CN113121212A - Aluminum-chromium solid solution brick for copper smelting furnace and manufacturing method thereof - Google Patents
Aluminum-chromium solid solution brick for copper smelting furnace and manufacturing method thereof Download PDFInfo
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- CN113121212A CN113121212A CN201911394022.XA CN201911394022A CN113121212A CN 113121212 A CN113121212 A CN 113121212A CN 201911394022 A CN201911394022 A CN 201911394022A CN 113121212 A CN113121212 A CN 113121212A
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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
- C04B35/10—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 aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/105—Refractories from grain sized mixtures containing chromium oxide or chrome ore
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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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- 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
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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
- C04B2235/70—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
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Abstract
The application discloses an aluminum-chromium solid solution brick for a copper smelting furnace and a manufacturing method thereof, wherein the aluminum-chromium solid solution brick comprises the following raw materials in percentage by mole: 48-53% of compact white corundum, 20-25% of brown corundum, 8-12% of Indian chromium concentrate, 10-15% of chromium oxide green and alpha-Al2O35% -8% and 3% -4% of a binding agent; the method comprises the steps of mixing the raw materials, conveying the mixed raw materials to a press machine for compression molding to obtain green bricks, and firing the green bricks in a kiln to obtain the finished product. This application forms through adopting raw materials with aluminium, chromium as the main part through ratio, compression moulding, firing, has improved among the prior art refractory material erosion too fast, the short problem of kiln life cycle that intensity is not high to the used material low cost of the product of this application, the manufacturing of being convenient for has greatly reduced the processing cost, has improved product output.
Description
Technical Field
The invention relates to the technical field of manufacturing of materials for copper smelting furnaces, in particular to an aluminum-chromium solid solution brick for a copper smelting furnace and a manufacturing method thereof.
Background
The copper smelting furnace mainly comprises a reverberatory furnace, a blast furnace, an electric furnace, a converter, an oxidation furnace and the like according to different working principles, wherein the oxidation furnace is a novel copper smelting furnace which is established in recent years, mainly represents various types of furnaces such as an Osmant furnace, an Isa furnace and an Incore furnace, and has the main working principle that: and (2) adding the mixed copper smelting raw materials at the top of the oxidation furnace, wherein the temperature is continuously increased in the process of descending the copper smelting raw materials in the oxidation furnace, the solid copper smelting raw materials are gradually changed into liquid after reaching a molten pool, and after top oxygen blowing operation, the liquid raw materials are discharged into water through a chute to form copper matte slag for further smelting process of the converter.
Because of the high temperature in the copper smelting furnace, a layer of refractory material is usually built in the lining of the copper smelting furnace to protect the furnace shell. In the traditional copper smelting furnace, high-alumina bricks are used as refractory materials, but because the high-alumina bricks have poor erosion resistance and heat erosion resistance, the high-alumina bricks are gradually replaced by more-performance magnesia-chrome bricks in the prior art; the magnesite-chrome bricks can be divided into common magnesite-chrome bricks, direct combination magnesite-chrome bricks, semi-recombination magnesite-chrome bricks and electric smelting recombination magnesite-chrome bricks according to different selected raw materials, wherein the electric smelting recombination magnesite-chrome bricks have relatively better performance indexes.
However, the service life of the oxidation furnace body built by electric melting and combining magnesia-chrome bricks at present can only reach 4-6 months, and the key point influencing the service life of the oxidation furnace is as follows: in areas with serious erosion, such as a molten pool, a slag line and the like, strong hot washing and slag erosion easily cause rapid peeling and erosion loss of refractory materials, and the fused magnesia-chrome bricks are combined in an oxidation furnace for low erosion resistance, so that the service cycle of a furnace body is shortened, a factory needs to repair and maintain the furnace continuously, the yield is influenced, and the maintenance cost is increased.
Disclosure of Invention
The invention aims to provide an aluminum-chromium solid solution brick for a copper smelting furnace and a manufacturing method thereof, and aims to solve the problem that the conventional cutter cannot be ground or needs to be replaced with a customized cutter bar after being ground.
