CN113956011B - Semi-hydrated phosphogypsum-based filling aggregate and preparation method thereof - Google Patents
Semi-hydrated phosphogypsum-based filling aggregate and preparation method thereof Download PDFInfo
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- CN113956011B CN113956011B CN202111485847.XA CN202111485847A CN113956011B CN 113956011 B CN113956011 B CN 113956011B CN 202111485847 A CN202111485847 A CN 202111485847A CN 113956011 B CN113956011 B CN 113956011B
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- hemihydrate
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 135
- 238000011049 filling Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 70
- 239000002893 slag Substances 0.000 claims abstract description 42
- 239000011780 sodium chloride Substances 0.000 claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011574 phosphorus Substances 0.000 claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- 239000002367 phosphate rock Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 18
- -1 phosphogypsum dihydrate Chemical class 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000004568 cement Substances 0.000 claims description 13
- 150000004683 dihydrates Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 230000000740 bleeding effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010440 gypsum Substances 0.000 description 9
- 229910052602 gypsum Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010878 waste rock Substances 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- FPYMUXNASDOMBA-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O.OP(O)(O)=O FPYMUXNASDOMBA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Classifications
-
- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F15/00—Methods or devices for placing filling-up materials in underground workings
- E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a phosphogypsum hemihydrate-based filling aggregate which is formed by granulating a phosphogypsum hemihydrate modified composition; the modified composition of phosphogypsum hemihydrate comprises: 100 weight portions of phosphorus-containing matrix, 0.5 to 3 weight portions of carbide slag and 0.2 to 0.4 weight portion of sodium chloride; the phosphorus-containing matrix comprises one or more of phosphogypsum hemihydrate, phosphogypsum dihydrate and phosphate rock tailings, and at least comprises phosphogypsum hemihydrate. Compared with the prior art, the phosphorus-containing matrix which is easy to convert quickly is granulated into balls to form filling aggregate with strength, and the carbide slag is added to further improve the strength of the filling aggregate, so that the obtained filling aggregate has a good crushing value and is convenient to store, and the caking phenomenon cannot be generated; the filler is used as a filling aggregate, has no harm to the environment, can obviously reduce the bleeding condition of slurry, shortens the final setting time, improves the strength of a filling body, reduces the filling cost, and has good economic benefit, environmental benefit and social benefit.
Description
Technical Field
The invention belongs to the technical field of gypsum building materials, and particularly relates to semi-hydrated phosphogypsum-based filling aggregate and a preparation method thereof.
Background
The phosphogypsum is solid waste residue discharged in the process of producing phosphoric acid, and 4-5 t of phosphogypsum can be produced when 1t of phosphoric acid is produced. At present, the comprehensive utilization rate of the phosphogypsum is low at home and abroad, so that a large amount of phosphogypsum needs to be stockpiled, a large amount of land resources are occupied, and phosphorus, sulfur, fluorine and the like in the phosphogypsum are easy to be carried by rainwater in the rainwater washing process, so that the environmental pollution is caused. Therefore, modification treatment of phosphogypsum has appeared in the prior art, in order to expand the utilization of phosphogypsum.
At present, the main consumption path of phosphogypsum is in the aspects of cement retarders, gypsum building materials, chemical raw materials and the like, and certainly, researchers research the phosphogypsum as an aggregate for mine filling, but the phosphogypsum is not an ideal filling material because the phosphogypsum has the characteristics of small permeability and slurry weakening when meeting water due to extremely fine particles. And because the production processes of the wet-process phosphoric acid are different, the components of the generated byproduct phosphogypsum are also different, and the difficulty of modification treatment and application of the phosphogypsum is further increased.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a high-strength semi-hydrated phosphogypsum-based filling aggregate and a preparation method thereof.
