CN110511052B - Foamed ceramic produced by using tailings of steel plant and preparation method thereof - Google Patents
Foamed ceramic produced by using tailings of steel plant and preparation method thereof Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 60
- 239000010959 steel Substances 0.000 title claims abstract description 60
- 239000000919 ceramic Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 72
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000004927 clay Substances 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 239000006004 Quartz sand Substances 0.000 claims abstract description 9
- 238000010304 firing Methods 0.000 claims description 34
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000002689 soil Substances 0.000 claims description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229910052863 mullite Inorganic materials 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 239000002734 clay mineral Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 238000005086 pumping Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
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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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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Abstract
The invention discloses foamed ceramic produced by utilizing tailings of an iron and steel plant, which is mainly prepared from the following raw materials in parts by weight: 50-60 parts of Luoyuan red tailings, 15-20 parts of furnace slag, 10-20 parts of steel slag, 5-10 parts of quartz sand, 4-10 parts of clay, 0.5-5 parts of foaming agent and 0.1-1 part of stabilizer; the sum of the weight parts of the raw material components is 100 parts; in the steel slag, CaO and MgO are more than or equal to 65 wt%, and in the slag, SiO is contained2+Al2O3More than or equal to 80wt percent. According to the invention, through compounding of the steel slag and the furnace slag, high value-added resource utilization of the tailings of the steel plant is realized. Correspondingly, the invention also discloses a preparation method of the foamed ceramic produced by utilizing the steel plant tailings.
Description
Technical Field
The invention relates to the field of inorganic non-metallic materials, in particular to foamed ceramic produced by utilizing tailings of an iron and steel plant and a preparation method thereof.
Background
The tailings produced in steel plants can be classified into granulated slag, slag and steel slag according to different production processes. Specifically, the granulated slag is iron-making blast furnace slag, and is rapidly cooled by water in a high-temperature molten state to form granulated foam, which is widely used for producing cement and concrete. The slag refers to slag floating on the surface of a smelting furnace in the pyrometallurgical process and can be used as raw materials of cement, slag bricks, slag glass and the like. The steel slag is the tailings generated after oxygen is introduced for decarbonization in the steel-making process. The three slag materials have different production processes, so that the chemical components and the physical and chemical properties of the slag materials have larger differences, and the application occasions of the slag materials also have larger differences.
The existing research for producing foamed ceramics by utilizing the tailings of the steel plant mainly focuses on the aspect of slag because the components of the slag are similar to those of other foamed ceramics. For example, Chinese patent CN108840710A discloses a method for producing a foamed ceramic building thermal insulation material by using lithium tailings and steel slag tailings, which adopts 50-60 parts of lithium tailings, 12-30 parts of steel slag tailings, 20-30 parts of clay raw materials, 2-4 parts of foaming materials and 40-50 parts of water as raw materials to prepare the foamed ceramic with the thermal conductivity coefficient of 0.05-0.062W/m.K, but the compressive strength of the foamed ceramic is only 0.55-1.0 MPa.
In the case of granulated slag and steel slag, the components thereof contain a large amount of CaO and MgO, so that the granulated slag and the steel slag are easy to melt at a low temperature, and the melt formed by melting has a low viscosity, which is not favorable for foaming.
Disclosure of Invention
The invention aims to solve the technical problem of providing foamed ceramic produced by utilizing the tailings of the steel plant, which has the advantages of low heat conductivity coefficient, high compressive strength, high utilization efficiency of the waste residues, energy conservation and environmental protection.
The invention also aims to solve the technical problem of providing a preparation method of the foamed ceramic produced by utilizing the tailings of the steel plant.
