Red mud-based filling cementing material as well as preparation method and application thereof
By combining red mud with acidic slag, fly ash and cement, a high-strength filling gelling material is formed, which solves the problems of insufficient strength of traditional filling materials and difficulty in treating red mud, and achieves the effect of efficient use of red mud and reducing environmental pollution.
Patent Information
- Application Number
- CN202411854726.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-17
- Publication Date
- 2025-03-25
Smart Images
Figure BDA0005191505500000061
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of mine filling materials, and in particular to a red mud-based filling gelling material and a preparation method and application thereof. Background Art
[0002] Red mud is a highly alkaline solid waste generated 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. At present, the main method of treating red mud is stockpiling, which will pollute land and water sources during the stockpiling process and also pose a high safety hazard. In order to improve the utilization rate of red mud, lime milk is used to deal with red mud under different processes. The process is relatively complicated, and the remaining alkali solution is prone to secondary pollution if it is not handled properly.
[0003] Traditional cement slurry (paste) filling materials are difficult to gel and solidify and form strength, and the filling body has poor corrosion resistance and cannot meet the requirements of filling design strength. Summary of the invention
[0004] The object of the present invention is to provide a red mud-based filling gelling material and a preparation method and application thereof, wherein the red mud-based gelling material can form high strength and improve filling quality.
[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0006] The present invention provides a red mud-based filling gelling material, comprising the following raw materials in parts by weight:
[0007] 100 parts of red mud, 10-20 parts of acidic slag, 10-15 parts of fly ash, and 10-12 parts of cement;
[0008] The acidic slag includes electrolytic manganese slag or phosphogypsum.
[0009] Preferably, the chemical composition of the red mud includes Al2O3, SiO2, CaO, Fe2O3, Na2O, TiO2 and K2O.
[0010] Preferably, the electrolytic manganese slag includes sulfate, waste acid and silicon oxide; and the phosphogypsum includes calcium sulfate dihydrate and waste acid.
[0011] Preferably, the fly ash is secondary fly ash.
[0012] Preferably, the cement is composite Portland cement.
[0013] The present invention provides a method for preparing the red mud-based filling gelling material described in the above technical solution, comprising the following steps:
[0014] mixing red mud with fly ash to obtain a solid phase mixture;
[0015] The solid phase mixture, acidic slag, water and cement are mixed, subjected to hydration reaction, and then cured to obtain a red mud-based filling cementitious material.
[0016] Preferably, the hydration reaction time is 12 to 36 hours.
[0017] Preferably, the curing time is 12 to 24 days.
[0018] The present invention provides the use of the red mud-based filling gelling material described in the above technical solution or the red mud-based filling gelling material prepared by the preparation method described in the above technical solution in mine filling.
[0019] The present invention provides a red mud-based filling cementitious material, which takes red mud as the main matrix and acidic slag (electrolytic manganese slag or phosphogypsum) as the acid activator. By utilizing sulfate, residual waste acid, silicon oxide in electrolytic manganese slag or calcium sulfate dihydrate and residual waste acid in phosphogypsum, acidic activation of red mud and effective blending of silicon, calcium and aluminum elements are achieved, thereby obtaining a high-strength filling body and realizing the bulk consumption of red mud. The successful application of red mud can greatly reduce the consumption of sand and gravel mines, soil mining and traditional materials, and open up low-carbon construction of highway projects. DETAILED DESCRIPTION
[0020] The present invention provides a red mud-based filling gelling material, comprising the following raw materials in parts by weight:
[0021] 100 parts of red mud, 10-20 parts of acidic slag, 10-15 parts of fly ash, and 10-12 parts of cement;
[0022] The acidic slag includes electrolytic manganese slag or phosphogypsum.
[0023] The raw material for preparing the red mud-based filling cementitious material provided by the present invention includes 100 parts of red mud. In the present invention, the chemical components of the red mud preferably include Al2O3, SiO2, CaO, Fe2O3, Na2O, TiO2 and K2O. The present invention has no special limitation on the source of the red mud and the specific content of the chemical components therein, and the red mud can be obtained in a manner well known in the art.