The invention provides a phosphogypsum hemihydrate-based filling aggregate which is formed by granulating a phosphogypsum hemihydrate modified composition;
the modified composition of semi-hydrated phosphogypsum comprises: 100 weight portions of phosphorus-containing matrix, 0.5 to 3 weight portions of carbide slag and 0.2 to 0.4 weight portion of sodium chloride;
the phosphorus-containing matrix comprises one or more of phosphogypsum hemihydrate, phosphogypsum dihydrate and phosphate rock tailings, and at least comprises phosphogypsum hemihydrate.
Preferably, the phosphorus-containing matrix comprises phosphogypsum dihydrate and phosphogypsum hemihydrate, or one of the phosphogypsum dihydrate and the phosphate rock tailings; the mass ratio of one of the dihydrate phosphogypsum and the phosphate rock tailings to the hemihydrate phosphogypsum is (35-50): (50-65).
Preferably, the mass ratio of the semi-hydrated phosphogypsum to the carbide slag is 10: (0.1-0.5).
Preferably, the modified composition of phosphogypsum hemihydrate comprises: 100 parts of semi-hydrated phosphogypsum, 1-3 parts of carbide slag and 0.2-0.4 part of sodium chloride;
or comprises the following steps: 65 parts of semi-hydrated phosphogypsum, 35 parts of dihydrate phosphogypsum, 1-3 parts of carbide slag and 0.2-0.4 part of sodium chloride;
or comprises the following steps: 50 parts of semi-hydrated phosphogypsum, 50 parts of phosphate rock tailings, 0.5-1.5 parts of carbide slag and 0.2-0.4 part of sodium chloride.
Preferably, the modified composition of phosphogypsum hemihydrate comprises: 100 parts of semi-hydrated phosphogypsum, 2.5 parts of carbide slag and 0.3 part of sodium chloride;
or comprises the following steps: 65 parts of semi-hydrated phosphogypsum, 35 parts of dihydrate phosphogypsum, 2.5 parts of carbide slag and 0.3 part of sodium chloride;
or comprises the following steps: 50 parts of semi-hydrated phosphogypsum, 50 parts of phosphate rock tailings, 1.5 parts of carbide slag and 0.3 part of sodium chloride.
Preferably, the hemihydrate phosphogypsum is a byproduct of phosphoric acid production by a hemihydrate phosphoric acid process; the free water content of the semi-hydrated phosphogypsum is 20-25 percent; the crystal water content of the semi-hydrated phosphogypsum is 5-9%.
Preferably, the average particle size of the phosphorite tailings is 10-75 μm; the free water content of the phosphate rock tailings is 10-12%.
The invention also provides a preparation method of the semi-hydrated phosphogypsum-based filling aggregate, which comprises the following steps:
atomizing the mixed aqueous solution of the carbide slag and sodium chloride, mixing the atomized mixed aqueous solution with a phosphorus-containing matrix, and granulating to obtain the semi-hydrated phosphogypsum-based filling aggregate.
The invention also provides filling slurry which comprises the semi-hydrated phosphogypsum-based filling aggregate.
Preferably, the mortar also comprises cement and tailings; the mass ratio of the cement to the tailings to the semi-hydrated phosphogypsum-based filling aggregate is 1: (2-4): (1-3).
The invention provides a semi-hydrated phosphorus gypsum-based filling aggregate which is formed by granulating a semi-hydrated phosphorus gypsum modified composition; the modified composition of semi-hydrated phosphogypsum comprises: 100 weight portions of phosphorus-containing matrix, 0.5 to 3 weight portions of carbide slag and 0.2 to 0.4 weight portion of sodium chloride; the phosphorus-containing matrix comprises one or more of phosphogypsum hemihydrate, phosphogypsum dihydrate and phosphate rock tailings, and at least comprises phosphogypsum hemihydrate. Compared with the prior art, the phosphorus-containing matrix which is easy to convert quickly is granulated and pelletized to form the filling aggregate with strength, and meanwhile, the carbide slag is added to further improve the strength of the filling aggregate, so that the obtained filling aggregate has a good crushing value, can completely replace sandstone, is convenient to store and does not generate caking phenomenon; the filler is used as a filling aggregate, has no harm to the environment, can obviously reduce the bleeding condition of slurry, shortens the final setting time, improves the strength of a filling body, reduces the filling cost, and has good economic benefit, environmental benefit and social benefit.
