CN113603451A - Calcination-free gypsum-based mine filler and preparation method thereof - Google Patents
Calcination-free gypsum-based mine filler and preparation method thereof Download PDFInfo
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- CN113603451A CN113603451A CN202110790361.0A CN202110790361A CN113603451A CN 113603451 A CN113603451 A CN 113603451A CN 202110790361 A CN202110790361 A CN 202110790361A CN 113603451 A CN113603451 A CN 113603451A
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- calcination
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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
- C04B28/30—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 magnesium cements or similar cements
-
- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
-
- 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
- C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a calcination-free gypsum-based mine filler and a preparation method thereof; the paint comprises the following components in percentage by weight: 75-81% of calcination-free desulfurized gypsum/phosphogypsum, 12-16% of magnesium oxide, 3-6% of magnesium sulfate, 1.2-1.9% of citric acid, 0.48-1.75% of sodium tripolyphosphate and 0.02-0.05% of water-retaining agent. The invention can be directly used for mine filling and pouring, and has the characteristics of high fluidity, good working performance, acid and erosion resistance, high later strength, high phosphogypsum consumption and the like.
Description
Technical Field
The invention relates to the field of mining engineering, in particular to a calcination-free gypsum-based mine filler and a preparation method thereof.
Background
With the demand of ecological restoration development, mine goaf treatment is concerned. Traditionally, dry filling is used, and some stones, gravels, soil, industrial waste residues and the like are manually or mechanically thrown to an area to be filled to form a compressible loose filling body. However, the filling mode has many defects, such as poor sealing performance, easy phenomena of surface subsidence, movement, deformation and the like, and the demand of the backfilled sandstone and the soil is large, so that the backfilling sandstone and the soil are not suitable for obtaining. In recent years, new filling technologies have appeared, such as compounding some tailings with cementing materials such as cement to prepare filling materials. For example, patent application publication nos.: CN112194451A, patent application name: a cementing agent composition for filling mine and its preparation method, this patent application regards tailings as the main material (dosage is 60-100), introduce kaolin, slag, cementing agent and excitant to prepare, have utilized the tailings waste effectively, but the whole process is relatively complicated, need to break, dry, ball-mill, etc., the economy is limited. As another example, patent application publication No.: CN112194443A, patent application name: the patent application mainly comprises red mud, slag, sodium bentonite, diatom mud, a cementing agent and an exciting agent, wherein the exciting agent activates the red mud to form strength, and the red mud needs to be crushed, dried, ball-milled and the like in the preparation process of the filling material. Some existing filling materials are mainly prepared by taking portland cement as a cementing component, and the rising of the price of the cement increases the filling cost, so that the economic benefit of mine filling mining is reduced, the application and development of the filling mining technology are restricted,
the problem of treatment and utilization of phosphogypsum is a worldwide problem, and China is the biggest phosphate fertilizer producing country in the world and is also the biggest phosphogypsum byproduct country. Due to the huge yield of the phosphogypsum, the market capacity of the comprehensive phosphogypsum utilization product is limited, and the complete utilization of the phosphogypsum cannot be realized at present. Because the phosphogypsum stockpiling quantity is large, a large amount of land resources are occupied, and the treatment of the phosphogypsum becomes an urgent and important subject. In the 2009 energy-saving and emission-reducing work plan of the state institute, comprehensive utilization of phosphogypsum is listed as a resource key project.
In recent years, more researches are carried out on the recycling of the phosphogypsum, and the product performance related to the phosphogypsum is also greatly improved. Such as the authorization notice number: CN104628349B, patent name: the phosphogypsum-based high-flow grouting material is prepared by using phosphorus-based high-strength gypsum as a basic raw material, using fly ash as a mineral admixture, using carbide slag and cement as an alkaline activator, modifying a grouting material by using whiskers, and adding a certain amount of retarder, a water reducing agent, a water-retaining agent and a water repellent. As another example, an authorization publication number: CN102173709B, patent name: the gypsum-base grouting material with adjustable performance is made up by using semi-hydrated gypsum and slag powder as basic raw material, using silicate cement as alkaline exciting agent and adding quartz sand, latex powder and chemical additives of high-effective water-reducing agent, high-effective retarder, antisettling agent, water repellent and air-entraining agent. From these patent products, portland cement is mostly used as an activating material, and various additives are added to improve fluidity and mechanical properties and early strength characteristics. When the products are prepared, the mixing amount of each additive has obvious influence on the performance of the grouting material, in addition, the required raw materials have various varieties and higher requirements on the components of the raw materials, and part of the raw materials can be put into use only by processing and screening. Therefore, the economic cost of using the phosphogypsum-based grouting material in mine filling is increased, the efficiency is reduced, and the application range of the phosphogypsum is restricted.