The application provides an aluminum-chromium solid solution brick for a copper smelting furnace, which comprises the following raw materials in percentage by mole: 48-53% of compact white corundum, 20-25% of brown corundum, 8-12% of Indian chromium concentrate, 10-15% of chromium oxide green and alpha-Al2O35-8% and 3-4% of binding agent.
Optionally, the dense white corundum is composed of four particle size particles of 5mm-3mm, 3mm-1mm, 1mm-0.1mm and 0.088 mm.
Optionally, the mole percentages of the four kinds of particle size particles are respectively 5mm-3 mm: 18% -23%, 3mm-1 mm: 10% -15%, 1mm-0.1 mm: 15% -20% and 0.088 mm: 5 to 10 percent.
Optionally, the brown corundum is composed of particles with two particle sizes of 3mm-1mm and 1mm-0.1 mm.
Optionally, the mole percentages of the two kinds of particle size particles are respectively 3mm-1 mm: 10% -15% and 1mm-0.1 mm: 10 to 15 percent.
Optionally, the binder is at least one of pulp or phosphoric acid.
The application also provides a manufacturing method of the aluminum-chromium solid solution brick for the copper smelting furnace, which comprises the following steps:
mixing the raw materials;
sending the mixed raw materials to a press machine for pressing to obtain a green brick;
and (5) firing the green brick in a kiln to obtain a finished product.
Optionally, the process method for firing the green brick in the kiln comprises:
preheating the green bricks to 240 ℃ and then putting the green bricks into a kiln;
raising the temperature in the kiln to 1630 ℃, stopping raising the temperature, and keeping the temperature for 16 hours;
cooling to 300 ℃ and then taking out of the kiln.
The application provides an aluminium chromium solid solution brick for copper smelting furnace forms through adopting raw materials with aluminium, chromium as the main part through ratio, press forming, firing, has improved among the prior art refractory material erosion too fast, the not high problem that leads to of intensity kiln life cycle is short to the used material cost of the product of this application is cheap, the manufacturing of being convenient for, has greatly reduced the processing cost, has improved product output.
Detailed Description
The application provides an aluminum-chromium solid solution brick for a copper smelting furnace, wherein the aluminum-chromium solid solution brick comprises the following raw materials in percentage by mole: 48-53% of compact white corundum, 20-25% of brown corundum, 8-12% of Indian chromium concentrate, 10-15% of chromium oxide green and alpha-Al2O35-8% and 3-4% of binding agent.
In the aspect of material selection, common materials mainly comprising aluminum and chromium are adopted, and the aim of optimizing the performance of the solid solution generated by combination is fulfilled based on the proportion of various raw materials. The technical indexes of the raw materials of the materials are shown in the following table:
the dense white corundum is a common refractory material manufacturing raw material, has higher melting point, quite high volume density and quite low porosity, has excellent wear resistance, slag resistance, volume stability and thermal shock resistance at high temperature, and is the most excellent refractory raw material in corundum series refractory raw materials. In the embodiment, dense white corundum with various particle sizes is mixed for use, for example, four types of corundum are used, such as 5mm-3mm, 3mm-1mm, 1mm-0.1mm and 0.088mm, so that the porosity can be further reduced during molding, and the brick blank can be more compact, wear-resistant and stable in structure after molding and firing; in actual production, the proportion with the best performance can be obtained through a plurality of tests on the proportion of each granularity.
The brown corundum is made up by using bauxite and coke (anthracite) as main raw material and adopting high-temp. smelting process in electric arc furnace, and its grinding tool is suitable for grinding metal with high tensile strength, such as various general-purpose steels, malleable cast iron and hard bronze, etc., and can also be used for making high-grade refractory material. The brown corundum has the characteristics of high purity, good crystallization, strong fluidity, low linear expansion coefficient and corrosion resistance. Practice of dozens of refractory production enterprises proves that the product has the characteristics of no detonation, no pulverization and no cracking in the application process. Particularly, the cost performance of the brown corundum refractory material is far higher than that of the traditional brown corundum refractory material, so that the brown corundum refractory material becomes the optimal aggregate and filler of the brown corundum refractory material. In this embodiment, two different particle sizes of brown corundum are also used as raw materials of the solid solution brick, for example, two types of brown corundum particles are included, namely 3mm-1mm and 1mm-0.1mm, so that when the brown corundum particles are mixed with other solid particles and then are pressed and molded, the brown corundum particles can be uniformly distributed in the brick blank, and the corrosion resistance of the solid solution brick is improved.
