CN115490491A - Phosphogypsum-based underground filling paste and preparation method thereof - Google Patents

Phosphogypsum-based underground filling paste and preparation method thereof Download PDF

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Publication number
CN115490491A
CN115490491A CN202211278555.3A CN202211278555A CN115490491A CN 115490491 A CN115490491 A CN 115490491A CN 202211278555 A CN202211278555 A CN 202211278555A CN 115490491 A CN115490491 A CN 115490491A
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China
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phosphogypsum
filling paste
cement
prepared
filling
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Inventor
吴立波
李剑秋
鲁顺有
董洪桥
李志飞
晏浩淋
曹雪
徐绍霞
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Guizhou Chuan Heng Chemical Co ltd
Guizhou Fulin Mining Co ltd
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Guizhou Chuan Heng Chemical Co ltd
Guizhou Fulin Mining Co ltd
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Priority to CN202211278555.3A priority Critical patent/CN115490491A/en
Publication of CN115490491A publication Critical patent/CN115490491A/en
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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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/08—Slag cements
    • C04B28/087—Phosphorus slags
    • 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
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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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)

Abstract

The invention provides a phosphogypsum-based underground filling paste which is prepared from the following raw materials: 1 part by weight of a cementing material; 6 to 8 weight portions of dihydrate phosphogypsum; 4-6 parts of phosphogypsum balls; the gel material is prepared from the following components in a mass ratio of 1: (1-2) cement and phosphorous slag. Compared with the prior art, the phosphogypsum-based underground filling paste provided by the invention adopts specific content components, can realize better integral interaction, has high utilization rate of solid waste, low cost and low bleeding rate, and the formed filler has excellent strength and performance, strong water resistance and high softening coefficient, and the toxicity leaching of the filler meets the environmental protection requirement.

Description

Phosphogypsum-based underground filling paste and preparation method thereof
Technical Field
The invention relates to the technical field of mine filling materials, in particular to phosphogypsum-based underground filling paste and a preparation method thereof.
Background
The phosphogypsum is solid waste residue discharged in the process of producing phosphoric acid, 4-5 t of phosphogypsum is produced when 1t of phosphoric acid is produced, the phosphorus slag is another industrial byproduct of the phosphating industry, and 8-10 t of phosphorus slag is discharged when 1t of yellow phosphorus is produced. The stacking of the phosphogypsum and the phosphorus slag not only occupies a large amount of land, but also easily carries harmful ions in the phosphogypsum and the phosphorus slag by rainwater, thereby polluting the environment. But the phosphorous slag can have obvious gelation property after certain treatment. Experimental research shows that the phosphogypsum has an excitation effect on hydration of phosphorus slag, can continuously generate a C-S-H gel crystal net structure with strength in a humid environment, and is further combined with the phosphogypsum to form an ettringite crystal so as to further harden the strength of a filling body.
In recent years, phosphogypsum is widely studied as an aggregate for mine filling, but the phosphogypsum is not an ideal filling material because the phosphogypsum has the characteristics of extremely fine particles, small permeability and slurry weakening when meeting water. The semi-hydrated phosphogypsum is granulated to form phosphogypsum balls to adjust the grain size gradation of the filling aggregate, so that the concentration of the filling slurry can be effectively improved, the bleeding rate of the filling slurry is reduced, the slurry is prevented from being separated, and meanwhile, the aggregate can further provide the strength performance of a filling body.
The Chinese invention patent with the publication number of CN1821547A discloses a method for forming a solidified filling body by phosphogypsum filling and an underground goaf, and the proportioning mode is as follows: fly ash: phosphogypsum =1:1:6 to 8 percent of admixture is added after being mixed, and the mixture is added with water and stirred evenly to prepare filling slurry with the concentration of 57 to 63 percent. However, the filling body ardealite prepared by the method has low utilization rate and high filling cost, the 28d average strength is only 1.08MPa, and the concentration is only 57-63%, so the bleeding rate is high, and the filling and drainage burden of an underground mine is caused.