In order to solve the technical problems, the invention provides foamed ceramic produced by utilizing tailings of an iron and steel plant, which is mainly prepared from the following raw materials in parts by weight:
50-60 parts of Luoyuan red tailings, 15-20 parts of furnace slag, 10-20 parts of steel slag, 5-10 parts of quartz sand, 4-10 parts of clay, 0.5-5 parts of foaming agent and 0.1-1 part of stabilizer;
the sum of the weight parts of the raw material components is 100 parts;
in the steel slag, CaO + Fe2O3More than or equal to 65 wt%, SiO in the slag2+Al2O3≥80wt％。
As an improvement of the technical scheme, the steel slag mainly comprises the following components in percentage by weight: SiO 22 15～18％，Al2O3 4～6.5％，Fe2O3 38～44％，TiO2 0.1～0.4％，CaO 27～35％，MgO 3～4％，K2O 0.01～0.5％，Na2O 0.01～0.5％。
As an improvement of the technical scheme, the slag mainly comprises the following components in percentage by weight: SiO 22 65～72％，Al2O3 15～20％，Fe2O3 2～3％，TiO2 0.1～0.5％，CaO 2～3％，MgO 0.5～1.5％，K2O 4～6％，Na2O 3～5％，LOI 1～1.5％。
As an improvement of the technical scheme, the clay is one or more of Luo Yuan sand-coated soil, washing mud or black mud.
As an improvement of the technical scheme, the Rouyuan sand-coated soil mainly comprises the following components in percentage by weight: SiO 22 70～75％，Al2O3 12～16％，Fe2O3 0.5～1.5％，CaO 0.3～0.5％，MgO 0.01～0.1％，K2O 4～6％，Na2O 3～5％，LOI 1～5％；
The washing mud mainly comprises the following components in percentage by weight: SiO 22 45～50％，Al2O3 32～36％，Fe2O3 2～3％，CaO 0.01～0.1％，MgO 0.3～0.5％，K2O 2～3％，Na2O 0.3～0.8％，LOI 8～12％；
The black mud mainly comprises the following components in percentage by weight: SiO 22 61～65％，Al2O3 20～24％，Fe2O3 1.5～3％，CaO 0.3～1％，MgO 0.3～0.5％，K2O 1～2％，Na2O 0.2～0.6％，LOI 5～10％；
As an improvement of the technical scheme, the foaming agent is one or more of silicon carbide, carbon powder or ceramic grinding block reclaimed materials; the stabilizing agent is manganese dioxide.
As an improvement of the technical scheme, the compressive strength of the low-thermal-conductivity foamed ceramic is more than or equal to 7MPa, the thermal conductivity coefficient is less than or equal to 0.1W/m.K, and the volume density is 170-250 kg/m3Water absorption not more than 0.5 percent, IRa≤1.0，Ir≤1.0。
Correspondingly, the invention also discloses a preparation method of the foamed ceramic produced by utilizing the steel plant tailings, which comprises the following steps:
(1) uniformly mixing various raw materials according to a formula to obtain a mixture;
(2) performing ball milling on the mixture to obtain slurry;
(3) carrying out spray granulation on the slurry to obtain powder;
(4) distributing the powder into a high-temperature sagger;
(5) and placing the high-temperature sagger in a kiln, and firing according to a preset firing curve to obtain a low-heat-conduction foamed ceramic finished product.
As an improvement of the above technical solution, the firing curve is:
the temperature rise rate is 600-800 ℃/h from room temperature to 1000 ℃;
heating rate of 400-550 ℃/h is adopted from 1000 ℃ to the firing temperature;
keeping the temperature at the firing temperature for 1-1.5 h;
the temperature reduction rate of 500-800 ℃/h is adopted from the firing temperature to 600 ℃;
cooling at the rate of 300-500 ℃/h from 600 ℃ to room temperature;
the firing temperature is 1140-1160 ℃, and the firing period is 5-8 h.
The implementation of the invention has the following beneficial effects:
1. according to the invention, the steel slag and the furnace slag are compounded for use, and the quartz sand is added in the formula, so that the high-temperature melt is thickened, and the foamed ceramic with low thermal conductivity is ensured to be obtained.
2. According to the invention, by compounding the steel slag and the furnace slag, the utilization rate of the steel plant tailings is greatly improved, and the high-added-value resource utilization of the steel plant tailings is realized.
