CN113307602A - Preparation method of red mud building material - Google Patents
Preparation method of red mud building material Download PDFInfo
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- CN113307602A CN113307602A CN202110645749.1A CN202110645749A CN113307602A CN 113307602 A CN113307602 A CN 113307602A CN 202110645749 A CN202110645749 A CN 202110645749A CN 113307602 A CN113307602 A CN 113307602A
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- red mud
- building material
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- mud
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- 239000004566 building material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 54
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 39
- 239000010452 phosphate Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000003825 pressing Methods 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- -1 aluminum tripolyphosphate trihydrate Chemical class 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000011019 hematite Substances 0.000 claims description 3
- 229910052595 hematite Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000009628 steelmaking Methods 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 abstract description 6
- 230000003179 granulation Effects 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 230000009967 tasteless effect Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 235000021317 phosphate Nutrition 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910004856 P—O—P Inorganic materials 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- HCWPIIXVSYCSAN-IGMARMGPSA-N Radium-226 Chemical compound [226Ra] HCWPIIXVSYCSAN-IGMARMGPSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- ZSLUVFAKFWKJRC-UHFFFAOYSA-N thorium Chemical compound [Th] ZSLUVFAKFWKJRC-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C04B28/34—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 cold phosphate binders
- C04B28/344—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 cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
- C04B2111/00258—Electromagnetic wave absorbing or shielding materials
-
- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
-
- 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
Abstract
The invention provides a preparation method of a red mud building material. The red mud building material is finally prepared by mixing the red mud, the shielding material and the gelled material to obtain the red mud phosphate gelled material, and carrying out mud forming, granulation, curing pressing and sintering treatment. The red mud building material comprises building components, decorative plates, pavement materials and other products with heat resistance below 1500 ℃, and has the characteristics of no toxicity, no radioactivity, high strength, compactness and the like. The method is simple and short in flow, and can shield the radioactivity of the red mud, so that the red mud reaches the national standard nuclide limit requirement of building materials. And the high-strength red mud building material which is nontoxic, tasteless, pollution-free, corrosion-resistant and high-temperature-resistant is obtained while the radioactivity is shielded. Thereby being capable of consuming and utilizing the red mud in a large scale and changing waste into valuable.
Description
Technical Field
The invention relates to the field of red mud recycling, in particular to a preparation method of a red mud building material.
Background
The red mud is used as solid waste in the electrolytic aluminum industry, has strong alkalinity, and some red mud also has radioactivity. By the end of 2020, at least 3 hundred million tons of electrolytic aluminum red mud in China can be stacked in the open air, and in order to avoid air pollution caused by floating of the electrolytic aluminum red mud in the air, watering is needed, and a certain humidity is kept, so that the electrolytic aluminum red mud is stored in a wet red mud block mode. Along with the industrial development of electrolytic aluminum, more and more red mud can be stacked, so that the environmental pollution is brought, the injury risk of people is increased, and the surrounding environment cannot realize green ecology.
How to treat and digest red mud is a long standing issue. Some investigation and study appear on the radioactivity of the red mud, but no practical industrial strategy exists; some researches and patents on dealkalization process of the strong basicity of the red mud appear, however, dealkalization not only has large investment, but also brings a series of problems of secondary environmental pollution and additional cost increase. At present, no simple industrial method for consuming a large amount of red mud and utilizing the red mud is available.
