CN112430108B - Method for preparing refractory material by using copper smelting slag as raw material - Google Patents
Method for preparing refractory material by using copper smelting slag as raw material Download PDFInfo
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- CN112430108B CN112430108B CN202011450445.1A CN202011450445A CN112430108B CN 112430108 B CN112430108 B CN 112430108B CN 202011450445 A CN202011450445 A CN 202011450445A CN 112430108 B CN112430108 B CN 112430108B
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- copper smelting
- smelting slag
- magnesite
- refractory material
- magnesia
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 56
- 239000010949 copper Substances 0.000 title claims abstract description 56
- 239000002893 slag Substances 0.000 title claims abstract description 54
- 238000003723 Smelting Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000011819 refractory material Substances 0.000 title claims abstract description 32
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 7
- 239000007767 bonding agent Substances 0.000 claims abstract description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 48
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 48
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 48
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 48
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002386 leaching Methods 0.000 claims description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000002910 solid waste Substances 0.000 abstract description 5
- 230000009970 fire resistant effect Effects 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052609 olivine Inorganic materials 0.000 description 4
- 239000010450 olivine Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- -1 pulp Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
-
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention belongs to the technical field of resource utilization of solid wastes, and particularly relates to a method for preparing a refractory material by using copper smelting slag as a raw material. The method for preparing the refractory material by taking the copper smelting slag as the raw material comprises the following steps: mixing copper smelting slag, magnesia and a bonding agent, and carrying out ball milling to obtain a mixture; and sequentially carrying out forming treatment, drying and sintering on the mixture to obtain the refractory material. The test result of the embodiment shows that the density of the refractory material obtained by the method is 1.752-2.359 g/cm3The density is moderate; the heat conductivity coefficient is 0.46-1.03W/mK, and the heat conductivity coefficient is low; the highest service temperature is 1250-1300 ℃, and the fire-resistant temperature is high; the compressive strength is 184.3-201.3 MPa, the compressive strength is high, the deformation is not easy, and the resource utilization of the copper smelting slag is realized.
Description
Technical Field
The invention belongs to the technical field of resource utilization of solid wastes, and particularly relates to a method for preparing a refractory material by using copper smelting slag as a raw material.
Background
Copper smelting slag is a main solid waste in the copper metallurgy industry, and the chemical components of copper ores may be different to a certain extent due to different grades and smelting processes of the copper ores, but the copper smelting slag generally contains iron, silicon, aluminum, magnesium, calcium, copper and zinc elements, a small amount of lead and other harmful elements in the form of oxides. In the past, copper smelting slag is generally used as an abrasive for derusting, building materials for building roads or stockpiling. Non-ferrous metallurgy enterprises dump copper smelting slag in the open air, not only occupy a large amount of land resources, but also can cause serious threat to the environment. Due to the coexistence of multiple metals such as copper, iron, lead, zinc and the like in the copper smelting slag, low crystallization degree and high dispersion of valuable elements, the technical problem that the valuable elements cannot be effectively utilized exists in the copper smelting slag, and the comprehensive utilization rate of the copper smelting slag is extremely low.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a refractory material from copper smelting slag as a raw material, and the method provided by the present invention uses copper smelting slag as a raw material, and the obtained refractory material has characteristics of high strength and low thermal conductivity, so that resource utilization of copper smelting slag is realized.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a method for preparing a refractory material by taking copper smelting slag as a raw material, which comprises the following steps:
mixing copper smelting slag, magnesia and a bonding agent, and carrying out ball milling to obtain a mixture;
and sequentially carrying out forming treatment, drying and sintering on the mixture to obtain the refractory material.
Preferably, the mass ratio of the copper smelting slag to the magnesia is (68-80): (20 to 32).
Preferably, the binder comprises one or more of resin, rubber, pulp and magnesium chloride.
Preferably, the ratio of the total mass of the copper smelting slag and the magnesia to the mass of the binding agent is 100: (0.5 to 14).
Preferably, the magnesite is prepared from low-grade magnesite; the content of magnesium oxide in the low-grade magnesite is less than or equal to 45 wt.%; the magnesite is prepared by a preparation method comprising the following steps:
sequentially crushing and calcining the low-grade magnesite to obtain magnesite light-burned powder;
leaching the magnesite light-burned powder by using an ammonium chloride aqueous solution to obtain a leaching solution;
and mixing the leachate with ammonia water, sequentially carrying out magnesium precipitation reaction and solid-liquid separation, and roasting the obtained solid phase to obtain the magnesia.