[0024] Based on the mass fraction of the red mud, the raw materials for preparing the red mud-based filling cementitious material provided by the present invention include 10 to 20 parts of acidic slag, preferably 12 to 18 parts, more preferably 13 to 16 parts, and further preferably 14 to 15 parts.
[0025] In the present invention, the acidic slag includes electrolytic manganese slag or phosphogypsum.
[0026] In the present invention, the electrolytic manganese slag includes sulfate, waste acid and silicon oxide, and the phosphogypsum preferably includes calcium sulfate dihydrate and waste acid; the present invention has no special restrictions on the source and specific components of the electrolytic manganese slag or phosphogypsum, and the electrolytic manganese slag or phosphogypsum of the corresponding components can be obtained in a manner well known in the art. The main components of phosphogypsum are CaSO4 (about 90%) and various impurities such as undecomposed phosphate ore, unwashed phosphoric acid, calcium fluoride, iron and aluminum compounds, acid insolubles, organic matter, etc.
[0027] Based on the mass fraction of the red mud, the raw materials for preparing the red mud-based filling cementitious material provided by the present invention include 10 to 15 parts of fly ash, preferably 12 to 14 parts. In the present invention, the fly ash is preferably secondary fly ash. The present invention has no special limitation on the source of the fly ash, and any commercially available product known in the art can be used.
[0028] Based on the mass fraction of the red mud, the raw materials for preparing the red mud-based filling cementitious material provided by the present invention include 10 to 12 parts of cement, more preferably 12 parts. In the present invention, the cement is preferably composite silicate cement; the present invention has no special limitation on the source of the cement, and any commercially available product known in the art can be used.
[0029] The present invention provides a method for preparing the red mud-based filling gelling material described in the above technical solution, comprising the following steps:
[0030] mixing red mud with fly ash to obtain a solid phase mixture;
[0031] The solid phase mixture, acidic slag, water and cement are mixed, subjected to hydration reaction, and then cured to obtain a red mud-based filling cementitious material.
[0032] The present invention preferably crushes the red mud, adds fly ash, and uniformly mixes the solid phase in a stirring pot; then adds acidic slag, stirs while adding water, stirs for 20 minutes, adds cement and mixes for 10 minutes, puts the mixture into a stainless steel mold, places it on a vibration table and vibrates it for 5 minutes, stands for hydration reaction, then demoulds and naturally cures.
[0033] In the present invention, the mass of water is 75-85% of the red mud, and more preferably 80%.
[0034] In the present invention, the hydration reaction time is preferably 12 to 36 hours, more preferably 24 hours.
[0035] In the present invention, the curing time is preferably 12 to 24 days.
[0036] The present invention provides the application of the red mud-based filling cementitious material described in the above technical solution or the red mud-based filling cementitious material prepared by the preparation method described in the above technical solution in mine filling. The present invention has no special limitation on the application method, and the application can be carried out according to methods well known in the art.
[0037] 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.
[0038] In the following examples, cement was purchased from Guiyang Conch Panjiang Cement Co., Ltd. and was a Conch brand composite silicate cement (P·C 42.5).
[0039] Red mud was obtained from Qingzhen Guang Aluminum Group Co., Ltd., and its chemical composition is shown in Table 1.
[0040] Table 1 Chemical composition of red mud
[0041] Element content / % <![CDATA[Al2O3]]> 28.33 <![CDATA[SiO2]]> 27.88 CaO 18.69 <![CDATA[Fe2O3]]> 9.82 <![CDATA[Na2O]]> 5.12 <![CDATA[TiO2]]> 4.43 <![CDATA[K2O]]> 2.39 <![CDATA[SO3]]> 1.3 MgO 1.2 <![CDATA[P2O5]]> 0.27
[0042] Fly ash was obtained from Qingzhen Guang Aluminum Group Co., Ltd. and its chemical composition is shown in Table 2.