3. The invention ensures that the foamed ceramic has relatively low heat conductivity coefficient (less than or equal to 0.1W/m.K) and relatively high compressive strength (more than or equal to 7MPa) by controlling the firing curve.
Drawings
FIG. 1 is a flow chart of a method for preparing a low thermal conductivity foamed ceramic according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings. It is only noted that the invention is intended to be limited to the specific forms set forth herein, including any reference to the drawings, as well as any other specific forms of embodiments of the invention.
The invention provides foamed ceramic produced by utilizing tailings of an iron and steel plant, which is mainly prepared from the following raw materials in parts by weight:
50-60 parts of Luoyuan red tailings, 15-20 parts of furnace slag, 10-20 parts of steel slag, 5-10 parts of quartz sand, 4-10 parts of clay, 0.5-5 parts of foaming agent and 0.1-1 part of stabilizer; the sum of the weight parts of the raw material components is 100 parts.
Wherein, the steel slag is tailings generated in the process of introducing oxygen to remove carbon in the process of a steel-making process after smelting, and the components of the steel slag contain more Ca and Fe; specifically, in the steel slag, CaO + Fe2O3Not less than 65 wt%. Preferably, the steel slag mainly comprises the following components in percentage by weight: SiO 22 15～18％，Al2O3 4～6.5％，Fe2O3 38～44％，TiO2 0.1～0.4％，CaO 27～35％，MgO 3～4％，K2O 0.01～0.5％，Na2O 0.01～0.5％。
Wherein the slag is a slag material floating on the surface of the molten liquid in the refining process. The composition thereof contains Si and Al in a large amount, and specifically, SiO is contained in the slag2+Al2O3More than or equal to 80wt percent. Preferably, the slag comprises the following components in percentage by weight: SiO 22 65～72％，Al2O3 15～20％，Fe2O3 2～3％，TiO2 0.1～0.5％，CaO 2～3％，MgO 0.5～1.5％，K2O 4～6％，Na23-5% of O and 1-1.5% of LOI. The slag contains Si and Al with higher components, which mainly exist in a primary mullite mineral phase, and can effectively thicken a high-temperature molten melt in the firing process, thereby ensuring the smooth development of a foaming process. Meanwhile, the slag and the steel slag are compounded, so that the recycling of the tailings of the steel plant is realized.
The Luoyuan red tailings are leftover materials and some sawdust and the like in the Luoyuan red processing process, and mainly comprise the following components in percentage by weight: SiO 22 68～73％，Al2O3 12～15％，Fe2O3 1.2～2％，CaO 0.5～1.5％，MgO 0.2～0.5％，K2O 4～5.5％，Na23-5% of O and 0.5-3% of LOI. Al in the Rouyan red tailings of the invention2O312-15 wt% of Al2O3Mainly from feldspar and mica; the mica can be gradually converted into mullite in the high-temperature sintering process, so that the strength is provided for the foamed ceramic; the feldspar mineral can promote the crystallization transformation of mullite and improve the strength. In addition, the existing amount of the Rouyan red tailings is rich, and the chemical components are stable, so that the addition amount of the Rouyan red tailings in the low-heat-conduction foamed ceramic is increased; meanwhile, the Rouyan red tailings do not need to be accumulated and homogenized for a large amount of time like traditional ceramic manufacturers, and the production efficiency is improved to a certain extent.
According to the invention, 10-20 parts of steel slag is added in the formula, so that the firing temperature of the foamed ceramic can be reduced; but because of its CaO and Fe2O3The content of CaO is high, CaO can be melted at 950-1000 ℃, the melt viscosity is low, gas generated by the foaming agent can easily escape through the melt, and the heat conductivity coefficient is increased. The present invention therefore solves this problem by a combination of the following means: firstly, compounding steel slag and furnace slag to increase the mullite content and thicken a high-temperature melt; and 5-10 parts of quartz sand is added in the formula, so that the effect of thickening the melt can be achieved, and the compressive strength of the foamed ceramic can be improved. Finally, 4-10 parts of clay is introduced into the formula, so that the melt viscosity can be effectively reduced, and the compressive strength of the foamed ceramic is improved. Preferably, the weight part of the clay is 5-10 parts.