The manufacture of building materials is one of the outlets of a large group of consumed red mud. As for conventional building materials and building products such as red mud cement, red mud wall bricks, red mud baking-free bricks and red mud pavement bricks, the radioactive raw material red mud is used, and the shielding radioactivity is the first factor. The building materials and products containing red mud have low general strength, and the improvement of the strength of the products containing red mud is the second factor. The acidic phosphate inorganic adhesive is a high-temperature-resistant inorganic binder and is widely applied to the aspects of casting sand mold curing, refractory material amorphous castable, ceramic heat-resistant coatings on the surfaces of aerospace alloy parts and the like. When the phosphate is mixed and glued with the red mud powder in the form of glue with a certain concentration, the water-soluble phosphate colloid forms a three-dimensional communication network among the red mud oxide particles, more than 70 percent of the red mud particles have the size of about 200nm, and the phosphate colloid network and the water-soluble phosphate colloid form a liquid-solid microscopic composite material. The phosphate adhesive has excellent wettability with oxide surface in red mud, can be fully spread and firmly adhered with each other. The strong basicity of red mud is a necessary condition for acid phosphate solidification. The red mud does not need dealkalization and can meet the requirement of phosphate solidification. The strong alkaline 'defect' of the red mud is changed into 'advantage'. Liquid phase phosphates may change from a solid phase at room temperature or upon heating, referred to as curing. The intrinsic strength (theoretical strength) of the cured phosphate can reach 110 MPa. Certain ceramic particles in the phosphate are driven to contact with various oxide particles in the red mud due to the fluidity of the glue, and are diffused at a higher temperature to form various solid solutions, the strength of the phosphate is superposed with the strength of the red mud, so that the strength of the microcosmic composite material is further increased, and the defect of low strength of the conventional red mud-clay and red mud-waste residue materials is eliminated.
Disclosure of Invention
The invention aims to provide a preparation method of a red mud building material, which adopts red mud, shielding materials and gelled materials as main raw materials to prepare the red mud building material, can realize large-scale industrial consumption and utilization of the red mud, and realizes changing waste into valuables.
In order to achieve the purpose, the invention provides a preparation method of a red mud building material, which comprises the following steps:
step 1, providing a main material and an auxiliary material, wherein the main material comprises red mud, a shielding material and a gelling material, and the auxiliary material comprises boric acid powder, polyethylene glycol powder and micro-powder wax powder;
step 2, adding water into the main materials and the auxiliary materials, uniformly stirring, standing and aging to obtain thick slurry;
step 3, sieving the thick mud, and forming a red mud premix after the water in the thick mud is evaporated;
step 4, granulating the red mud premix at room temperature to prepare a flowing mud granule;
step 5, filling the flowing mud pellets into a mold, and pressing and forming to form a green body;
and 6, sintering the green body to form the red mud building material.
Red mud is red mud blocks which are used in a red mud piling yard for removing macroscopic impurities; the shielding material is one or more of iron powder, hematite powder, magnetite powder, iron-making waste slag powder, steel-making waste slag powder, strontium oxide, bismuth oxide, boron oxide and zirconium oxide; the gelled material is water-soluble high-temperature phosphate inorganic glue.
The preparation method of the water-soluble high-temperature phosphate inorganic adhesive comprises the following steps: a small amount of magnesia-alumina spinel, magnesia, quartz, alumina and zirconia are added into the water-soluble phosphate inorganic glue to form the 1500 ℃ resistant water-soluble high-temperature phosphate inorganic glue.
The content of the red mud in the main material is more than 90 wt%; the content of the boric acid powder, the polyethylene glycol powder and the micro powder wax powder is less than 1 wt% of the main material.
In the step 2, the water/solid ratio of the thick slurry is 1: 5-1: 10.
The stirring process in the step 2 comprises primary stirring and fine stirring; the initial stirring speed is 10-20 rpm, and the stirring time is 15-25 min; the fine stirring speed is 50-80 rpm, and the stirring time is 15-25 min.
In the step 3, the water content of the red mud premix is 6-8%.
Step 5, room temperature pressing or warm pressing is adopted;
the room temperature pressing process is that the flowing mud granules are put into a closed steel die at room temperature, and the pressing pressure is 25-200 Mpa, so that green bodies are obtained; the warm pressing process is that the flowing mud particles are heated to 90-110 ℃, put into a die and applied with pressing pressure of 25-100 MPa to obtain a green body.
The step 6 adopts vacuum sintering treatment, and the vacuum sintering treatment specifically comprises the following steps: providing a vacuum sintering furnace, placing the green body in the vacuum sintering furnace, gradually raising the temperature in the vacuum sintering furnace, firstly removing air adsorbed by the red mud phosphate glued green body, then discharging adsorbed water, and then discharging crystal water and volatilizing a lubricant; the phosphate is subjected to condensation reaction at the primary curing temperature to generate aluminum tripolyphosphate and aluminum tripolyphosphate trihydrate; after the mixture is completely cured, phosphate reacts to generate hexagonal aluminum metaphosphate; the strength of the green body is gradually improved within the temperature range of 500-700 ℃, and when the temperature is 545-555 ℃, the hexagonal aluminum metaphosphate is converted into the cubic aluminum metaphosphate; and (3) preserving the heat for 1-3 hours at the temperature of 800-1100 ℃, wherein oxides in the red mud and oxides decomposed from phosphate are diffused and consolidated to form a high-temperature glass phase or a ceramic phase, and the strength of a sintered blank is remarkably improved in the strengthening and compacting process to form the red mud building material.