The Chinese invention patent with the publication number of CN103964804A discloses a pumpable phosphogypsum and yellow phosphorus slag filling paste with low bleeding rate and a preparation method thereof, wherein the filling formula is yellow phosphorus slag: phosphogypsum =1: (2-8), the concentration of the prepared filling slurry is 63-68%, the bleeding rate of the slurry is 2.0-3.5%, the early strength of 7d is 0.20-0.50MPa, and the strength of 28d is 1.0-3.0 MPa. Although the method effectively reduces the water content secreted by the filling slurry and meets the requirement of filling body conveying, the early strength is too low, the water resistance is poor, and harmful ions in phosphogypsum and phosphorous slag cannot be effectively solidified.
In conclusion, how to utilize phosphorus chemical solid waste in a large amount and in a resource manner and effectively reduce the filling cost is a technical problem to be solved urgently in the field, so that the development of the preparation method of the phosphogypsum-based underground filling paste which has low cost, high solid waste rate and meets the requirements of environmental protection has important significance.
Disclosure of Invention
In view of the above, the invention aims to provide the phosphogypsum-based underground filling paste and the preparation method thereof, the phosphogypsum-based underground filling paste provided by the invention has the advantages of high solid waste utilization rate, low cost and low bleeding rate, the formed filling body has excellent strength and performance, strong water resistance and high softening coefficient, and the toxic leaching of the filling body meets the environmental protection requirement.
The invention provides phosphogypsum-based underground filling paste which is prepared from the following raw materials:
1 part by weight of a cementing material;
6 to 8 weight portions of dihydrate phosphogypsum;
4-6 parts of phosphogypsum balls;
the gelled material is prepared from the following components in a mass ratio of 1: (1-2) cement and phosphorous slag.
Preferably, the cement is one or more of 425 portland cement, cement clinker and 525 cement.
Preferably, the phosphorous slag is in a micro powder state, the 28d activity is 72-92%, and the average particle size is 10-20 μm.
Preferably, the phosphogypsum ball is obtained by granulating semi-hydrated phosphogypsum through a disc, the crushing value is 10-35%, the free water content is less than or equal to 10%, and the particle size is 1-25 mm.
Preferably, the phosphogypsum-based downhole filling paste further comprises:
additives accounting for 0.4 to 0.6 percent of the total mass of the cementing materials, the dihydrate phosphogypsum and the phosphogypsum balls;
the additive is prepared from an early strength agent, a pumping agent and a high-efficiency water reducing agent.
Preferably, the early strength agent is a chloride salt and/or a sulfate salt.
Preferably, the high-efficiency water reducing agent is a polycarboxylic acid high-performance water reducing agent.
Preferably, the mass ratio of the early strength agent to the pumping agent to the high efficiency water reducing agent is 1: (0.6-0.8): (0.2-0.4).
The invention also provides a preparation method of the phosphogypsum-based underground filling paste, which comprises the following steps:
pre-stirring the cementing material, the dihydrate phosphogypsum and the phosphogypsum balls to obtain a dry material; and adding water and stirring to obtain the phosphogypsum-based underground filling paste.
Preferably, the amount of the added water is such that the concentration of the obtained phosphogypsum-based underground filling paste is 77-85%.
The invention provides a phosphogypsum-based underground filling paste which is prepared from the following raw materials: 1 part by weight of a cementing material; 6 to 8 weight portions of dihydrate phosphogypsum; 4-6 parts of phosphogypsum balls; the gel material is prepared from the following components in a mass ratio of 1: (1-2) cement and phosphorous slag. Compared with the prior art, the phosphogypsum-based underground filling paste provided by the invention adopts specific content components, can realize better integral interaction, has high utilization rate of solid waste, low cost and low bleeding rate, and the formed filler has excellent strength and performance, strong water resistance and high softening coefficient, and the toxicity leaching of the filler meets the environmental protection requirement.