Desulfurized gypsum is an industrial byproduct obtained by desulfurizing and purifying flue gas generated by burning sulfur-containing fuels (coal, oil, etc.). The flue gas desulfurization technology meets the national policy requirements of energy conservation and emission reduction, but also brings about the emission of a large amount of desulfurization byproducts, namely desulfurization gypsum. At present, the desulfurized gypsum is mainly used as a retarder for producing gypsum products and common cement, but a large amount of gypsum is still stacked in a specific storage yard, which not only occupies land and causes environmental pollution, but also greatly wastes resources, so that the development of the desulfurized gypsum resource utilization technology for filling pits has obvious social, economic and ecological benefits.
Disclosure of Invention
The invention aims to provide a calcination-free gypsum-based mine filler and a preparation method thereof by utilizing industrial waste calcination-free desulfurized gypsum/phosphogypsum, reasonably utilizing resources and improving and exciting the potential performance of the waste through technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a calcination-free gypsum-based mine filler which comprises the following components in percentage by weight:
preferably, the solubility constant of the calcination-free desulfurized gypsum/phosphogypsum is 5-25, and the water content is 18-22 wt%.
Preferably, the magnesium oxide is light-burned active magnesium oxide, wherein the active content of the light-burned active magnesium oxide is more than 65%.
Preferably, the magnesium sulfate is magnesium sulfate heptahydrate and white crystals, and the mass fraction of the magnesium sulfate is more than 50%.
Preferably, the citric acid is citric acid monohydrate, and the mass fraction of the citric acid is more than 99%.
Preferably, the sodium tripolyphosphate is of an industrial grade, and the mass fraction of the sodium tripolyphosphate is more than 90%.
Preferably, the water retention agent is methyl cellulose ether and is white powder.
The invention also provides a preparation method of the calcination-free gypsum-based mine filler, which comprises the following steps: weighing the required calcination-free desulfurized gypsum/phosphogypsum, magnesium oxide, magnesium sulfate, citric acid, sodium tripolyphosphate and water-retaining agent according to the proportion, fully and uniformly stirring to form mixed powder, adding mixing water accounting for 35-40 wt% of the weight of the powder, and fully stirring for 2-3 minutes. The method can be used for pumping filling construction.
The invention can be used for filling, reinforcing, repairing and the like of mines and partial waste underground spaces.
The invention is different from the prior mine filling grouting material taking portland cement as a cementing material, and takes the calcination-free desulfurized gypsum/phosphogypsum as a base material, and utilizes the reaction of active magnesium oxide and magnesium sulfate to form a new cementing material system, namely the magnesium oxysulfate calcium cement; soluble phosphoric acid and citric acid contained in the calcination-free desulfurized gypsum/phosphogypsum are used as modifiers to accelerate the synthesis and water resistance of the magnesium calcium oxysulfate cement, and sodium tripolyphosphate is used as a dispersing agent to play the roles of reducing water and improving fluidity, and the introduced methyl cellulose ether ensures the stability of the filler in the pumping process.
Compared with other developed gypsum-based grouting materials, the invention has the following beneficial effects:
1) the usage amount of the original calcination-free desulfurized gypsum/phosphogypsum is large and can reach over 75 percent;
2) setting and hardening are fast, and final setting can be achieved within 150-240 min;
2) the fluidity is high, the initial fluidity can reach 300mm, and pumping and pouring are easy;
3) the water resistance is strong, the underwater soaking has no decomposition phenomenon, the strength loss is little, and the softening coefficient is large;
4) compared with other phosphogypsum-based grouting materials, the high-strength grouting material has the compression strength of 1-3 MPa mostly in 28d, and the compression strength of the grouting material can reach 15-20 MPa in 28 d.