The primary curing temperature is 250-350 ℃, and the strength of the red mud building material is 75-100 Mpa.
The invention has the beneficial effects that: the invention provides a preparation method of a red mud building material. The red mud building material is finally prepared by mixing the red mud, the shielding material and the gelled material to obtain the red mud phosphate gelled material, and carrying out mud forming, granulation, curing pressing and sintering treatment. The red mud building material comprises building components, decorative plates, pavement materials and other products with heat resistance below 1500 ℃, and has the characteristics of no toxicity, no radioactivity, high strength, compactness and the like. The method is simple and short in flow, and can shield the radioactivity of the red mud, so that the red mud reaches the national standard nuclide limit requirement of building materials. And the high-strength red mud building material which is nontoxic, tasteless, pollution-free, corrosion-resistant and high-temperature-resistant is obtained while the radioactivity is shielded. Thereby being capable of consuming and utilizing the red mud in a large scale and changing waste into valuable.
Detailed Description
To further illustrate the technical means adopted by the present invention and the effects thereof, the following detailed description is given with reference to the preferred embodiments of the present invention.
The invention adopts a production method which is simple to operate and can realize large-scale industrialization, and the radioactivity of the red mud can be shielded, so that the red mud reaches the national standard nuclide limit requirement of building materials. While shielding radioactivity, the high-strength red mud building material which is nontoxic, tasteless, pollution-free, corrosion-resistant and high-temperature-resistant is obtained, and a reliable technical guarantee is provided for large-scale consumption and utilization of red mud.
Specifically, the invention provides a preparation method of a red mud building material, which comprises the following steps:
step 1, providing main materials and auxiliary materials, wherein the main materials comprise red mud, shielding materials and gelling materials, and the auxiliary materials comprise boric acid powder, polyethylene glycol powder and micro-powder wax powder.
Specifically, the content of the red mud in the main material is more than 90 wt%. The red mud is directly used as red mud blocks for removing macroscopic impurities such as branches, leaves and miscellaneous stone blocks in a red mud piling field. The raw material red mud is large in consumption, the red mud which is piled for a long time or produced newly does not need to be distinguished, drying, crushing, grinding and granularity grading are not needed, the working procedures are few, and the production cost is greatly reduced.
The shielding material is one or more of iron powder, hematite powder, magnetite powder, iron-making waste slag powder, steel-making waste slag powder and strontium oxide, bismuth oxide, boron oxide and zirconium oxide, and can shield the radioactivity of radioactive substances such as radioactive radium-226, thorium-232 and the like.
The gelled material is water-soluble high-temperature phosphate inorganic glue. The preparation method of the water-soluble high-temperature phosphate inorganic adhesive comprises the following steps: a small amount of fillers such as magnesia-alumina spinel, magnesia, quartz, alumina, zirconia and the like are added into the water-soluble phosphate inorganic adhesive to form the 1500 ℃ resistant water-soluble high-temperature phosphate inorganic adhesive.
The content of the boric acid powder, the polyethylene glycol powder and the micro powder wax powder is less than 1 wt% of the main material.
And 2, adding water into the main material and the auxiliary material, uniformly stirring, standing and aging to obtain the thick slurry.
Specifically, the content of the water added in the step 2 depends on the water content in the red mud, the water in the thick slurry is the added water plus the water contained in the red mud, and the water/solid ratio of the thick slurry is 1: 5-1: 10. Optionally, the water/solid ratio of the thick slurry is 1:5, 1:7, or 1: 10.