Specifically, the clay is one or more of Luoyuan sand-coated soil, washing mud or black mud.
Wherein, the Luoyuan sand-coated soil refers to sand on the surface layer of Luoyuan red mine, and mainly comprises the following components in percentage by weight: SiO 22 70～75％，Al2O3 12～16％，Fe2O3 0.5～1.5％，CaO 0.3～0.5％，MgO 0.01～0.1％，K2O 4～6％，Na23-5% of O and 1-5% of LOI; the Royuan sand-coated soil contains higher amount of SiO2A part of SiO2Quartz crystal exists, so that high-temperature melt can be effectively thickened; there is also a portion of SiO2The clay mineral exists in the form of clay mineral, and can be decomposed at high temperature to form primary mullite crystals and thicken high-temperature melt.
Wherein the washing mud is waste mud obtained by washing the Luo Yuan sand-covered soil. The washing mud comprises the following components in percentage by weight: SiO 22 45～50％，Al2O3 32～36％，Fe2O3 2～3％，CaO 0.01～0.1％，MgO 0.3～0.5％，K2O 2～3％，Na20.3-0.8% of O and 8-12% of LOI; the content of alumina in the washing mud is as high as 32-36%, the washing mud is mainly in the form of clay minerals, and the washing mud can be decomposed at high temperature to form primary mullite, thicken high-temperature melt and improve the compressive strength of the foamed ceramic. In addition, the washing mud contains low alkaline earth metal and alkali metal, and the melt viscosity cannot be further reduced.
Wherein the black mud mainly comprises the following components in percentage by weight: SiO 22 61～65％，Al2O3 20～24％，Fe2O3 1.5～3％，CaO 0.3～1％，MgO 0.3～0.5％，K2O 1～2％，Na2O 0.2～0.6％，LOI 5～10％。
Preferably, in the invention, the clay is selected from Luo Yuan sand-covered soil and/or water-washed clay. The materials are all the Luoyuan red tailings, so that the comprehensive utilization efficiency of the Luoyuan red tailings can be effectively improved.
In order to reduce the heat conductivity coefficient of the foamed ceramic, the formula of the foamed ceramic also contains 0.5-5 parts of foaming agent; the foaming agent is selected from one or more of silicon carbide, carbon powder or ceramic grinding block reclaimed materials (the main components are silicon carbide and resin); preferably, silicon carbide is selected. The foaming agent can be decomposed to generate gas in the high-temperature sintering process, and the gas is matched with the grain slag of a steel mill, so that the heat conductivity coefficient of the foamed ceramic is greatly reduced. Preferably, the foaming agent is added in an amount of 0.5 to 3 parts by weight.
In addition, in order to optimize the foaming effect and reduce the thermal conductivity and the volume density, a small amount of stabilizer needs to be added into the formula. Specifically, in the invention, the addition amount of the stabilizer is 0.1-1 part, and the stabilizer is manganese dioxide. Manganese dioxide decomposes at about 900 ℃ to release oxygen, promoting decomposition of the blowing agent. Preferably, the addition weight part of the stabilizer is 0.5-1 part.
In order to improve various properties of the low thermal conductivity foamed ceramic of the present invention, a specific preparation method needs to be matched, and specifically, referring to fig. 1, the preparation method of the low thermal conductivity foamed ceramic of the present invention includes the following steps:
s1: uniformly mixing various raw materials according to a formula to obtain a mixture;
s2: performing ball milling on the mixture to obtain slurry;
wherein the fineness of the slurry is that the screen residue of a 250-mesh screen is less than 0.5%.
S3: carrying out spray granulation on the slurry to obtain powder;
specifically, after the slurry is aged in a slurry tank for 24-48 hours, pumping the slurry to a spray tower for spray drying and granulation; the proportion of particles with more than 40 meshes in the powder obtained by granulation is more than or equal to 20 wt%, and the powder with the particle grading has better fluidity and is beneficial to the subsequent material distribution process.