In addition, the preparation method provided by the invention is simple in process, mild in condition and suitable for large-scale industrial production.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a phosphogypsum-based underground filling paste which is prepared from the following raw materials:
1 part by weight of a cementing material;
6 to 8 weight portions of dihydrate phosphogypsum;
4-6 parts of phosphogypsum balls;
the gelled material is prepared from the following components in a mass ratio of 1: (1-2) cement and phosphorous slag.
At present, most of mine fillers in China are low in concentration and serious in segregation, and are difficult to achieve high concentration or paste filling, so that the problem that the mine is difficult to drain due to the fact that a filled mine easily secretes more water is solved; meanwhile, at present, the phosphogypsum is used as a filling aggregate to carry out cemented filling with cementing materials such as cement and the like, so that the lime-sand ratio is high, the filling cost is high, and the water resistance and the environmental protection of a filling body are less considered.
Aiming at the technical problems, the invention provides the phosphogypsum-based underground filling paste which has low cost, high solid waste rate, low bleeding rate, high strength and strong water resistance and meets the requirements of filling and environmental protection, and the filling paste has the following characteristics: the toothpaste-like slurry which is not layered, separated and weeping can solve the problems that: the method comprises the following steps of (1) solving the problems of low slurry concentration and easy segregation, (2) solving the problem of difficult underground drainage, (3) reducing filling cost, and (4) consuming solid wastes.
In the invention, the gel material is prepared from the following components in a mass ratio of 1: (1-2) the cement and phosphorous slag composition is preferably 1:1.5.
in the present invention, the cement is preferably one or more of 425 portland cement, cement clinker and 525 cement, more preferably 425 portland cement. The source of the cement is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the phosphorous slag is preferably in a fine powder state, the 28d activity is preferably 72 to 92%, more preferably 80 to 85%, and the average particle size is preferably 10 to 20 μm, more preferably 15 to 16 μm. The source of the phosphorous slag is not particularly limited in the invention, and solid waste slag of the phosphorization industry, which is well known to those skilled in the art, can be adopted.
In the invention, the phosphogypsum balls are preferably obtained by granulating semi-hydrated phosphogypsum by a disc, the crushing value is preferably 10-35%, more preferably 15-30%, the free water content is preferably less than or equal to 10%, more preferably less than or equal to 5%, and the particle size is preferably 1-25 mm, more preferably 4-20 mm.
The invention has no special limitation on the source of the dihydrate phosphogypsum and the raw material phosphogypsum of the phosphogypsum ball, and solid waste residue of the phosphorization industry well known to a person skilled in the art can be adopted.
In the invention, the phosphogypsum-based underground filling paste is prepared from the following raw materials:
1 part by weight of a cementing material;
6 to 8 weight portions of dihydrate phosphogypsum;
4-6 parts of phosphogypsum balls;
the gel material is prepared from the following components in a mass ratio of 1: (1-2) cement and phosphorous slag.
According to the invention, through an orthogonal test, numerical simulation is carried out on the orthogonal test result by using MATLAB software to obtain the optimal range of the phosphorus-to-slag ratio of the cement, the phosphogypsum balls and the phosphogypsum dihydrate in the formula, so that the minimum amount of cementing materials is used to consume the maximum amount of phosphorus chemical solid waste, the prepared filling paste slurry has good fluidity, the slump is 23-28 cm, almost no bleeding exists, the problem of difficult drainage of underground filling mines can be effectively solved, and simultaneously, the formed filling body has excellent strength and water resistance and high softening coefficient, and the toxicity leaching of the filling body meets the environmental protection requirement.
In the present invention, the phosphogypsum-based downhole filling paste preferably further comprises:
0.4 to 0.6 percent of admixture, preferably 0.5 percent of the total mass of the cementing material, the dihydrate phosphogypsum and the phosphogypsum ball.
In the invention, the additive is preferably prepared from an early strength agent, a pumping agent and a high-efficiency water reducing agent.
