CN112429986B - Full-solid-waste underground filling cementing material for high-sulfur tailings and preparation method thereof - Google Patents
Full-solid-waste underground filling cementing material for high-sulfur tailings and preparation method thereof Download PDFInfo
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- CN112429986B CN112429986B CN202011409533.7A CN202011409533A CN112429986B CN 112429986 B CN112429986 B CN 112429986B CN 202011409533 A CN202011409533 A CN 202011409533A CN 112429986 B CN112429986 B CN 112429986B
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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
- 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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- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
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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
- 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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- 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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a full-solid waste underground filling cementing material for high-sulfur tailings and a preparation method thereof. The filling material is prepared from the full-solid-waste underground filling cementing material for the high-sulfur tailings and the high-sulfur tailings according to a certain mixing ratio, the 28d compressive strength and the 28d shrinkage rate both meet the requirements of JC/T2478-.
Description
Technical Field
The invention relates to the technical field of underground filling cementing materials, in particular to a full-solid waste underground filling cementing material for high-sulfur tailings and a preparation method thereof.
Background
The metal elements in some non-ferrous metal ores are usually present in the ores in the form of sulfides, such as lead-zinc ores, iron ores, copper ores and the like, and tailings remaining after ore dressing from such ores are generally rich in sulfur elements, and are called high-sulfur tailings. The tailings can be used as filling aggregate to be compounded with ordinary silica cement to prepare filling materials, and have certain environmental and economic benefits, but the problems are obvious. Such as: in the later stage of hydration, excessive sulfate continuously dissolved out from tailings can continuously react with ions or hydration products (CH, C-A-H and the like) in the pore solution to generate expansive ettringite or dihydrate gypsum crystals, huge internal stress is generated inside the filling body, the filling body structure with strength is damaged, and further the problems of poor volume stability, serious later strength shrinkage and the like of the filling body can be caused, and even the filling body is automatically cracked and disintegrated. Therefore, the application of the high-sulfur tailings in underground cemented filling is a great industrial problem. In addition, the ordinary portland cement as a cementing material is not suitable for the situation that high-sulfur tailings are used as filling aggregates because the ordinary portland cement has no sulfate corrosion resistance.
Disclosure of Invention
In view of the above, the invention aims to provide a full-solid waste underground filling cementing material for high-sulfur tailings, so as to solve the problems of poor volume stability and serious later strength shrinkage of the existing tailing filling material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the full-solid waste underground filling cementing material for the high-sulfur tailings comprises a matrix slurry A: 80-90 parts of excitation slurry B: 10-20 parts; the base body slurry A comprises slag, phosphorous slag, fly ash and water, the mass ratio of the slag to the phosphorous slag to the fly ash is (0.3-0.5) to (0.8-1) to 1, and the mass of the water is the sum of the mass of the slag to the phosphorous slag to the fly ash; the excitation slurry B comprises carbide slag, solid sulfur ash and water, the mass ratio of the carbide slag to the solid sulfur ash is (0.5-2) to 1, and the mass of the water is the sum of the mass of the carbide slag and the mass of the solid sulfur ash.
Optionally, Al in the fly ash2O3The content is 32-50%.
Optionally, the content of CaO in the carbide slag is 60-80%.
Optionally, Al in the fluidized bed combustion ash2O310-20% of SO3The content is 0-15%.
The second purpose of the invention is to provide a method for preparing the above full-solid waste underground filling cementing material for high-sulfur tailings, which comprises the following steps:
1) mixing the slag, the phosphorus slag, the fly ash, the water and a grinding body, sealing and grinding, setting the grinding rotation speed to be 300-600rpm, grinding until the median particle size of slurry particles is 3.0-3.5 mu m, and filtering to obtain a substrate slurry A;
2) mixing, sealing and grinding the carbide slag, the solid sulfur ash slag, the water and a grinding body, setting the grinding rotation speed to be 300-600rpm, grinding until the median particle size of slurry particles is 2.0-3.0 mu m, and filtering to obtain excitation slurry B;
3) and mixing the matrix slurry A with the excitation slurry B to obtain the full-solid-waste underground filling cementing material for the high-sulfur tailings.
Optionally, the mass of the grinding body in the step 1) is 2-3 times of the total mass of the slag, the phosphorous slag, the fly ash and the water, and the grading of the grinding body is 10 mm: 5 mm: 2.5 mm: 0.6mm ═ 2: 3: 4 by mass ratio.
Optionally, the mass of the grinding body in the step 2) is 2-3 times of the total mass of the carbide slag, the solid sulfur ash slag and the water, and the grading of the grinding body is 10 mm: 5 mm: 2.5 mm: 0.6mm ═ 2: 3: 4 by mass ratio.