Drawings
FIG. 1 is a schematic view of the preparation process of the phosphogypsum hemihydrate-based filling aggregate provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a phosphogypsum hemihydrate-based filling aggregate which is formed by granulating a phosphogypsum hemihydrate modified composition; the modified composition of phosphogypsum hemihydrate comprises: 100 weight portions of phosphorus-containing matrix, 0.5 to 3 weight portions of carbide slag and 0.2 to 0.4 weight portion of sodium chloride; the phosphorus-containing matrix comprises one or more of phosphogypsum hemihydrate, phosphogypsum dihydrate and phosphate rock tailings, and at least comprises phosphogypsum hemihydrate.
The modified composition of the semi-hydrated phosphogypsum takes a phosphorus-containing matrix as a main component; the phosphorus-containing matrix comprises one or more of phosphogypsum hemihydrate, phosphogypsum dihydrate and phosphate rock tailings, and at least comprises phosphogypsum hemihydrate; preferably, the phosphorus-containing matrix consists of phosphogypsum hemihydrate or one or both of phosphogypsum dihydrate and phosphate rock tailings and phosphogypsum hemihydrate, and further preferably, the phosphorus-containing matrix consists of phosphogypsum hemihydrate or one of phosphogypsum dihydrate and phosphate rock tailings and phosphogypsum hemihydrate; the mass ratio of one of the phosphogypsum dihydrate and the phosphate rock tailings to the phosphogypsum hemihydrate is preferably (35-50): (50-65); the semi-hydrated phosphogypsum is a by-product of phosphoric acid production by a semi-hydrated phosphoric acid process; the free water content of the semi-hydrated phosphogypsum is preferably 20-25%; the crystal water content of the semi-hydrated phosphogypsum is preferably 5-9%, more preferably 6-8%, and still more preferably 6.5-7.5%; in the examples provided by the invention, the crystal water content of the hemihydrate phosphogypsum is specifically 7.2%, 6.5% or 7.4%; the dihydrate phosphogypsum is a product converted from the hemihydrate phosphogypsum and can also be a byproduct generated in a phosphoric acid process by a dihydrate method; the phosphate rock tailings are fine-grained ores obtained by mineral separation in a phosphate rock separation plant; the average particle size of the phosphate rock tailings is preferably 10-75 mu m; the free water content of the phosphate rock tailings is preferably 10-12%.
The semi-hydrated phosphogypsum modified composition provided by the invention takes carbide slag and sodium chloride as modifiers to modify semi-hydrated phosphogypsum; the mass ratio of the semi-hydrated phosphogypsum to the carbide slag is preferably 10: (0.1 to 0.5), more preferably 10: (0.2 to 0.4), preferably 10: (0.25-0.4).
Preferably, in the present invention, the phosphogypsum hemihydrate modified composition comprises: 100 parts of semi-hydrated phosphogypsum, 1-3 parts of carbide slag and 0.2-0.4 part of sodium chloride;
or comprises the following steps: 65 parts of semi-hydrated phosphogypsum, 35 parts of dihydrate phosphogypsum, 1-3 parts of carbide slag and 0.2-0.4 part of sodium chloride;
or comprises the following steps: 50 parts of semi-hydrated phosphogypsum, 50 parts of phosphorite tailings, 0.5-1.5 parts of carbide slag and 0.2-0.4 part of sodium chloride.
Further preferably, the modified composition of phosphogypsum hemihydrate comprises: 100 parts of semi-hydrated phosphogypsum, 2.5 parts of carbide slag and 0.3 part of sodium chloride;
or comprises the following steps: 65 parts of semi-hydrated phosphogypsum, 35 parts of dihydrate phosphogypsum, 2.5 parts of carbide slag and 0.3 part of sodium chloride;
or comprises the following steps: 50 parts of semi-hydrated phosphogypsum, 50 parts of phosphorite tailings, 1.5 parts of carbide slag and 0.3 part of sodium chloride.