[0043] Table 2 Composition of fly ash
[0044] Element content / % <![CDATA[SiO2]]> 51.52 <![CDATA[Al2O3]]> 27.93 <![CDATA[Fe2O3]]> 9.63 <![CDATA[TiO2]]> 2.72 CaO 2.11 <![CDATA[SO3]]> 1.75 <![CDATA[Na2O]]> 1.52 <![CDATA[K2O]]> 1.45 MgO 0.837 <![CDATA[P2O5]]> 0.153 <![CDATA[V2O5]]> 0.0848 ZnO 0.0556
[0045] Example 1
[0046] The red mud-based filling cementitious material provided in this embodiment includes 100 parts of red mud, 15 parts of acidic slag, 12 parts of fly ash, and 12 parts of cement; the acidic slag is electrolytic manganese slag, and the electrolytic manganese slag comes from fresh manganese slag produced by electrolytic manganese enterprises.
[0047] The preparation method of the red mud-based filling gelling material in this embodiment is as follows:
[0048] (1) weighing red mud and crushing it, then weighing fly ash, and mixing the solid phase in a stirring pot;
[0049] (2) Weigh the electrolytic manganese slag and add it into a stirring pot. Add tap water while stirring until the mass of the water is 80% of the red mud. Stir for 20 minutes.
[0050] (3) After adding cement and mixing for 10 minutes, the mixture was put into a 40 mm × 160 mm stainless steel mold, placed on a vibration table and vibrated for 5 minutes. After standing for 24 hours, the mixture was demoulded and placed in a plastic water tank for natural curing. After the curing time was 3 days, 7 days, 14 days and 24 days respectively, the samples were taken out.
[0051] Example 2
[0052] The red mud-based filling cementitious material provided in this embodiment includes 100 parts of red mud, 10 parts of acidic slag, 10 parts of fly ash, and 10 parts of cement; the acidic slag is phosphogypsum, and the phosphogypsum comes from fresh phosphogypsum produced by phosphorus chemical enterprises.
[0053] The preparation method of the red mud-based filling gelling material in this embodiment is as follows:
[0054] (1) weighing red mud and crushing it, then weighing fly ash, and mixing the solid phase in a stirring pot;
[0055] (2) Weigh the electrolytic manganese slag and add it into a stirring pot. Add tap water while stirring until the mass of the water is 75% of the red mud. Stir for 20 minutes.
[0056] (3) After adding cement and mixing for 10 minutes, the mixture was put into a 40 mm × 160 mm stainless steel mold, placed on a vibration table and vibrated for 5 minutes. After standing for 24 hours, the mixture was demoulded and placed in a plastic water tank for natural curing. After the curing time was 3 days, 7 days, 14 days and 24 days respectively, the samples were taken out.
[0057] Example 3
[0058] The red mud-based filling cementitious material provided in this embodiment includes 100 parts of red mud, 20 parts of acidic slag, 15 parts of fly ash, and 12 parts of cement; the acidic slag is electrolytic manganese slag, and the electrolytic manganese slag comes from fresh manganese slag produced by electrolytic manganese enterprises.
[0059] The preparation method of the red mud-based filling gelling material in this embodiment is as follows:
[0060] (1) weighing red mud and crushing it, then weighing fly ash, and mixing the solid phase in a stirring pot;
[0061] (2) Weigh the electrolytic manganese slag and add it into a stirring pot. Add tap water while stirring until the mass of the water is 85% of the red mud. Stir for 20 minutes.
[0062] (3) After adding cement and mixing for 10 minutes, the mixture was put into a 40 mm × 160 mm stainless steel mold, placed on a vibration table and vibrated for 5 minutes. After standing for 24 hours, the mixture was demoulded and placed in a plastic water tank for natural curing. After the curing time was 3 days, 7 days, 14 days and 24 days respectively, the samples were taken out.