Compared with the prior art, the full-solid-waste underground filling cementing material for the high-sulfur tailings has the following advantages:
based on the excellent sulfate erosion resistance and the synergistic hydration principle of the alkali-activated cementing material, the invention designs and prepares the full-solid waste underground filling cementing material for the high-sulfur tailings by using granulated blast furnace slag, phosphorous slag, fly ash, carbide slag, solid sulfur ash slag and tap water as main raw materials and using wet grinding to treat the solid raw materials as a main means; under the system, the slag and phosphorous slag are firstly hydrated to provide strength under the excitation action of carbide slag and sulfur-fixing slag, the internal gap formed by micro-shrinkage provides a required space environment for continuous crystal growth of ettringite and other hydration products, and SO dissolved from high-sulfur tailings is dissolved in an alkaline environment provided by the carbide slag and the sulfur-fixing slag in the middle and later periods of hydration4 2-The fly ash with insufficient early hydration capability but rapid later strength development can be continuously excited to generate fine hydration products to play a filling roleThe compactness and the mechanical strength of the hardened body are improved; when the invention is applied to underground filling of high-sulfur tailings, when the cement-sand ratio is 1: 6 and the slurry concentration is 68%, the compressive strengths of 7d mortar and 28d mortar are respectively greater than 0.9MPa and 2.0MPa, and the 28d shrinkage rate is less than 6%, so that the requirements of JC/T2478-; compared with common Portland cement, the mortar ratio can be reduced by 33 percent, and the 28d shrinkage rate can be reduced by more than 34 percent.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail with reference to examples.
The chemical compositions of the raw materials of the all-solid-waste underground-filling cementing materials for high-sulfur tailings of examples 1 to 4 of the present invention are shown in table 1, wherein the tailings are obtained from a pyrite beneficiation plant, and the SO of the tailings is shown in table 13The content is 27.6 percent, belonging to high-sulfur tailings.
TABLE 1
| Species of | CaO | SiO2 | Al2O3 | MgO | SO3 | P2O5 | Fe2O3 | Loss | Total |
| Slag of mine | 38.6 | 36.9 | 12.3 | 7.5 | 2.3 | - | - | 2.3 | 99.9 |
| Phosphorous slag | 47.2 | 37.5 | 3.4 | 1.2 | - | 2.3 | - | 8.1 | 99.7 |
| Fly ash | 1.2 | 48.7 | 37.9 | 0.1 | 0.3 | 0.1 | 0.3 | 11.2 | 99.8 |
| Carbide slag | 65 | 2.6 | 1.3 | 0.2 | 0.5 | - | 0.2 | 29.9 | 100 |
| Solid sulfur ash | 26.7 | 32.4 | 13.5 | 1.5 | 10.2 | - | 6.9 | 7.1 | 100 |
| Tailings | 10.2 | 17.4 | 6.8 | 3.1 | 27.6 | - | 25.2 | 9.6 | 99.9 |
The raw material composition of the all-solid-waste underground filling cementing material for high-sulfur tailings of the examples 1 to 4 of the invention is shown in table 2.
TABLE 2
The all-solid-waste underground filling cementing material for the high-sulfur tailings in the embodiments 1 to 4 is prepared by the following method:
1) weighing raw materials according to the raw material formula in the table 2;
2) mixing the weighed slag, phosphorus slag, fly ash, tap water and a grinding body, carrying out sealed grinding, setting the grinding rotation speed to be 300-600rpm, grinding until the median particle size of slurry particles in a ball milling tank is 3.0-3.5 mu m, and filtering to obtain wet grinding slurry A, namely substrate slurry A, wherein the consumption of the tap water is the sum of the mass of the slag, the phosphorus slag and the fly ash, namely the mass ratio of the tap water to the (slag, the phosphorus slag and the fly ash) is 1: 1;
3) mixing the weighed carbide slag, the solid sulfur ash, tap water and a grinding body, sealing and grinding, setting the grinding speed to be 300-600rpm, grinding until the median particle size of slurry particles in a ball grinding tank is 2.0-3.0 mu m, and filtering to obtain wet grinding slurry B, namely excitation slurry B, wherein the using amount of the tap water is the sum of the mass of the carbide slag and the solid sulfur ash, namely the mass ratio of the tap water to the (carbide slag and the solid sulfur ash) is 1: 1;
4) and mixing the prepared wet grinding slurry A and the prepared wet grinding slurry B according to the raw material proportion in the table 2 to obtain the full-solid waste underground filling cementing material for the high-sulfur tailings.
Wherein, the wet grinding slurry A and the wet grinding slurry B can be stored separately, and the two slurries are mixed to prepare the full solid waste underground filling cementing material for the high-sulfur tailings.
Moreover, in order to ensure grinding efficiency and grinding energy consumption as high as possible, in the preparation process of the full solid waste underground filling cementing material for high-sulfur tailings according to each embodiment of the invention, the mass of the grinding body is preferably 2.5 times of the mass of the grinding raw material, namely, the mass of the grinding body in the step 2) is 2.5 times of the total mass of the slag, the phosphorous slag, the fly ash and the water, and the mass of the grinding body in the step 3) is 2.5 times of the total mass of the carbide slag, the solid sulfur slag and the water, and the grading of the grinding body is preferably as follows by mass ratio: 10 mm: 5 mm: 2.5 mm: 0.6 mm-2: 3: 4.