The stirring process in the step 2 comprises primary stirring and fine stirring. The initial stirring speed is 10-20 rpm, and the stirring time is 15-25 min; the fine stirring speed is 50-80 rpm, and the stirring time is 15-25 min. During the stirring process, there is an exothermic reaction between the mixed materials and water, so care should be taken to eliminate local agglomerated lumps.
Preferably, the stirring time for both the initial stirring and the fine stirring is 20 min.
And 3, sieving the thick mud, and forming the red mud premix after the water in the thick mud is evaporated.
Specifically, in the step 3, the thick slurry is sieved through a square-hole sieve with 25 meshes (which is equivalent to a vibrating sieve with 20 meshes).
The water content of the red mud premix is 6-8%.
And 4, granulating the red mud premix at room temperature to prepare the flowing mud granules.
Specifically, the step 4 adopts manual granulation or granulation by a granulator.
In the step 4, since the granulation is carried out at room temperature and the temperature is far lower than the primary curing temperature of the phosphate, hard agglomeration is not formed between the granules, so that the flowing mud granules with fluidity are prepared.
And 5, filling the flowing mud particles into a mold, and pressing and forming to form a green body.
And the step 5 adopts room temperature pressing or warm pressing. And the room temperature pressing process is that the flowing mud granules are put into a closed steel die at room temperature, and the pressing pressure is 25-200 Mpa, so that green bodies are obtained. The warm pressing process is that the flowing mud particles are heated to 90-110 ℃, put into a die and applied with pressing pressure of 25-100 MPa to obtain a green body.
Preferably, the fluid mud pellets are heated to 100 ℃ during warm pressing.
And 6, sintering the green body to form the red mud building material.
Specifically, step 6 adopts a vacuum sintering process, and the vacuum sintering process specifically includes: and providing a vacuum sintering furnace, placing the green body in the vacuum sintering furnace, gradually raising the temperature in the vacuum sintering furnace, firstly removing air adsorbed by the red mud phosphate glued green body, then discharging adsorbed water, and then discharging crystal water and volatilizing a lubricant. The phosphate is subjected to condensation reaction at the primary curing temperature to generate aluminum tripolyphosphate and aluminum tripolyphosphate trihydrate, and one molecule of H is removed from P-O-H and P-O-H2O, becomes a linear P-O-P bond, and has partial cohesive force. After complete curing, the phosphate reacts to form hexagonal aluminum metaphosphate and the linear P-O-P changes to a cyclic P-O-P structure which provides the bonding force. The strength of the green body is gradually improved within the temperature range of 500-700 ℃. And at a temperature of 545 ℃ to 555 ℃, the hexagonal aluminum metaphosphate is converted into the cubic aluminum metaphosphate. Keeping the temperature at 800-1100 ℃ for 1-3 hours, preferably 2 hours, in the red mudThe oxide of the red mud is diffused and consolidated with the oxide decomposed from the phosphate to form a high-temperature glass phase or ceramic phase, such as calcium iron aluminate, magnesium aluminum silicate, aluminum silicate and the like, the densification process is strengthened, the strength of a sintering blank is obviously improved, and the red mud building material is formed. The strength of the red mud building material tends to be the maximum value and reaches 75-100 MPa.
The primary curing temperature is 250-350 ℃, preferably 300 ℃.
The red mud building material comprises various building components, decorative plates, pavement materials and other products (such as blocks, particles and powder materials) with heat resistance below 1500 ℃.
In conclusion, the invention provides a preparation method of the red mud building material. The red mud building material is finally prepared by mixing the red mud, the shielding material and the gelled material to obtain the red mud phosphate gelled material, and carrying out mud forming, granulation, curing pressing and sintering treatment. The red mud building material comprises building components, decorative plates, pavement materials and other products with heat resistance below 1500 ℃, and has the characteristics of no toxicity, no radioactivity, high strength, compactness and the like. The method is simple and short in flow, and can shield the radioactivity of the red mud, so that the red mud reaches the national standard nuclide limit requirement of building materials. And the high-strength red mud building material which is nontoxic, tasteless, pollution-free, corrosion-resistant and high-temperature-resistant is obtained while the radioactivity is shielded. Thereby being capable of consuming and utilizing the red mud in a large scale and changing waste into valuable.