In the present invention, the early strength agent is preferably a chloride salt and/or a sulfate salt, more preferably a chloride salt. The source of the early strength agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
The type and source of the pumping agent are not particularly limited in the present invention, and any pumping aid known to those skilled in the art may be used.
In the present invention, the high-efficiency water reducing agent is preferably a polycarboxylic acid-based high-performance water reducing agent. The source of the early strength agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the mass ratio of the early strength agent, the pumping agent and the high efficiency water reducing agent is preferably 1: (0.6-0.8): (0.2 to 0.4), more preferably 1:0.7:0.3.
the invention provides the strength of a filling body and cures toxic and harmful ions by using cement and phosphorus slag as cementing materials, and simultaneously utilizes phosphogypsum balls and dihydrate phosphogypsum to carry out grading adjustment, thereby improving the slurry concentration of the filling paste, reducing the bleeding rate, effectively preventing the slurry from segregating, simultaneously using the phosphogypsum balls as aggregates to further provide the strength performance of the filling body, reducing the sand-lime ratio, increasing the utilization rate of solid wastes and reducing the filling cost; in addition, the additive is added, so that the concentration of the filling paste can be further improved by 2-5%, the strength of the filling body can be further improved by 10-15%, and the optimal addition amount is 0.4-0.6%.
The invention also provides a preparation method of the phosphogypsum-based underground filling paste, which comprises the following steps:
pre-stirring the cementing material, the dihydrate phosphogypsum and the phosphogypsum balls to obtain a dry material; and adding water and stirring to obtain the phosphogypsum-based underground filling paste.
In the invention, the cementing material, the dihydrate phosphogypsum and the phosphogypsum ball are the same as those in the technical scheme, and are not described again.
The pre-stirring device is not particularly limited by the present invention, and a mortar stirrer well known to those skilled in the art can be used. In the present invention, the preliminary stirring time is preferably 10s to 60s, more preferably 20s to 40s.
In a preferred embodiment of the invention, an additive is also added, namely, the cementing material, the dihydrate phosphogypsum, the phosphogypsum balls and the additive are pre-stirred to obtain a dry material.
In the present invention, the amount of water added is preferably such that the concentration of the resulting phosphogypsum-based downhole filling paste is 75-85%, more preferably 77-83%. In the invention, the concentration of the slurry can reach 75-85% under the condition of meeting the conveying requirement, almost no bleeding exists, and the problem of difficult drainage of the underground filling mine can be effectively solved; meanwhile, the minimum amount of cementing materials is used for consuming the maximum amount of phosphorus chemical industry solid waste, the filling cost is low, the formed filling body has excellent strength performance, strong water resistance and high softening coefficient, and the toxic leaching of the filling body meets the requirement of environmental protection.
The stirring device is not particularly limited in the present invention, and a mortar stirrer well known to those skilled in the art may be used. In the present invention, the stirring time is preferably 1min to 5min, more preferably 2min to 4min.
In a preferred embodiment of the invention, the preparation method of the phosphogypsum-based underground filling paste comprises the following steps of: micro-powder of the phosphorous slag: dihydrate phosphogypsum: phosphogypsum ball =0.4:0.6: (6-8): (4-6), adding an additive according to 0.4-0.6% of the total mass of the materials, mixing and stirring the mixture with water to prepare filling paste slurry with the concentration of 75-85%. The preparation method provided by the invention is simple in process, mild in condition and suitable for large-scale industrial production.
The invention utilizes the phosphogypsum ball matched with the dihydrate phosphogypsum to adjust the filling aggregate gradation, so that the slurry achieves the effect of high concentration and no segregation; the phosphogypsum has an excitation effect on the hydration of the phosphorus slag, and the phosphorus slag and the cement are selected for matching use, so that the following beneficial effects are realized:
(1) Under the condition of the same filling requirement (strength and environmental protection), the formula has high solid waste consumption rate and low filling cost;
(2) The phosphogypsum balls are matched with dihydrate phosphogypsum, and the grading of the filling aggregate is adjusted, so that the filling slurry is high in concentration, low in bleeding rate and free of segregation, and the problems of full pipe conveying and difficult underground drainage can be effectively solved.