Preferably, the concentration of the ammonium chloride aqueous solution is 2-3 mol/L; the ratio of the volume of the ammonium chloride aqueous solution to the mass of the magnesite light-burned powder is (9-10) L: 1 kg.
Preferably, the concentration of the ammonia water is 5-8 mol/L, and the volume ratio of the leaching solution to the ammonia water is (0.8-1.2): 1; the temperature of the magnesium precipitation reaction is 40-50 ℃, and the time is 60-70 min.
Preferably, the ball-to-material ratio of the ball mill is (1.5-2): 1, the rotation speed is 300-500 rpm, and the time is 20-25 min.
Preferably, the forming process is cold press forming; the pressure of the cold press molding is 50-200 MPa, and the pressure maintaining time is 10-30 min.
Preferably, the sintering temperature is 1350-1400 ℃, and the time is 2-8 h.
The invention provides a method for preparing a refractory material by taking copper smelting slag as a raw material, which comprises the following steps: mixing copper smelting slag, magnesia and a bonding agent, and carrying out ball milling to obtain a mixture; and sequentially carrying out forming treatment, drying and sintering on the mixture to obtain the refractory material. In the invention, the copper smelting slag contains rich Fe and SiO2And Al2O3Can be sintered and fused with MgO in magnesia, MgO and SiO2The reaction produces forsterite and enstatite of high melting point, and MgO and Fe2O3Or Al2O3The reaction generates corresponding magnesia spinel with high melting point, which is beneficial to improving the refractoriness of the material and obtaining the refractory material with good compressive strength and low heat conductivity coefficient.
The test result of the embodiment shows that the density of the refractory material prepared by the method is 1.752-2.359 g/cm3The density is moderate; the heat conductivity coefficient is 0.46-1.03W/mK, and the heat conductivity coefficient is low; the highest service temperature is 1250-1300 ℃, and the fire-resistant temperature is high; the compressive strength is 184.3-201.3 MPa, the compressive strength is high, and the deformation is difficult. The method provided by the invention well utilizes the solid waste of the copper smelting slag, and achieves the purpose of slag-free resource utilization of the copper smelting slag.
Drawings
FIG. 1 is a flow chart of the method for preparing refractory material by using copper smelting slag as raw material according to the present invention.
Detailed Description
The invention provides a method for preparing a refractory material by taking copper smelting slag as a raw material, which comprises the following steps:
mixing copper smelting slag, magnesia and a bonding agent, and carrying out ball milling to obtain a mixture;
and sequentially carrying out forming treatment, drying and sintering on the mixture to obtain the refractory material.
In the present invention, the components are commercially available products well known to those skilled in the art, unless otherwise specified.
FIG. 1 is a flow chart showing a method for producing a refractory material from copper smelting slag according to the present invention, and the method according to the present invention will be described in detail with reference to FIG. 1.
According to the invention, copper smelting slag, magnesia and a binding agent are mixed and subjected to ball milling to obtain a mixture.
The source of the copper smelting slag is not particularly limited in the present invention, and any source of the copper smelting slag known to those skilled in the art may be used. The chemical composition of the copper smelting slag is not particularly limited, and the chemical composition of the copper smelting slag known by the person skilled in the art can be adopted. In an embodiment of the invention, the chemical composition of the copper smelting slag comprises: cu 0.27 wt.%, fe45.54wt.%, S0.26 wt.%, SiO 0.27 wt.%2 27.37wt.％，CaO 2.37wt.％，MgO 1.19wt.％，Al2O3 3.96wt.％。
In the invention, the magnesite is preferably prepared from low-grade magnesite; the content of magnesium oxide in the low-grade magnesite is preferably less than or equal to 45 wt.%.
In the present invention, the magnesite is preferably prepared by a preparation method comprising the following steps:
sequentially crushing and calcining the low-grade magnesite to obtain magnesite light-burned powder;
leaching the magnesite light-burned powder by using an ammonium chloride aqueous solution to obtain a leaching solution;
and mixing the leachate with ammonia water, sequentially carrying out magnesium precipitation reaction and solid-liquid separation, and roasting the obtained solid phase to obtain the magnesia.
The low-grade magnesite is sequentially crushed and calcined to obtain magnesite light-burned powder.