As described above, it will be apparent to those skilled in the art that various other changes and modifications can be made based on the technical solution and the technical idea of the present invention, and all such changes and modifications should fall within the protective scope of the appended claims.
Claims (10)
1. The preparation method of the red mud building material is characterized by comprising the following steps:
step 1, providing a main material and an auxiliary material, wherein the main material comprises red mud, a shielding material and a gelling material, and the auxiliary material comprises boric acid powder, polyethylene glycol powder and micro-powder wax powder;
step 2, adding water into the main materials and the auxiliary materials, uniformly stirring, standing and aging to obtain thick slurry;
step 3, sieving the thick mud, and forming a red mud premix after the water in the thick mud is evaporated;
step 4, granulating the red mud premix at room temperature to prepare a flowing mud granule;
step 5, filling the flowing mud pellets into a mold, and pressing and forming to form a green body;
and 6, sintering the green body to form the red mud building material.
2. The method for preparing the red mud building material according to claim 1, wherein the red mud is red mud blocks from which macroscopic impurities are removed in a red mud yard; the shielding material is one or more of iron powder, hematite powder, magnetite powder, iron-making waste slag powder, steel-making waste slag powder, strontium oxide, bismuth oxide, boron oxide and zirconium oxide; the gelled material is water-soluble high-temperature phosphate inorganic glue.
3. The preparation method of the red mud building material of claim 2, wherein the preparation method of the water-soluble high-temperature phosphate inorganic adhesive comprises the following steps: a small amount of magnesia-alumina spinel, magnesia, quartz, alumina and zirconia are added into the water-soluble phosphate inorganic glue to form the 1500 ℃ resistant water-soluble high-temperature phosphate inorganic glue.
4. The method for preparing the red mud building material of claim 1, wherein the content of the red mud in the main material is more than 90 wt%; the content of the boric acid powder, the polyethylene glycol powder and the micro powder wax powder is less than 1 wt% of the main material.
5. The preparation method of the red mud building material of claim 1, wherein in the step 2, the water/solid ratio of the thick mud slurry is 1: 5-1: 10.
6. The method for preparing the red mud building material of claim 1, wherein the stirring process in the step 2 is divided into primary stirring and fine stirring; the initial stirring speed is 10-20 rpm, and the stirring time is 15-25 min; the fine stirring speed is 50-80 rpm, and the stirring time is 15-25 min.
7. The method for preparing the red mud building material of claim 1, wherein in the step 3, the water content of the red mud premix is 6-8%.
8. The method for preparing the red mud building material of claim 1, wherein the step 5 adopts room temperature pressing or warm pressing;
the room temperature pressing process is that the flowing mud granules are put into a closed steel die at room temperature, and the pressing pressure is 25-200 Mpa, so that green bodies are obtained; the warm pressing process is that the flowing mud particles are heated to 90-110 ℃, put into a die and applied with pressing pressure of 25-100 MPa to obtain a green body.
9. The preparation method of the red mud building material of claim 1, wherein the step 6 adopts a vacuum sintering treatment, and the vacuum sintering treatment specifically comprises: providing a vacuum sintering furnace, placing the green body in the vacuum sintering furnace, gradually raising the temperature in the vacuum sintering furnace, firstly removing air adsorbed by the red mud phosphate glued green body, then discharging adsorbed water, and then discharging crystal water and volatilizing a lubricant; the phosphate is subjected to condensation reaction at the primary curing temperature to generate aluminum tripolyphosphate and aluminum tripolyphosphate trihydrate; after the mixture is completely cured, phosphate reacts to generate hexagonal aluminum metaphosphate; the strength of the green body is gradually improved within the temperature range of 500-700 ℃, and when the temperature is 545-555 ℃, the hexagonal aluminum metaphosphate is converted into the cubic aluminum metaphosphate; and (3) preserving the heat for 1-3 hours at the temperature of 800-1100 ℃, wherein oxides in the red mud and oxides decomposed from phosphate are diffused and consolidated to form a high-temperature glass phase or a ceramic phase, and the strength of a sintered blank is remarkably improved in the strengthening and compacting process to form the red mud building material.
10. The method for preparing the red mud building material of claim 9, wherein the primary curing temperature is 250-350 ℃, and the strength of the red mud building material is 75-100 Mpa.
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