[0063] Example 4
[0064] The red mud-based filling cementitious material provided in this embodiment includes 100 parts of red mud, 16 parts of acidic slag, 13 parts of fly ash, and 11 parts of cement; the acidic slag is phosphogypsum, and the phosphogypsum comes from fresh phosphogypsum produced by phosphorus chemical enterprises.
[0065] The preparation method of the red mud-based filling gelling material in this embodiment is as follows:
[0066] (1) weighing red mud and crushing it, then weighing fly ash, and mixing the solid phase in a stirring pot;
[0067] (2) Weigh the electrolytic manganese slag and add it into a stirring pot. Add tap water while stirring until the mass of the water is 80% of the red mud. Stir for 20 minutes.
[0068] (3) After adding cement and mixing for 10 minutes, the mixture was put into a 40 mm × 160 mm stainless steel mold, placed on a vibration table and vibrated for 5 minutes. After standing for 24 hours, the mixture was demoulded and placed in a plastic water tank for natural curing. After the curing time was 3 days, 7 days, 14 days and 24 days respectively, the samples were taken out.
[0069] Detection Methods
[0070] The strength is tested according to the "Test Method for Strength of Cement Mortar" (GB / T17671-2021);
[0071] The initial and final setting time is tested according to the "Test Methods for Water Consumption, Setting Time and Stability of Cement Standard Consistency" (GB / T1346-2011);
[0072] The slump is tested according to the Standard for Test Methods of Ordinary Concrete Mixture Performance (GB / T50080-2016);
[0073] The fluidity is tested according to the "Method for Determination of Fluidity of Cement Mortar" (GBT2419-2005).
[0074] The test results are shown in Tables 3-4.
[0075] Table 3 Strength data of Examples 1 to 4
[0076]
[0077] Table 4 Initial and final setting time, fluidity and slump data of Examples 1 to 4
[0078] Case Example 1 Example 2 Example 3 Example 4 Initial setting time / h 6.5 5.5 5.2 5.1 Final setting time / h 12.5 13.5 12.5 12.6 Average diameter / cm, fluidity 27.5 24.45 23.25 23.65 Reading / cm, slump 22 23 26 25
[0079] It can be seen from Tables 3 and 4 that the red mud-based filling cementitious material provided by the present invention has high strength.
[0080] In addition, the appropriate initial setting time and final setting time will not affect the transportation and pouring of concrete mixture and the construction progress of concrete engineering, which has practical engineering significance.
[0081] 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 red mud-based filling cementitious material, characterized in that: The preparation comprises the following raw materials in parts by weight: 100 parts of red mud, 10-20 parts of acidic slag, 10-15 parts of fly ash, and 10-12 parts of cement; The acidic slag includes electrolytic manganese slag or phosphogypsum.
2. The red mud-based filling cementitious material according to claim 1, characterized in that: The chemical components of the red mud include Al2O3, SiO2, CaO, Fe2O3, Na2O, TiO2 and K2O.
3. The red mud-based filling cementitious material according to claim 1, characterized in that: The electrolytic manganese slag includes sulfate, waste acid and silicon oxide; the phosphogypsum includes calcium sulfate dihydrate and waste acid.
4. The red mud-based filling cementitious material according to claim 1, characterized in that: The fly ash is secondary fly ash.
5. The red mud-based filling cementitious material according to claim 1, characterized in that: The cement is composite silicate cement.
6. The method for preparing the red mud-based filling cementitious material according to any one of claims 1 to 5, characterized in that: The following steps are involved: mixing red mud with fly ash to obtain a solid phase mixture; The solid phase mixture, acidic slag, water and cement are mixed, subjected to hydration reaction, and then cured to obtain a red mud-based filling cementitious material.
7. The preparation method according to claim 6, characterized in that: The hydration reaction time is 12 to 36 hours.
8. The preparation method according to claim 6, characterized in that: The curing time is 12 to 24 days.
9. Use of the red mud-based filling cementitious material according to any one of claims 1 to 5 or the red mud-based filling cementitious material prepared by the preparation method according to any one of claims 6 to 8 in mine filling.