The invention has no source of the low-grade magnesiteWith special restrictions, it is sufficient to use a source of low-grade magnesite, which is well known to those skilled in the art. In an embodiment of the present invention, the chemical composition of the low-grade magnesite comprises: 43.56 wt.% MgO, 0.98 wt.% CaO, SiO23.88wt.％，Al2O3 2.05wt.％，Fe2O3 1.47wt.％，LOI 47.62wt.％。
In the present invention, the particle size of the low-grade magnesite particles obtained after crushing is preferably 2 mm. In the present invention, the crushing is preferably performed by grinding. In the present invention, the crushing apparatus is preferably a double roll crusher.
In the present invention, the temperature of the calcination is preferably 800 ℃; the time is preferably 1 to 3 hours, and more preferably 1.5 to 2.5 hours.
After the magnesite light-burned powder is obtained, the magnesite light-burned powder is leached by using an ammonium chloride aqueous solution to obtain a leaching solution.
In the invention, the concentration of the ammonium chloride aqueous solution is preferably 2-3 mol/L, and more preferably 2.2-2.8 mol/L. In the invention, the ratio of the volume of the ammonium chloride aqueous solution to the mass of the magnesite light-burned powder is preferably (9-10) L: 1kg, more preferably (9.2 to 9.8) L: 1 kg. In the invention, the leaching temperature is preferably 110-120 ℃, and more preferably 112-118 ℃; the time is preferably 60 to 80min, and more preferably 65 to 75 min.
After leaching, the solid-liquid mixture obtained by leaching is preferably subjected to solid-liquid separation to obtain a liquid-phase leaching solution. The solid-liquid separation is not particularly limited in the present invention, and a solid-liquid separation known to those skilled in the art may be employed.
After the leachate is obtained, the leachate is mixed with ammonia water, magnesium precipitation reaction and solid-liquid separation are sequentially carried out, and the obtained solid phase is roasted to obtain the magnesia.
In the invention, the concentration of the ammonia water is preferably 5-8 mol/L, and more preferably 5.5-7.5 mol/L. In the invention, the volume ratio of the leachate to the ammonia water is preferably (0.8-1.2): 1, more preferably (0.9 to 1.1): 1. in the invention, the temperature of the magnesium precipitation reaction is preferably 40-50 ℃, and more preferably 42-48 ℃; the time is preferably 60 to 70min, and more preferably 62 to 68 min. In the present invention, the magnesium precipitation reaction is preferably carried out under stirring; the stirring speed is preferably 450-550 rpm, and more preferably 460-540 rpm. In the invention, the magnesium precipitation reaction generates magnesium hydroxide precipitate.
The solid-liquid separation is not particularly limited in the present invention, and a solid-liquid separation known to those skilled in the art may be employed.
In the invention, the roasting temperature is preferably 450-500 ℃, and more preferably 460-490 ℃; the time is preferably 30 to 60min, and more preferably 35 to 55 min. In the present invention, the apparatus for calcination is preferably an electric furnace.
In the invention, the purity of the magnesite is preferably more than or equal to 98%.
In the invention, the mass ratio of the copper smelting slag to the magnesia is preferably (68-80): (20-32), more preferably (70-78): (22-30).
In the present invention, the binder preferably includes one or more of resin, rubber, pulp, and magnesium chloride. The resin, rubber and pulp are not particularly limited in the present invention, and those known to those skilled in the art can be used. In an embodiment of the present invention, the resin is polyvinyl chloride (PVC). In the invention, the solid content of the paper pulp is preferably 35-40%.
In the present invention, the magnesium chloride is preferably provided in the form of a magnesium chloride solution; the concentration of the magnesium chloride solution in percentage by mass is not particularly limited in the present invention, and the concentration of the magnesium chloride solution known to those skilled in the art may be used. In an embodiment of the present invention, the magnesium chloride solution has a concentration of 5% by mass.
In the present invention, the ratio of the total mass of the copper smelting slag and the magnesia to the mass of the binder is preferably 100: (0.5 to 14), more preferably 100: (1-13), more preferably 100: (5-10).
In the invention, the ball-to-material ratio of the ball mill is preferably (1.5-2): 1, more preferably (1.8 to 1.9): 1; the rotation speed of the ball milling is preferably 300-500 rpm, more preferably 350-450 rpm; the ball milling time is preferably 20-25 min, and more preferably 21-24 min. The invention promotes the uniform dispersion and mixing of the copper smelting slag and the magnesia through ball milling.