S4: distributing the powder into a high-temperature sagger;
s5: placing the high-temperature sagger in a kiln, and sintering according to a preset sintering curve to obtain a high-fire-resistant-strength low-heat-conduction foamed ceramic finished product
Wherein the firing curve is as follows:
the temperature rise rate is 600-800 ℃/h from room temperature to 1000 ℃; heating rate of 400-550 ℃/h is adopted from 1000 ℃ to the firing temperature; keeping the temperature at the firing temperature for 1-1.5 h; the temperature reduction rate of 500-800 ℃/h is adopted from the firing temperature to 600 ℃; cooling at the rate of 300-500 ℃/h from 600 ℃ to room temperature; the firing temperature is 1140-1160 ℃, and the firing period is 6-10 h.
The invention adopts a faster heating rate below 1000 ℃, so that the air pressure in the high-temperature liquid phase is released quickly, the density of formed bubble nuclei is large, the aperture is reduced, the open porosity (water absorption) is reduced, the number of gaps on the hole wall is reduced, and the compressive strength of the foamed ceramic is greatly improved. According to experiments, when the temperature rise rate of 200 ℃/h is adopted, the compressive strength of the foamed ceramic is only 0.9-1.18 MPa, and the temperature rise rate is increased to 600 ℃/h, so that the compressive strength can be increased to 7-10 MPa. When the temperature rise rate is more than 800 ℃/h, organic matters in the minerals cannot be decomposed in time, and various defects can be caused. Preferably, the temperature rise rate is 600-700 ℃/h below 1000 ℃.
When the temperature is higher than 1000 ℃, the heating rate is properly reduced, and the foaming agent (SiC) and MnO can be effectively promoted2The thermal conductivity coefficient of the foamed ceramics is reduced. Preferably, the temperature is raised at a rate of 400 to 500 ℃ from 1000 ℃ to the firing temperature. Furthermore, the sintering temperature is kept for 1-1.5 h, the heat preservation time is properly prolonged, the clay mineral phase in the green body can be promoted to be fully decomposed, mullite crystals are separated out, and the compressive strength of the foamed ceramic is improved.
In the cooling process, the temperature is reduced from the firing temperature to 600 ℃ at a cooling rate of 500-800 ℃/h, and the cooling rate can ensure that crystals in the high-temperature melt are fully separated out, so that the foamed ceramic is reinforced. The temperature is reduced from 600 ℃ to room temperature at a rate of 300-500 ℃.
Preferably, the firing temperature is 1140-1160 ℃, and the firing period is 5-8 h.
Under the synergistic effect of the formula and the preparation method, the compressive strength of the foamed ceramic obtained by the invention is more than or equal to 7MPa, the heat conductivity coefficient is less than or equal to 0.1W/m.K, and the volume density is 170-250 kg/m3Water absorption not more than 0.5 percent, IRa≤1.0，Ir≤1.0。
The invention is further illustrated by the following specific examples:
example 1
The embodiment provides a foamed ceramic produced by utilizing tailings of an iron and steel plant, which comprises the following components in percentage by weight:
50 parts of Luoyuan red tailings, 18 parts of furnace slag, 15 parts of steel slag, 8 parts of quartz sand, 6 parts of clay, 2.9 parts of foaming agent and 0.1 part of stabilizing agent;
wherein the clay is black mud, the foaming agent is ceramic grinding block reclaimed material, and the stabilizing agent is MnO2；
Wherein the steel slag comprises the following components: SiO 22 17.1％，Al2O3 6.3％，Fe2O3 38.5％，TiO20.4％，CaO 34.2％，MgO 3.2％，K2O 0.05％，Na2O 0.25％；
The slag consists of the following components: SiO 22 67.1％，Al2O3 16.9％，Fe2O3 2.3％，TiO2 0.4％，CaO 2.3％，MgO 0.9％，K2O 5.3％，Na2O 3.7％，LOI 1.1％；
The preparation method comprises the following steps:
(1) uniformly mixing various raw materials according to a formula to obtain a mixture; a
(2) Performing ball milling on the mixture to obtain slurry;
wherein the fineness of the slurry is that the screen residue of a 250-mesh screen is 0.5%.
