate, 20-25 parts of modified straw and 70-80 parts of water.
2. The mine filling material according to claim 1, characterized in that: The acidic wastewater comprises the leachate from the electrolytic manganese slag reservoir and / or the leachate from the phosphogypsum slag reservoir; the pH value of the acidic wastewater is 2-4.
3. The mine filling material according to claim 1 or 2, characterized in that: The particle size of the construction waste is 50 to 120 μm.
4. The mine filling material according to claim 3, characterized in that: The preparation method of the modified straw comprises the following steps: The modified straw is obtained by mixing the heat-treated straw with a silane coupling agent solution for modification.
5. The mine filling material according to claim 4, characterized in that: The length of the straw is 0.5 to 1 cm; The water temperature of the heat treatment is 80-90° C. and the time is 1-2 hours.
6. The mine filling material according to claim 5, characterized in that: The mass volume ratio of the straw and the silane coupling agent solution is 1g:10-20mL; The concentration of the silane coupling agent solution is 5-10%.
7. The mine filling material according to any one of claims 4 to 6, characterized in that: The modification time is 1 to 2 hours, and the temperature is 50 to 60°C.
8. The method for preparing the mine filling material according to any one of claims 1 to 7, characterized in that: It includes the following steps: (1) solid-phase mixing red mud, cement, construction waste, cellulose ether, and sodium silicate to obtain a mixture; (2) Mixing the mixed material, acidic wastewater, modified straw and water to obtain the mine filling material.
9. The method for preparing a mine filling material according to claim 8, characterized in that: The mixing speed in step (1) is 100-150 rpm and the mixing time is 0.5-1 h.
10. The method for preparing a mine filling material according to claim 8 or 9, characterized in that: The stirring speed of the mixing in step (2) is 100-150 rpm, and the stirring time is 0.5-1 h; the frequency of the vibration stirring is 100-150 Hz, and the vibration stirring time is 5-10 min.