After the mixture is obtained, the mixture is sequentially subjected to forming treatment, drying and sintering to obtain the refractory material.
The mixture is molded to obtain a molded blank. In the present invention, the forming process is preferably cold press forming. In the invention, the pressure of the cold press molding is preferably 50-200 MPa, more preferably 75-175 MPa, and still more preferably 100-150 MPa; the pressure maintaining time is preferably 10 to 30min, and more preferably 15 to 25 min. In the present invention, the molding die in the molding process is preferably a steel die. After the molding treatment, the invention preferably performs demolding to obtain the molded blank.
After a forming blank is obtained, the forming blank is dried to obtain a blank to be sintered. In the invention, the drying temperature is preferably 102-108 ℃, and more preferably 104-106 ℃; the time is preferably 4 to 8 hours, and more preferably 5 to 7 hours. In the present invention, the drying device is preferably a drying oven. According to the invention, through drying, water absorbed in the process of preparing the formed blank is primarily removed, and internal stress cracking caused by subsequent sintering is prevented.
After a blank to be sintered is obtained, the blank to be sintered is sintered to obtain the refractory material. In the invention, the sintering temperature is preferably 1350-1400 ℃, and more preferably 1360-1390 ℃; the time is preferably 2 to 8 hours, and more preferably 2.5 to 7.5 hours. In the present invention, the sintering temperature is preferably obtained by raising the temperature; the heating rate is preferably 5-20 ℃/min, more preferably 8-12 ℃/min, and most preferably 10 ℃/min. In the present invention, the sintering is preferably performed under air atmosphere conditions. The invention leads the slag to generate phase change and microstructure change through sintering, which is beneficial to the olivine phase in the slag to be rapidly converted into the forsterite phase and the spinel phase of the high melting point phase.
After sintering, the invention preferably cools the sintered product to obtain the refractory material. In the present invention, the cooling is preferably furnace cooling.
In order to further illustrate the present invention, the method for preparing refractory material using copper smelting slag as raw material according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The chemical composition of the low-grade magnesite comprises: 43.56 wt.% MgO, 0.98 wt.% CaO, SiO23.88wt.％，Al2O3 2.05wt.％，Fe2O3 1.47wt.％，LOI 47.62wt.％；
The chemical composition of the copper smelting slag comprises: cu 0.27 wt.%, Fe45.54 wt.%, S0.26 wt.%, SiO 0.27 wt.%227.37wt.％，CaO 2.37wt.％，MgO 1.19wt.％，Al2O3 3.96wt.％；
Putting 10kg of low-grade magnesite into a double-roll crusher to be crushed until the particle size is 2mm, and calcining the obtained low-grade magnesite particles for 3 hours at 800 ℃ to obtain 5.15kg of magnesite light-burned powder;
leaching the magnesite light-burned powder by using 50L of 2.5mol/L ammonium chloride aqueous solution at the leaching temperature of 110 ℃ for 80min to obtain leachate;
mixing the leachate with 26L of ammonia water with the concentration of 8mol/L, performing magnesium precipitation reaction for 60min at 550rpm and 40 ℃, performing solid-liquid separation, and roasting the obtained solid phase at 500 ℃ for 30min to obtain magnesia with the purity of 99.81% and the mass of 2.92 kg;
750g of copper smelting slag, 250g of magnesia and 5g of paper pulp (with a solid content of 40%) are mixed in a ball-to-feed ratio of 1.9: 1. ball milling is carried out for 20min under the condition that the ball milling rotating speed is 350rpm, and a mixture is obtained;
placing the mixture into a cylindrical steel mold with the diameter of 500mm, molding under the pressure condition of 200MPa, keeping the pressure for 15min, demolding, placing in a drying oven at 105 ℃ for drying for 6h, then placing a to-be-sintered blank obtained by drying in an electric furnace, heating to 1400 ℃ at the speed of 10 ℃/min, preserving heat for 5h for sintering, and finally cooling along with the furnace to obtain the refractory material.
The refractory obtained in this example had a diameter of 500mm and a thickness of 100 mm.
The obtained refractory material is mainly spinel phase and olivine phase by X-ray diffraction test.