(3) Carrying out spray granulation on the slurry to obtain powder;
(4) distributing the powder into a high-temperature sagger;
(5) and (3) placing the high-temperature sagger in a kiln for firing to obtain a low-heat-conduction foamed ceramic finished product.
Wherein, when the sintering is carried out by adopting a roller kiln, the sintering temperature is 1140 ℃, and the sintering period is 8 h.
Example 2
The embodiment provides a foamed ceramic produced by utilizing tailings of an iron and steel plant, which comprises the following components in percentage by weight:
54 parts of Luoyuan red tailings, 16 parts of furnace slag, 14 parts of steel slag, 6 parts of quartz sand, 8 parts of clay, 1.8 parts of foaming agent and 0.2 part of stabilizing agent;
wherein the clay is washed with water, the foaming agent is silicon carbide, and the stabilizer is MnO2。
Wherein the steel slag comprises the following components: SiO 22 17.1％，Al2O3 6.3％，Fe2O3 38.5％，TiO20.4％，CaO 34.2％，MgO 3.2％，K2O 0.05％，Na2O 0.25％；
The slag consists of the following components: SiO 22 67.1％，Al2O3 16.9％，Fe2O3 2.3％，TiO2 0.4％，CaO 2.3％，MgO 0.9％，K2O 5.3％，Na2O 3.7％，LOI 1.1％；
The preparation method comprises the following steps:
(1) uniformly mixing various raw materials according to a formula to obtain a mixture;
(2) performing ball milling on the mixture to obtain slurry;
wherein the fineness of the slurry is that the screen residue of a 250-mesh screen is 0.5%.
(3) Carrying out spray granulation on the slurry to obtain powder;
(4) distributing the powder into a high-temperature sagger;
(5) and (3) placing the high-temperature sagger in a kiln for firing to obtain a low-heat-conduction foamed ceramic finished product.
Wherein, when the roller kiln is adopted for sintering, the sintering temperature is 1145 ℃, and the sintering period is 6 h.
Example 3
The embodiment provides a foamed ceramic produced by utilizing tailings of an iron and steel plant, which comprises the following components in percentage by weight:
58 parts of Luoyuan red tailings, 17 parts of furnace slag, 12 parts of steel slag, 5 parts of quartz sand, 6 parts of washing mud, 1.6 parts of silicon carbide and MnO20.4 part;
wherein the steel slag comprises the following components: SiO 22 16.6％，Al2O3 5.9％，Fe2O3 41.1％，TiO20.4％，CaO 31.9％，MgO 3.7％，K2O 0.1％，Na2O 0.3％。
The slag consists of the following components: SiO 22 69.7％，Al2O3 15.8％，Fe2O3 2.6％，TiO2 0.2％，CaO 2.4％，MgO 0.6％，K2O 4.4％，Na2O 3.1％，LOI 1.2％；
The preparation method is the same as that of example 2.
Example 4
The present example provides a foamed ceramic produced from tailings of an iron and steel plant, and the formulation and the raw material components thereof are the same as those in example 3.
The preparation method was the same as that of example 2 except for the firing profile.
The firing curve is as follows: the temperature rise rate of 620 ℃/h is adopted from room temperature to 1000 ℃;
the temperature rise rate of 450 ℃/h is adopted from 1000 ℃ to 1145 ℃;
keeping the temperature for 1.5h at the firing temperature;
the temperature reduction rate of 560 ℃/h is adopted from the sintering temperature to 600 ℃;
from 600 ℃ to room temperature, the cooling rate of 400 ℃/h is adopted;
the foamed ceramics in the embodiments 1-6 are tested, wherein the method specified in JGT 511-2017 is adopted to test various performances; the test results are shown in the following table:
while the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (8)
1. The foamed ceramic produced by utilizing the tailings of the steel plant is characterized by mainly comprising the following raw materials in parts by weight:
50-60 parts of Luoyuan red tailings, 15-20 parts of furnace slag, 10-20 parts of steel slag, 5-10 parts of quartz sand, 4-10 parts of clay, 0.5-5 parts of foaming agent and 0.1-1 part of stabilizer;
the sum of the weight parts of the raw material components is 100 parts;
in the steel slag, CaO + Fe2O3More than or equal to 65 wt%, SiO in the slag2+Al2O3≥80wt％；
The foaming agent is silicon carbide.