When the full-solid-waste underground filling cementing material for the high-sulfur tailings is used for underground filling of the tailings, a proper glue-sand ratio and slurry concentration can be regulated, controlled and selected according to the characteristics (sulfur content, fineness and the like) of the tailings and specific construction requirements, and the full-solid-waste underground filling cementing material for the high-sulfur tailings, the high-sulfur tailings and other materials are mixed to prepare a filling material and used for underground filling.
For the characteristics of the high-sulfur tailings selected in each embodiment of the invention, the mass ratio of slurry to mortar is set to be 1: 4-6, the mass concentration is 68%, and the full-solid-waste underground filling cementing material for the high-sulfur tailings and the high-sulfur tailings of each embodiment of the invention are mixed to prepare the filling material and used for underground filling. The compression strength tests of 7d and 28d are carried out according to JGJ/T70-2009 'basic performance test method for building mortar', the shrinkage rate test of 28d is carried out according to JC/T2478-.
TABLE 3
As can be seen from Table 3, compared with the comparative example 1, when the invention is applied to underground filling of high-sulfur tailings, the compressive strengths of the 7d mortar and the 28d mortar in the examples 1 to 4 are respectively greater than 0.9MPa and 2.0MPa when the mortar-sand ratio is 1: 6 and the slurry concentration is 68%, and the requirements of JC/T2478-; the 28d shrinkage rate of the embodiments 1 to 4 is less than 6 percent, and the requirements of JC/T2478-; compared with the ordinary Portland cement (comparative example 1), the mortar ratio can be reduced by 33 percent, and the 28d shrinkage rate can be reduced by more than 34 percent.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The full-solid-waste underground filling cementing material for the high-sulfur tailings is characterized by comprising a matrix slurry A: 80-90 parts of excitation slurry B: 10-20 parts of a stabilizer; the base body slurry A consists of slag, phosphorous slag, fly ash and water, the mass ratio of the slag to the phosphorous slag to the fly ash is (0.3-0.5) to (0.8-1) to 1, and the mass of the water is the sum of the mass of the slag to the phosphorous slag to the fly ash; the excitation slurry B consists of carbide slag, solid sulfur ash and water, the mass ratio of the carbide slag to the solid sulfur ash is (0.5-2) to 1, and the mass of the water is the sum of the mass of the carbide slag and the mass of the solid sulfur ash;
the full-solid-waste underground filling cementing material for the high-sulfur tailings is prepared by the following method:
1) mixing the slag, the phosphorus slag, the fly ash, the water and a grinding body, sealing and grinding, setting the grinding rotation speed to be 300-600rpm, grinding until the median particle size of slurry particles is 3.0-3.5 mu m, and filtering to obtain a substrate slurry A;
2) mixing, sealing and grinding the carbide slag, the solid sulfur ash slag, the water and a grinding body, setting the grinding rotation speed to be 300-600rpm, grinding until the median particle size of slurry particles is 2.0-3.0 mu m, and filtering to obtain excitation slurry B;
3) and mixing the matrix slurry A with the excitation slurry B to obtain the full-solid-waste underground filling cementing material for the high-sulfur tailings.
2. The all-solid-waste underground filling cementitious material for high-sulfur tailings according to claim 1, wherein Al in the fly ash is2O3The content is 32-50%.
3. The full solid waste underground filling cementitious material for high sulfur tailings of claim 1, wherein the content of CaO in the carbide slag is 60-80%.
4. The full solid waste underground filling cementitious material for high sulfur tailings of claim 1, wherein the Al in the solid sulfur slag is2O310-20% of SO3The content is 0-15%.
5. The all-solid-waste underground filling cementitious material for high-sulfur tailings according to claim 1, wherein the mass of the grinding body in the step 1) is 2-3 times of the total mass of the slag, the phosphorous slag, the fly ash and the water, and the grading of the grinding body is 10 mm: 5 mm: 2.5 mm: 0.6mm = 2: 3: 4 in terms of mass ratio.
6. The full solid waste underground filling cementitious material for high sulfur tailings of claim 1, wherein the mass of the grinding body in the step 2) is 2-3 times of the total mass of the carbide slag, the solid sulfur ash slag and the water, and the grading of the grinding body is 10 mm: 5 mm: 2.5 mm: 0.6mm = 2: 3: 4 in terms of mass ratio.
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| CN114804714B (en) * | 2022-05-07 | 2023-03-10 | 安徽铜冠产业技术研究院有限责任公司 | Expanding agent containing high-sulfur tailings and application method thereof |
| CN115872682A (en) * | 2022-12-26 | 2023-03-31 | 安徽马钢嘉华新型建材有限公司 | Preparation method of cementing material for high-sulfur tailing cemented filling |
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| CN1295178C (en) * | 2004-06-25 | 2007-01-17 | 中南大学 | Method and system for treating high sulfur contained tails as binding filler aggregates |
| CN101781111A (en) * | 2010-03-01 | 2010-07-21 | 长沙矿山研究院 | Cementing material for mine filling and preparation method thereof |
| CN105565735B (en) * | 2015-11-30 | 2018-05-18 | 北京建研昆仑科技有限公司 | Sulfur-bearing tailings curing agent and sulfur-bearing tailing cemented filling material and the consolidated fill method of mine worked-out section |
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