Example 2
The chemical composition of the low-grade magnesite comprises: 43.56 wt.% MgO, 0.98 wt.% CaO, SiO23.88wt.％，Al2O3 2.05wt.％，Fe2O3 1.47wt.％，LOI 47.62wt.％；
The chemical composition of the copper smelting slag comprises: cu 0.27 wt.%, Fe45.54 wt.%, S0.26 wt.%, SiO 0.27 wt.%227.37wt.％，CaO 2.37wt.％，MgO 1.19wt.％，Al2O3 3.96wt.％；
Putting 10kg of low-grade magnesite into a double-roll crusher to be crushed until the particle size is 2mm, and calcining the obtained low-grade magnesite particles for 2 hours at 800 ℃ to obtain 5.2kg of magnesite light-burned powder;
leaching the magnesite light-burned powder by using 52L of 2mol/L ammonium chloride aqueous solution at the leaching temperature of 115 ℃ for 70min to obtain leachate;
mixing the leachate with 30.6L of 7mol/L ammonia water, performing magnesium precipitation reaction at 500rpm and 45 ℃ for 65min, performing solid-liquid separation, and roasting the obtained solid phase at 480 ℃ for 50min to obtain magnesia with the purity of 99.76% and the mass of 3.06 kg;
680g of copper smelting slag, 320g of magnesia and 65g of magnesium chloride solution with the mass percent concentration of 5 percent are mixed, and the ratio of balls to materials is 1.8: 1. ball milling for 20min under the condition that the ball milling rotating speed is 400rpm to obtain a mixture;
placing the mixture into a cylindrical steel die with the diameter of 500mm, forming under the pressure condition of 50MPa, keeping the pressure for 25min, demolding, placing in a drying oven at 105 ℃ for drying for 6h, then placing a blank to be sintered obtained by drying in an electric furnace, heating to 1350 ℃ at the speed of 10 ℃/min, preserving heat for 8h for sintering, and finally cooling along with the furnace to obtain the refractory material.
The refractory obtained in this example had a diameter of 500mm and a thickness of 100 mm.
The obtained refractory material is mainly spinel phase and olivine phase by X-ray diffraction test.
Example 3
The chemical composition of the low-grade magnesite comprises: 43.56 wt.% MgO, 0.98 wt.% CaO, SiO23.88wt.％，Al2O3 2.05wt.％，Fe2O3 1.47wt.％，LOI 47.62wt.％；
The chemical composition of the copper smelting slag comprises: cu 0.27 wt.%, Fe45.54 wt.%, S0.26 wt.%, SiO 0.27 wt.%227.37wt.％，CaO 2.37wt.％，MgO 1.19wt.％，Al2O3 3.96wt.％；
Putting 10kg of low-grade magnesite into a double-roll crusher to be crushed until the particle size is 2mm, and calcining the obtained low-grade magnesite particles for 1h at 800 ℃ to obtain 5.27kg of magnesite light-burned powder;
47.43L of ammonium chloride aqueous solution with the concentration of 3mol/L is used for leaching the magnesite light-burned powder, the leaching temperature is 120 ℃, and the leaching time is 60min, so as to obtain a leaching solution;
mixing the leachate with 39L of ammonia water with the concentration of 5mol/L, performing magnesium precipitation reaction for 70min at the conditions of 450rpm and 50 ℃, performing solid-liquid separation, and roasting the obtained solid phase at 450 ℃ for 60min to obtain magnesia with the purity of 99.51% and the mass of 3.15 kg;
mixing 800g of copper smelting slag, 200g of magnesia and 140g of polyvinyl chloride (PVC) according to a ball-to-feed ratio of 1.7: 1. ball milling for 20min under the condition that the ball milling rotating speed is 450rpm to obtain a mixture;
placing the mixture into a cylindrical steel mold with the diameter of 500mm, molding under the pressure condition of 100MPa, keeping the pressure for 20min, demolding, placing in a drying oven at 105 ℃ for drying for 6h, then placing a blank to be sintered obtained by drying in an electric furnace, heating to 1400 ℃ at the speed of 10 ℃/min, preserving heat for 2h for sintering, and finally cooling along with the furnace to obtain the refractory material.
The obtained refractory material is mainly spinel phase and olivine phase by X-ray diffraction test.
The refractory obtained in examples 1 to 3 was tested, and the test standards and test results are shown in Table 1.