The semi-hydrated phosphorus gypsum-based filling aggregate provided by the invention is formed by granulating the semi-hydrated phosphorus gypsum modified composition; the grain diameter of the semi-hydrated phosphogypsum-based filling aggregate is preferably 5-20 mm; the free water content of the phosphogypsum hemihydrate-based filling aggregate is preferably less than 5 percent, and more preferably less than 3 percent.
The phosphorus-containing matrix which is easy to convert quickly is granulated and pelletized to form filling aggregate with strength, and meanwhile, the carbide slag is added to further improve the strength of the filling aggregate, so that the obtained filling aggregate has a good crushing value, can completely replace sandstone, is convenient to store and does not cause caking; the filler is used as a filling aggregate, has no harm to the environment, can obviously reduce the bleeding condition of slurry, shortens the final setting time, improves the strength of a filling body, reduces the filling cost, and has good economic benefit, environmental benefit and social benefit.
The invention also provides a preparation method of the semi-hydrated phosphogypsum-based filling aggregate, which comprises the following steps: atomizing the mixed aqueous solution of the carbide slag and sodium chloride, mixing the atomized mixed aqueous solution with a phosphorus-containing matrix, and granulating to obtain the semi-hydrated phosphogypsum-based filling aggregate.
Wherein, the sources of all raw materials are not specially limited and can be sold in the market; the types and contents of the carbide slag, the sodium chloride and the phosphorus-containing matrix are the same as those of the carbide slag, the sodium chloride and the phosphorus-containing matrix, and are not described in detail herein.
Referring to fig. 1, fig. 1 is a schematic view of a preparation process of a semi-hydrated phosphogypsum-based filling aggregate provided by the invention.
Atomizing the mixed aqueous solution of the carbide slag and sodium chloride, mixing the atomized mixed aqueous solution with a phosphorus-containing matrix, and granulating; wherein the mass concentration of the carbide slag and the sodium chloride in the mixed aqueous solution is preferably 8-10%; the mixing is preferably carried out in a disk granulator, and the mixed aqueous solution of the carbide slag and the sodium chloride is atomized into the phosphorus-containing matrix by using a spraying system while rotating for granulation.
After granulation and pelletization, natural air drying is preferred, and in the present invention, it is preferred to place the pellets in a well-ventilated place so that they can be quickly air-dried.
And (3) preferably piling the naturally air-dried material until the free water content is less than 5 percent, and more preferably less than 3 percent, thus obtaining the semi-hydrated phosphogypsum-based filling aggregate.
The method has simple process, and the prepared semi-hydrated phosphogypsum-based filling aggregate has good crushing value, can completely replace sandstone, is convenient to store and does not generate caking phenomenon.
The invention also provides filling slurry which comprises the semi-hydrated phosphogypsum-based filling aggregate.
Preferably, the mortar also comprises cement and tailings; the mass ratio of the cement to the tailings to the semi-hydrated phosphogypsum-based filling aggregate is preferably 1: (2-4): (1 to 3), more preferably 1:3:2.
the semi-hydrated phosphogypsum-based filling aggregate provided by the invention is used for preparing filling slurry to fill a mine, so that the mine filling cost can be reduced, and solid waste can be consumed.
In order to further illustrate the present invention, the present invention provides a semi-hydrated phosphogypsum-based filling aggregate and a preparation method thereof, which will be described in detail with reference to examples.
The reagents used in the following examples are all commercially available.