2. The foamed ceramic produced from steel plant tailings as claimed in claim 1, wherein the steel slag mainly comprises the following components in percentage by weight: SiO 22 15～18％，Al2O3 4～6.5％，Fe2O338～44％，TiO2 0.1～0.4％，CaO 27～35％，MgO 3～4％，K2O 0.01～0.5％，Na2O 0.01～0.5％。
3. The foamed ceramic produced from steel plant tailings as claimed in claim 2, wherein the slag consists essentially of the following components in weight percent: SiO 22 65～72％，Al2O3 15～20％，Fe2O32～3％，TiO2 0.1～0.5％，CaO 2～3％，MgO 0.5～1.5％，K2O 4～6％，Na2O 3～5％，LOI 1～1.5％。
4. The foamed ceramic produced from steel plant tailings of claim 3, wherein the clay is selected from one or more of a Luo Yuan sand-covered soil, a washing mud, or a black mud.
5. The foamed ceramic produced from steel plant tailings of claim 4, wherein the Rouyuan sand-coated soil is mainly composed of the following components in percentage by weight: SiO 22 70～75％，Al2O3 12～16％，Fe2O3 0.5～1.5％，CaO 0.3～0.5％，MgO 0.01～0.1％，K2O 4～6％，Na2O 3～5％，LOI 1～5％；
The washing mud mainly comprises the following components in percentage by weight: SiO 22 45～50％，Al2O332～36％，Fe2O32～3％，CaO 0.01～0.1％，MgO 0.3～0.5％，K2O 2～3％，Na2O 0.3～0.8％，LOI 8～12％；
The black mud mainly comprises the following components in percentage by weight: SiO 22 61～65％，Al2O3 20～24％，Fe2O31.5～3％，CaO 0.3～1％，MgO 0.3～0.5％，K2O 1～2％，Na2O 0.2～0.6％，LOI 5～10％。
6. The foamed ceramic produced from tailings of a steel plant according to claim 5, wherein the compressive strength of the low thermal conductivity foamed ceramic is not less than 7MPa, the thermal conductivity is not more than 0.1W/m.K, and the bulk density is 170-250 kg/m3Water absorption not more than 0.5 percent, IRa≤1.0，Ir≤1.0。
7. A method for preparing the foamed ceramic produced by using the steel plant tailings as claimed in any one of claims 1 to 6, comprising:
(1) uniformly mixing various raw materials according to a formula to obtain a mixture;
(2) performing ball milling on the mixture to obtain slurry;
(3) carrying out spray granulation on the slurry to obtain powder;
(4) distributing the powder into a high-temperature sagger;
(5) and placing the high-temperature sagger in a kiln, and firing according to a preset firing curve to obtain a low-heat-conduction foamed ceramic finished product.
8. The method for preparing the foamed ceramic produced by using the tailings of the steel plant according to claim 7, wherein the firing curve is as follows:
the temperature rise rate is 600-800 ℃/h from room temperature to 1000 ℃;
heating rate of 400-550 ℃/h is adopted from 1000 ℃ to the firing temperature;
keeping the temperature at the firing temperature for 1-1.5 h;
the temperature reduction rate of 500-800 ℃/h is adopted from the firing temperature to 600 ℃;
cooling at the rate of 300-500 ℃/h from 600 ℃ to room temperature;
the firing temperature is 1140-1160 ℃, and the firing period is 5-8 h.
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