Chromium oxide green is also known as IIIDichromium oxide, chromium oxide, molecular weight 151.99. Is hexagonal, green powder. Density 5.21g/cm3The Mohs hardness of the corundum is 8.5-9 and is close to that of corundum (Al)2O3) Second only to diamond but beyond quartz SiO2Yellow jade Al2〔SiO4〕(F，OH)2And zircon ZrSiO4). The refractive index is 2.5 (good covering rate), and the specific heat capacity (20 ℃) is 0.17J/(g.K). It is insoluble in water, acid and organic solvent, slightly soluble in concentrated sodium hydroxide solution, hot sodium bromate solution, hot concentrated perchloric acid solution or boiling mixed sulfuric-phosphoric acid. To light, atmosphere and corrosive gas (H)2S、SO2Etc.) are extremely stable and excellent in weather resistance. Is stable when heated, has a melting point of 2265 ℃ and a boiling point of 3000 ℃, and is a high-quality refractory material.
Alumina of the formula Al2O3Molecular weight 101.96. Alumina as the main component. White powder. Having different crystal forms, commonly alpha-Al2O3And gamma-Al2O3. The corundum in nature is alpha-Al2O3Hexagonal close-packed crystal, alpha-Al2O3Has a melting point of 2015 +/-15 ℃, a density of 3.965g/cm and a hardness of 8.8, and is insoluble in water, acid or alkali. gamma-Al2O3Belongs to cubic close packed crystal, is insoluble in water, but can be dissolved in acid and alkali.
In the present application, the binder is used to influence the formation of solid solution, which may be at least one of not limited to pulp or phosphoric acid, and the solid solution effect with phosphoric acid is better than that with pulp.
The application also provides a manufacturing method of the aluminum-chromium solid solution brick for the copper smelting furnace, which comprises the following steps:
firstly, mixing the raw materials; solid stirring equipment can be adopted for mixing, and full mixing among all particles is guaranteed.
Secondly, conveying the mixed raw materials to a press machine for compression molding to obtain a green brick; specifically, the mixed raw materials are fed into a hopper of a press machine through the hopper, and the press machine is manually fed and operated to extrude the shape of a green brick.
Finally, putting the green brick into a kiln for firing to obtain a finished product; specifically, the green bricks can be placed on a frame body with a preheating function in order, the green bricks are preheated to 240 ℃, and then the whole frame body is put into a kiln; and then gradually increasing the temperature in the kiln to 1630 ℃, wherein the temperature is required to be slowly and stably increased, the temperature increase rate is generally required to be not more than 38 ℃ per hour, the temperature increase is stopped when the temperature reaches 1630 ℃, the temperature is slowly reduced to 300 ℃ after the temperature is maintained for 16 hours, the temperature is taken out of the kiln for air cooling, a product is prepared, and similarly, the temperature reduction process is also required to be slowly and stably performed, and the temperature reduction rate is not more than 66 ℃ per hour.
Example one
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm: 23%, 3mm-1 mm: 10%, 1mm-0.1 mm: 15% and 0.088 mm: 5%), brown corundum (3mm-1 mm: 10% and 1mm-0.1 mm: 10%), indian chrome concentrate 8%, chromium oxide green 11%, alpha-Al2O35% and 3% of a binder (pulp).
The raw materials are prepared into a solid solution brick product I by adopting the method.