In addition, numerical simulation is carried out on the orthogonal test result by using MATLAB software through an orthogonal test, so that the optimal ranges of the cement phosphorus slag ratio, the gypsum ball ratio and the dihydrate phosphogypsum ratio in the formula are obtained.
The invention provides a phosphogypsum-based underground filling paste which is prepared from the following raw materials: 1 part by weight of a cementing material; 6 to 8 weight portions of dihydrate phosphogypsum; 4-6 parts of phosphogypsum balls; the gel material is prepared from the following components in a mass ratio of 1: (1-2) cement and phosphorous slag. Compared with the prior art, the phosphogypsum-based underground filling paste provided by the invention adopts specific content components, so that the integral better interaction can be realized, the obtained phosphogypsum-based underground filling paste has the advantages of high solid waste utilization rate, low cost and low bleeding rate, the formed filler has excellent strength performance, strong water resistance and high softening coefficient, and the toxic leaching of the filler meets the environmental protection requirement.
In addition, the preparation method provided by the invention is simple in process, mild in condition and suitable for large-scale industrial production.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available, and the chemical indexes are shown in table 1 below.
Chemical index data of each raw material in example of Table 1
Figure BDA0003897630480000071
Wherein the cement is ordinary 425 portland cement with the average particle size of 16.88 μm; the phosphorus slag is in a micro powder state, the activity is 82 percent in 28 days, and the average grain diameter is 15.57 mu m; the phosphogypsum balls are obtained by granulating semi-hydrated phosphogypsum through a disc, the crushing value is 15-30%, the free water content is less than or equal to 5%, and the particle size range is 4.75-20 mm.
The additive is a self-made composite additive, and is prepared from an early strength agent (sodium chloride), a pumping agent and a high-efficiency water reducing agent (a polycarboxylic acid high-performance water reducing agent) according to the mass ratio of 1:0.7:0.3, and the preparation.
Example 1
Cement is prepared from the following raw materials in percentage by mass: micro-powder of the phosphorous slag: dihydrate phosphogypsum: phosphogypsum ball =0.4:0.6:6: and 4, weighing each raw material, adding an additive accounting for 0.5 percent of the total mass of the raw materials, adding the raw materials into a mortar stirrer for pre-stirring for 30s, weighing water with corresponding mass, pouring the water into the stirrer to be mixed with dry materials, and stirring for 3min again to prepare filling paste slurry with the concentration of 81wt percent, namely the phosphogypsum-based underground filling paste.
Example 2
The preparation process provided in example 1 was used with the difference that: cement is prepared from the following raw materials in percentage by mass: micro-powder of the phosphorous slag: dihydrate phosphogypsum: phosphogypsum ball =0.4:0.6:6: and 6, adding an additive accounting for 0 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 78 weight percent.
Example 3
The preparation process provided in example 1 was used with the difference that: cement is prepared from the following raw materials in percentage by mass: micro-powder of the phosphorous slag: dihydrate phosphogypsum: phosphogypsum ball =0.4:0.6:6: and 6, adding an additive accounting for 0.5 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 82 weight percent.
Example 4
The preparation process provided in example 1 was used with the difference that: cement is prepared from the following raw materials in percentage by mass: micro-powder of the phosphorous slag: dihydrate phosphogypsum: phosphogypsum ball =0.4:0.6:8: and 4, adding an additive accounting for 0 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 77 percent by weight.
Example 5
The preparation process provided in example 1 was used with the difference that: cement is prepared from the following raw materials in percentage by mass: micro-powder of the phosphorous slag: dihydrate phosphogypsum: phosphogypsum ball =0.4:0.6:8: and 4, adding an additive accounting for 0.5 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 81 weight percent.