TABLE 1 results of performance test of the refractory obtained in examples 1 to 3
As can be seen from Table 1, the density of the refractory material prepared by the method provided by the invention is 1.752-2.359 g/cm3The density is moderate; the heat conductivity coefficient is 0.46-1.03W/mK, and the heat conductivity coefficient is low; the highest service temperature is 1250-1300 ℃, and the fire-resistant temperature is high; the compressive strength is 184.3-201.3 MPa, the compressive strength is high, and the deformation is difficult. The method provided by the invention well utilizes the solid waste of the copper smelting slag, and achieves the purpose of slag-free resource utilization of the copper smelting slag.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for preparing a refractory material by taking copper smelting slag as a raw material comprises the following steps:
mixing copper smelting slag, magnesia and a bonding agent, and carrying out ball milling to obtain a mixture;
sequentially carrying out forming treatment, drying and sintering on the mixture to obtain the refractory material;
the mass ratio of the copper smelting slag to the magnesia is (68-80): (20-32);
the bonding agent is one or more of polyvinyl chloride resin, rubber, paper pulp and magnesium chloride.
2. The method according to claim 1, characterized in that the ratio of the total mass of copper smelting slag and magnesite clinker to the mass of binder is 100: (0.5 to 14).
3. The method of claim 1, wherein the magnesite is prepared from low grade magnesite; the content of magnesium oxide in the low-grade magnesite is less than or equal to 45 wt.%; the magnesite is prepared by a preparation method comprising the following steps:
sequentially crushing and calcining the low-grade magnesite to obtain magnesite light-burned powder;
leaching the magnesite light-burned powder by using an ammonium chloride aqueous solution to obtain a leaching solution;
and mixing the leachate with ammonia water, sequentially carrying out magnesium precipitation reaction and solid-liquid separation, and roasting the obtained solid phase to obtain the magnesia.
4. The method according to claim 3, wherein the concentration of the aqueous ammonium chloride solution is 2 to 3 mol/L; the ratio of the volume of the ammonium chloride aqueous solution to the mass of the magnesite light-burned powder is (9-10) L: 1 kg.
5. The method according to claim 3, wherein the concentration of the ammonia water is 5-8 mol/L, and the volume ratio of the leaching solution to the ammonia water is (0.8-1.2): 1; the temperature of the magnesium precipitation reaction is 40-50 ℃, and the time is 60-70 min.
6. The method according to claim 1, wherein the ball milling has a ball-to-material ratio of (1.5-2): 1, the rotation speed is 300-500 rpm, and the time is 20-25 min.
7. The method of claim 1, wherein the forming process is cold press forming; the pressure of the cold press molding is 50-200 MPa, and the pressure maintaining time is 10-30 min.
8. The method according to claim 1, wherein the sintering temperature is 1350-1400 ℃ and the sintering time is 2-8 h.
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| US5374593A (en) * | 1992-02-21 | 1994-12-20 | Les Sables Olimag, Inc. | Preparation of refractory materials from asbestos tailings |
| CN107285778A (en) * | 2017-06-27 | 2017-10-24 | 中南大学 | A kind of preparation method of high temperature resistant forsterite type refractory material |
| CN107500727A (en) * | 2017-09-25 | 2017-12-22 | 北京科技大学 | A kind of method that ceramic material is prepared using pyrometallurgical smelting copper ashes |
| CN108191421A (en) * | 2018-02-23 | 2018-06-22 | 北京科技大学 | A kind of method that forsterite refractory is prepared using dilval tailings |
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| CN102167602A (en) * | 2010-12-20 | 2011-08-31 | 昆明理工大学 | Manufacturing method of refractory material applicable to melting and reduction of Fe from copper ash |
| JP2016191128A (en) * | 2015-03-31 | 2016-11-10 | 株式会社Istc | Copper smelting slag treatment method |
| CN110156353B (en) * | 2019-05-31 | 2021-04-30 | 北方民族大学 | Method for combined treatment of copper slag and magnesium slag and application |
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| US5374593A (en) * | 1992-02-21 | 1994-12-20 | Les Sables Olimag, Inc. | Preparation of refractory materials from asbestos tailings |
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| CN107500727A (en) * | 2017-09-25 | 2017-12-22 | 北京科技大学 | A kind of method that ceramic material is prepared using pyrometallurgical smelting copper ashes |
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Effective date of registration: 20231115 Address after: 650000 block a, No. 625, 2nd Ring West Road, high tech Zone, Kunming, Yunnan Patentee after: YUNNAN COPPER Co.,Ltd. SOUTHWEST COPPER BRANCH Address before: Kunming University of science and technology foundation building, 253 Xuefu Road, Kunming City, Yunnan Province, 650093 Patentee before: Kunming University of Science and Technology |