Therefore, the invention provides the filling material which has lower requirements on raw material components, does not need secondary processing or screening and has less material types and can be used in a large range, and the prepared grouting material has the characteristics of high setting and hardening speed, high mechanical property, high anti-permeability capability, large consumption of original desulfurization gypsum/phosphogypsum and the like besides high fluidity.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
The following examples are prepared by uniformly mixing calcination-free desulfurized gypsum/phosphogypsum, magnesium oxide, magnesium sulfate, citric acid, sodium tripolyphosphate and methyl cellulose ether in a field mixer according to a certain proportion, and adjusting the components according to the engineering application requirements to obtain the required performance.
The calcination-free phosphogypsum is untreated calcination-free phosphogypsum of a phosphorization plant, and is untreated calcination-free desulfurized gypsum of a thermal power plant.
Example 1
The components and weight percentages thereof in the embodiment are as follows:
the calcination-free phosphogypsum, the magnesium oxide, the magnesium sulfate, the citric acid, the sodium tripolyphosphate and the methyl cellulose ether in the components are prepared into the filler powder by the process. Adding tap water accounting for 40 wt% of the powder mass, and stirring for 3 minutes to obtain flowable slurry. The initial fluidity reaches 330mm, the final setting is reached at 220min, and the 7d strength is tested to be 13.5MPa, the 14d strength is tested to be 17.5MPa, the 28d strength is tested to be 21.5MPa, and the softening coefficient is tested to be 0.75.
Example 2
The components and weight percentages thereof in the embodiment are as follows:
the calcination-free phosphogypsum, the magnesium oxide, the magnesium sulfate, the citric acid, the sodium tripolyphosphate and the methyl cellulose ether in the components are prepared into grouting material powder according to the process. Adding tap water accounting for 35 wt% of the powder mass, and stirring for 3 minutes to obtain flowable slurry. The initial fluidity reaches 310mm, the final setting is reached in 210min, and the 7d strength is 11.0MPa, the 14d strength is 14.5MPa, the 28d strength is 21.5MPa and the softening coefficient is 0.80.
Example 3
The components and weight percentages thereof in the embodiment are as follows:
the calcination-free phosphogypsum, the magnesium oxide, the magnesium sulfate, the citric acid, the sodium tripolyphosphate and the methyl cellulose ether in the components are prepared into grouting material powder according to the process. Adding tap water accounting for 38 wt% of the powder mass, and stirring for 2.5 minutes to obtain flowable slurry. The initial fluidity reaches 310mm, the final setting time is 150min, and the test shows that the 7d strength is 12.0MPa, the 14d strength is 16.5MPa, the 28d strength is 22.5MPa, and the softening coefficient is 0.83.
Example 4
The components and weight percentages thereof in the embodiment are as follows:
the calcination-free phosphogypsum, the magnesium oxide, the magnesium sulfate, the citric acid, the sodium tripolyphosphate and the methyl cellulose ether in the components are prepared into the filler powder by the process. Adding tap water accounting for 38 wt% of the powder mass, and stirring for 3 minutes to obtain flowable slurry. The initial fluidity reaches 300mm, the final setting time is 240min, and the test shows that the 7d strength is 10.0MPa, the 14d strength is 15.0MPa, the 28d strength is 18.5MPa, and the softening coefficient is 0.78.
The results of the grouting tests for examples 1-4 are shown in Table 1.
TABLE 1 grouting material Performance test results of examples 1-4
Example 5
The components and weight percentages thereof in the embodiment are as follows:
the calcination-free desulfurized gypsum, the magnesium oxide, the magnesium sulfate, the citric acid, the sodium tripolyphosphate and the methyl cellulose ether in the components are prepared into grouting material powder according to the process. Adding tap water accounting for 38 wt% of the powder mass, and stirring for 2.5 minutes to obtain flowable slurry. The initial fluidity reaches 310mm, the final setting time is 180min, and the 7d strength is 11.0MPa, the 14d strength is 14.5MPa, the 28d strength is 20.5MPa and the softening coefficient is 0.80.
Example 6
The components and weight percentages thereof in the embodiment are as follows:
the calcination-free desulfurized gypsum, the magnesium oxide, the magnesium sulfate, the citric acid, the sodium tripolyphosphate and the methyl cellulose ether in the components are prepared into grouting material powder according to the process. Adding tap water accounting for 35 wt% of the powder mass, and stirring for 3 minutes to obtain flowable slurry. The initial fluidity reaches 310mm, the final setting time is 210min, and the test shows that the 7d strength is 11.0MPa, the 14d strength is 14.5MPa, the 28d strength is 21.5MPa, and the softening coefficient is 0.80.