Example 6
The preparation process provided in example 1 was used with the difference that: cement is prepared from the following raw materials in percentage by mass: micro-powder of the phosphorous slag: dihydrate phosphogypsum: phosphogypsum ball =0.4:0.6:8: and 6, adding an additive accounting for 0.5 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 83 weight percent.
Comparative example 1
The preparation process provided in example 1 was used with the difference that: cement is prepared from the following raw materials in percentage by mass: dihydrate phosphogypsum =1:10, adding an additive accounting for 0 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 70 weight percent.
Comparative example 2
The preparation process provided in example 1 was used, with the difference that: cement is prepared from the following raw materials in percentage by mass: dihydrate phosphogypsum =1:12, adding an additive accounting for 0 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 71 weight percent.
Comparative example 3
The preparation process provided in example 1 was used with the difference that: cement is prepared from the following raw materials in percentage by mass: micro-powder of the phosphorous slag: dihydrate phosphogypsum =0.4:0.6:12, adding an additive accounting for 0 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 72 percent by weight.
Comparative example 4
The preparation process provided in example 1 was used with the difference that: phosphorus slag micropowder according to the following raw material mass ratio: dihydrate phosphogypsum =1:12, adding an additive accounting for 0 percent of the total mass of the raw materials to finally prepare filling paste slurry with the concentration of 72 percent by weight.
The physical and mechanical properties of the slurry of the filling paste prepared by the above preparation method were measured, and the results are shown in table 2.
Table 2 data of physical and mechanical properties of filling paste slurries prepared by different preparation methods
Figure BDA0003897630480000091
The physical mechanical property test standard refers to: the GB/T50080 common concrete mixture performance test method is standard; wherein, the stirred slurry of the filling paste is poured into a test mould with the thickness of 70.7mm multiplied by 70.7mm, the test block is stricken off after the slurry is initially set, and the test block is placed in a constant temperature and humidity curing box (the temperature is 20 +/-1 ℃, and the humidity is 90%) for curing after the slurry is finally set.
Further, a toxicity leaching experiment was performed on a test block formed of the filling paste slurry prepared by the above preparation method, and the results are shown in table 3.
Table 3 toxicity leaching experimental data of test blocks formed by filling paste slurries prepared by different preparation methods
Figure BDA0003897630480000101
The above toxicity leaching experiment standard references: a method for leaching out toxic solid waste, horizontal oscillation method (HJ 557-2010).
As can be seen from Table 2: compared with the comparative example 3, the ash-waste ratio of the examples 2 and 4 is the same, but the coarse aggregates with different proportions are added, the concentration is increased by 6-7%, the strength is increased by 80-100%, and meanwhile, the setting time and the bleeding rate are obviously reduced, so that the underground drainage burden is basically not caused, and the phosphogypsum ball serving as the filling aggregate has an excellent effect; according to the softening coefficients of the examples 1-6 and the comparative examples 1-4, the softening coefficient is generally in the range of 0.9-1.1, and the requirement that the strength of the underground humid environment is not reduced is met; compared with the examples 2 and 4, the examples 3 and 5 have the advantages that after 5 percent of the additive is added, the slurry concentration is increased, the bleeding rate is reduced, the fluidity is increased, and the strength is increased, which shows that the additive has good effect; comparative examples 2-4, the ratio of ash to waste is the same, the ratio of cement to phosphorous slag is different, the filling body without phosphorous slag has higher early strength and tends to be stable for long-term strength, and the added phosphorous slag has obvious improvement effect on the middle and later strength of the filling body, mainly because silicate glass in the phosphorous slag mainlyThe mineral component is dicalcium silicate (2 CaO. SiO) 2 ) And a small amount of tricalcium aluminate (3 CaO. Al) 2 O 3 ) The hydration reaction speed of the dicalcium silicate is slow, so that the dicalcium silicate mainly provides middle and later-stage strength; comparative example 4 found that phosphogypsum cementing only by using phosphorous slag as a gelling agent does not achieve good cementing effect.