The semi-hydrated phosphogypsum used in the examples is derived from No. 1 fresh semi-hydrated phosphogypsum produced by Hechuan Chemicals GmbH, guizhou, and the specific parameters are shown in the following table:
| water P% | Total P/% | Co-crystal P/%) | Water F/%) | Total F/%) | Free water/% | Water of crystallization/%) | pH |
| 0.48 | 0.87 | 0.57 | 0.24 | 0.59 | 17.52 | 6.05 | 3.82 |
The specific parameters of the carbide slag used in the examples are given in the following table:
the specific parameters of the tailings used in the examples are given in the following table:
| total P/% | Total F/%) | Water P/%) | Water F/%) | pH | Water content% |
| 5.77 | 0.52 | 0.1 | 0.01 | 7.3 | 10.54 |
The specific parameters of the dihydrate gypsum (i.e. aged gypsum) used in the examples are given in the following table:
| free water/%) | Water of crystallization/%) | pH | Total P/%) | Total F/%) | Water P/%) | Water F/%) |
| 12.85 | 19.47 | 3.48 | 0.74 | 0.79 | 0.41 | 0.11 |
The type of cement used in the examples and comparative examples was ordinary 425 cement.
Comparative example 1
The source of the waste rock of the phosphate rock is the waste rock stripped in mining, the waste rock with the particle size range of 5-20 mm is selected after crushing, and the specific parameters are shown in the following table.
Example 1
2.5 parts by weight of carbide slag and 0.3 part by weight of sodium chloride were mixed with water to prepare a mixed solution having a mass concentration of 10%.
100 parts by weight of hemihydrate phosphogypsum with 7.2 percent of crystal water is conveyed to a disc granulator for rotary granulation, and simultaneously, the mixed solution is atomized and added into the hemihydrate phosphogypsum by a spraying system until the particle size is 10mm.
And placing the granulated and pelletized materials in a warehouse with good ventilation capacity for natural air drying, and then piling until the free water content is less than 3 percent to obtain the semi-hydrated phosphogypsum-based filling aggregate.
Example 2
Prepared according to the preparation procedure of example 1, except that the raw materials consist of: 65 parts of hemihydrate phosphogypsum with crystal water of 6.5 percent, 35 parts of dihydrate phosphogypsum, 2.5 parts of carbide slag and 0.3 part of sodium chloride.
Example 3
Prepared according to the preparation procedure of example 1, except that the raw materials consist of: 50 parts of hemihydrate phosphogypsum with 7.4 percent of crystal water, 50 parts of tailings, 1.5 parts of carbide slag and 0.3 part of sodium chloride.
Performance measurement was performed on the phosphogypsum hemihydrate-based filling aggregate obtained in examples 1 to 3 to obtain experimental results as shown in Table 1 below.
TABLE 1 measurement results of the properties of the filling aggregate
| Water content% | Crush value/%) | |
| Comparative example 1 | 0.11 | 15.6 |
| Example 2 | 2.72 | 17.4 |
| Example 3 | 3.6 | 27.8 |
| Example 4 | 1.86 | 23.5 |
From the test results, it can be seen that: examples 1-3 had higher water content and crush values than comparative example 1, indicating that the strength of the gypsum pellets was slightly less than that of crushed stone.
Comparative example 2
According to the semi-hydrated phosphogypsum: and (3) adding water to prepare filling slurry with the solid content of 74 percent, wherein the tailings = 1.
Comparative example 3
According to the cement: tailing: comparative example 1=1, and water was added to prepare a filling slurry having a solid content of 76%.
Example 4
According to the cement: tailing: example 2=1, and water was added to prepare a filling slurry having a solid content of 76%.
Example 5
According to the cement: tailing: example 3=1, and water was added to prepare a filler slurry having a solid content of 76%.
Example 6
According to the cement: tailing: example 4=1, and water was added to prepare a filler slurry having a solid content of 76%.
The performance of the filling slurry prepared by the method is measured according to JGJ _ T70-2009 building mortar basic performance test method standard, and the test results shown in the following table 2 are obtained.