Example 7
The components and weight percentages thereof in the embodiment are as follows:
the calcination-free desulfurized gypsum, the magnesium oxide, the magnesium sulfate, the citric acid, the sodium tripolyphosphate and the methyl cellulose ether in the components are prepared into grouting material powder according to the process. Adding tap water accounting for 38 wt% of the powder mass, and stirring for 3 minutes to obtain flowable slurry. The initial fluidity reaches 310mm, the final setting time is 150min, and the test shows that the 7d strength is 12.0MPa, the 14d strength is 16.5MPa, the 28d strength is 22.5MPa, and the softening coefficient is 0.83.
The results of the grouting tests for examples 5-7 are shown in Table 2.
TABLE 2 grouting Material Performance test results of examples 5-7
In conclusion, the invention provides the mine karst cave filling grouting material which takes the calcination-free desulfurized gypsum/phosphogypsum as a base material, is assisted by a small amount of active magnesium oxide and magnesium sulfate, has better working performance and can automatically level.
The grouting material provided by the invention has three significance:
the application range of the gypsum can be widened, a large amount of desulfurized gypsum/phosphogypsum solid waste is consumed, and the resource recycling is realized;
secondly, a novel grouting material suitable for filling and pouring the abandoned mine is provided, most of Portland cement is replaced, and the economic cost is reduced;
the grouting material provided by the invention provides an efficient method for simultaneously solving the problems of waste materials and waste space in the mine industry.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The mine filling material based on calcination-free gypsum is characterized by comprising the following components in percentage by weight:
2. the calcination-free gypsum-based mine filler according to claim 1, wherein the calcination-free desulfurized gypsum/phosphogypsum has a solubility constant of 5-25 and a water content of 18-22 wt%.
3. The calcination-free gypsum-based mine filler according to claim 1, wherein the magnesium oxide is light-burned active magnesium oxide, and the active content of the light-burned active magnesium oxide is more than 65%.
4. The calcination-free gypsum-based mine filler according to claim 1, wherein the magnesium sulfate is magnesium sulfate heptahydrate, white crystals, and the mass fraction of the magnesium sulfate is more than 50%.
5. The calcination-free gypsum-based mine filling material of claim 1, wherein the citric acid is citric acid monohydrate, industrial grade, and the mass fraction is more than 99%.
6. The calcination-free gypsum-based mine filler according to claim 1, wherein the sodium tripolyphosphate is technical grade and has a mass fraction greater than 90%.
7. The calcination-free gypsum-based mine filler according to claim 1, wherein the water retention agent is methyl cellulose ether and is white powder.
8. The method for preparing the calcination-free gypsum-based mine filler according to any one of claims 1 to 7, comprising: weighing the required calcination-free desulfurized gypsum/phosphogypsum, magnesium oxide, magnesium sulfate, citric acid, sodium tripolyphosphate and water-retaining agent according to the proportion, fully and uniformly stirring to form mixed powder, adding mixing water accounting for 35-40 wt% of the weight of the powder, and fully stirring for 2-3 minutes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349465A (en) * | 2021-12-30 | 2022-04-15 | 熊晨 | Novel sulfur-oxygen-magnesium-calcium cement-based material and use method thereof |
| CN115490493A (en) * | 2022-09-29 | 2022-12-20 | 上海胜义环境科技有限公司 | Baking-free brick taking phosphogypsum as base material and preparation method thereof |
| CN116854450A (en) * | 2023-03-15 | 2023-10-10 | 四川省建材工业科学研究院有限公司 | Activating treatment agent for preparing sintered insulating bricks from water-based drilling cuttings |
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2021
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349465A (en) * | 2021-12-30 | 2022-04-15 | 熊晨 | Novel sulfur-oxygen-magnesium-calcium cement-based material and use method thereof |
| CN115490493A (en) * | 2022-09-29 | 2022-12-20 | 上海胜义环境科技有限公司 | Baking-free brick taking phosphogypsum as base material and preparation method thereof |
| CN116854450A (en) * | 2023-03-15 | 2023-10-10 | 四川省建材工业科学研究院有限公司 | Activating treatment agent for preparing sintered insulating bricks from water-based drilling cuttings |
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