As can be seen from Table 3: the toxic leachate of the filler in examples 1-6 and comparative examples 1-2 meets the standard requirement of solid waste type I, and the leachate in comparative example 3 and comparative example 4 has F ion content higher than the standard requirement (more than 10 ppm), which indicates that the cementing material in the formula can not fully solidify the F ions of the filler aggregates.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The phosphogypsum-based underground filling paste is prepared from the following raw materials:
1 part by weight of a cementing material;
6 to 8 weight portions of dihydrate phosphogypsum;
4-6 parts of phosphogypsum balls;
the gel material is prepared from the following components in a mass ratio of 1: (1-2) cement and phosphorous slag.
2. The phosphogypsum-based downhole filling paste according to claim 1, wherein the cement is one or more of 425 portland cement, cement clinker and 525 cement.
3. The phosphogypsum-based underground filling paste as claimed in claim 1, wherein the phosphorus slag is in a micro powder state, the 28d activity is 72-92%, and the average particle size is 10-20 μm.
4. The phosphogypsum-based underground filling paste as claimed in claim 1, wherein the phosphogypsum balls are obtained by disk granulation of semi-hydrated phosphogypsum, the crushing value is 10-35%, the free water content is less than or equal to 10%, and the particle size is 1-25 mm.
5. The phosphogypsum-based downhole filling paste according to any one of claims 1-4, wherein the phosphogypsum-based downhole filling paste further comprises:
additives accounting for 0.4 to 0.6 percent of the total mass of the cementing materials, the dihydrate phosphogypsum and the phosphogypsum balls;
the additive is prepared from an early strength agent, a pumping agent and a high-efficiency water reducing agent.
6. The phosphogypsum-based downhole filling paste according to claim 5, wherein the early strength agent is a chloride salt and/or a sulphate salt.
7. The phosphogypsum-based downhole filling paste according to claim 5, wherein the high-efficiency water-reducing agent is a polycarboxylic acid-based high-performance water-reducing agent.
8. The phosphogypsum-based underground filling paste according to claim 5, wherein the mass ratio of the early strength agent to the pumping agent to the high-efficiency water reducing agent is 1: (0.6-0.8): (0.2-0.4).
9. A method of preparing the phosphogypsum-based downhole packing paste of any one of claims 1 to 4, comprising the steps of:
pre-stirring the cementing material, the dihydrate phosphogypsum and the phosphogypsum balls to obtain a dry material; and adding water and stirring to obtain the phosphogypsum-based underground filling paste.
10. The method of claim 9, wherein the amount of water added is such that the concentration of the resulting phosphogypsum-based downhole filling paste is 77-85%.
CN202211278555.3A 2022-10-19 2022-10-19 Phosphogypsum-based underground filling paste and preparation method thereof Pending CN115490491A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1821547A (en) * 2006-03-30 2006-08-23 中南大学 Method for forming solidified filler by filling phosphorous gypsum in downhole goaf
CN103964804A (en) * 2014-05-12 2014-08-06 中南大学 Low-bleeding-rate pumpable phosphogypsum and yellow phosphorus slag filling paste and preparation method of paste
CN113956011A (en) * 2021-12-07 2022-01-21 贵州川恒化工股份有限公司 Semi-hydrated phosphogypsum-based filling aggregate and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1821547A (en) * 2006-03-30 2006-08-23 中南大学 Method for forming solidified filler by filling phosphorous gypsum in downhole goaf
CN103964804A (en) * 2014-05-12 2014-08-06 中南大学 Low-bleeding-rate pumpable phosphogypsum and yellow phosphorus slag filling paste and preparation method of paste
CN113956011A (en) * 2021-12-07 2022-01-21 贵州川恒化工股份有限公司 Semi-hydrated phosphogypsum-based filling aggregate and preparation method thereof

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Application publication date: 20221220