TABLE 2 measurement results of properties of the filling slurries
From the test results, it can be seen that: comparative example 3 is the same as comparative example 1 in the ratio of ash to waste, but the addition of coarse aggregate increases the strength to a certain extent but does not reduce the bleeding of the slurry; in contrast, in examples 4 to 6, the slurry setting time was shortened, the bleeding rate was decreased, and the strength of the filler was significantly increased, as compared with comparative examples 2 and 3. The phosphogypsum hemihydrate-based filling aggregate has good filling effect.
Claims (8)
1. The phosphogypsum hemihydrate-based filling aggregate is characterized by being formed by granulating a phosphogypsum hemihydrate modified composition;
the modified composition of semi-hydrated phosphogypsum comprises: 100 parts of phosphorus-containing matrix, 0.5 to 3 parts of carbide slag and 0.2 to 0.4 part of sodium chloride;
the phosphorus-containing matrix comprises one or more of phosphogypsum hemihydrate, phosphogypsum dihydrate and phosphate rock tailings, and at least comprises phosphogypsum hemihydrate;
the phosphorus-containing matrix comprises one of phosphogypsum dihydrate and phosphate rock tailings and phosphogypsum hemihydrate; the mass ratio of one of the dihydrate phosphogypsum and the phosphate rock tailings to the hemihydrate phosphogypsum is (35 to 50): (50 to 65);
the mass ratio of the semi-hydrated phosphogypsum to the carbide slag is 10: (0.1 to 0.5).
2. The phosphogypsum hemihydrate-based filling aggregate of claim 1, wherein the phosphogypsum hemihydrate modified composition comprises: 100 parts of semi-hydrated phosphogypsum, 1 to 3 parts of carbide slag and 0.2 to 0.4 part of sodium chloride;
or comprises the following steps: 65 parts of semi-hydrated phosphogypsum, 35 parts of dihydrate phosphogypsum, 1 to 3 parts of carbide slag and 0.2 to 0.4 part of sodium chloride;
or comprises the following steps: 50 parts of semi-hydrated phosphogypsum, 50 parts of phosphate rock tailings, 0.5 to 1.5 parts of carbide slag and 0.2 to 0.4 part of sodium chloride.
3. The phosphogypsum hemihydrate-based filling aggregate of claim 1, wherein the phosphogypsum hemihydrate modified composition comprises: 100 parts of semi-hydrated phosphogypsum, 2.5 parts of carbide slag and 0.3 part of sodium chloride;
or comprises the following steps: 65 parts of semi-hydrated phosphogypsum, 35 parts of dihydrate phosphogypsum, 2.5 parts of carbide slag and 0.3 part of sodium chloride;
or comprises the following steps: 50 parts of semi-hydrated phosphogypsum, 50 parts of phosphate rock tailings, 1.5 parts of carbide slag and 0.3 part of sodium chloride.
4. The semi-hydrated phosphogypsum-based filling aggregate of claim 1, which is a by-product of the phosphoric acid production of the semi-hydrated phosphoric acid process; the free water content of the semi-hydrated phosphogypsum is 20% -25%; the crystal water content of the semi-hydrated phosphogypsum is 5% -9%.
5. The semi-hydrated phosphogypsum-based filling aggregate as claimed in claim 1, which is characterized in that the average particle size of the phosphate rock tailings is 10 to 75 μm; the free water content of the phosphate ore tailings is 10% -12%.
6. The method for preparing a phosphogypsum hemihydrate-based filling aggregate according to claim 1, which comprises:
atomizing the mixed aqueous solution of the carbide slag and sodium chloride, mixing the atomized mixed aqueous solution with a phosphorus-containing matrix, and granulating to obtain the semi-hydrated phosphogypsum-based filling aggregate.
7. A filling slurry comprising the phosphogypsum hemihydrate-based filling aggregate according to any one of claims 1 to 5.
8. The filler slurry according to claim 7, further comprising cement and tailings; the mass ratio of the cement to the tailings to the semi-hydrated phosphogypsum-based filling aggregate is 1: (2 to 4): (1 to 3).
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