Example two
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm: 18%, 3mm-1 mm: 15%, 1mm-0.1 mm: 15% and 0.088 mm: 5%), brown corundum (3mm-1 mm: 10% and 1mm-0.1 mm: 10%), indian chrome concentrate 8%, chromium oxide green 10%, alpha-Al2O35% and 4% of a binder (phosphoric acid).
The solid solution brick product II is prepared from the raw materials by adopting the method.
EXAMPLE III
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm: 18%, 3mm-1 mm: 10%, 1mm-0.1 mm: 15% and 0.088 mm: 5%), brown corundum (3mm-1 mm: 10% and 1mm-0.1 mm: 10%), indian chrome concentrate 10%, chromium oxide green 10%, alpha-Al2O38 percent and 4 percent of binding agent (phosphoric acid).
The solid solution brick product III is prepared from the raw materials by adopting the method.
Example four
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm: 18%, 3mm-1 mm: 10%, 1mm-0.1 mm: 15% and 0.088 mm: 10%), brown corundum (3mm-1 mm: 10% and 1mm-0.1 mm: 10%), indian chromium concentrate 12%, chromium oxide green 11%, alpha-Al2O35% and 4% of a binder (pulp).
The solid solution brick product IV is prepared from the raw materials by adopting the method.
EXAMPLE five
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm: 18%, 3mm-1 mm: 10%, 1mm-0.1 mm: 15% and 0.088 mm: 5%), brown corundum (3mm-1 mm: 10% and 1mm-0.1 mm: 15%), indian chromium concentrate 12%, chromium oxide green 11%, alpha-Al2O35% and 4% of a binder (pulp).
The solid solution brick product V is prepared from the raw materials by adopting the method.
EXAMPLE six
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm: 18%, 3mm-1 mm: 10%, 1mm-0.1 mm: 15% and 0.088 mm: 5%), brown corundum (3mm-1 mm: 15% and 1mm-0.1 mm: 10%), indian chromium concentrate 12%, chromium oxide green 11%, alpha-Al2O35% and 4% of a binder (pulp).
The solid solution brick product VI is prepared from the raw materials by adopting the method.
EXAMPLE seven
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm:18%, 3mm-1 mm: 10%, 1mm-0.1 mm: 15% and 0.088 mm: 5%), brown corundum (3mm-1 mm: 10% and 1mm-0.1 mm: 10%), indian chrome concentrate 8%, chrome oxide green 15%, alpha-Al2O35% and 4% of a binder (phosphoric acid).
The solid solution brick product seven is prepared from the raw materials by adopting the method.
Example eight
The aluminum-chromium solid solution brick for the copper smelting furnace manufactured by the technical scheme comprises the following raw materials in percentage by mole: dense white corundum (5mm-3 mm: 18%, 3mm-1 mm: 10%, 1mm-0.1 mm: 20% and 0.088 mm: 5%), brown corundum (3mm-1 mm: 10% and 1mm-0.1 mm: 10%), indian chrome concentrate 8%, chromium oxide green 10%, alpha-Al2O35% and 4% of a binder (phosphoric acid).
The solid solution brick product eight is prepared from the raw materials by adopting the method.
The following table shows the parameters of the solid solution brick product prepared in the first embodiment, which is taken as an example, compared with the parameters of the magnesia-chrome brick product in the prior art. The chemical composition indexes are measured by a fluorescence analyzer, the volume density and the porosity are obtained by a weighing method, and the compressive strength, the refractoriness under load and the thermal shock stability are measured by special equipment.
As can be seen from the above table, the method and the product provided by the application have lower porosity, higher volume density and compressive strength, and better thermal shock stability than the magnesia-chrome brick, and in practical application, the alumina-chrome solid solution brick is adopted to replace electric melting and is combined with the magnesia-chrome brick to be used in an oxidation furnace, so that the magnesia-chrome brick can be continuously used for 8-12 months, and the service life of the furnace is greatly prolonged.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims (8)
1. An aluminum-chromium solid solution brick for a copper smelting furnace is characterized in that the aluminum-chromium solid solution brick comprises the following raw materials in percentage by mole: 48-53% of compact white corundum, 20-25% of brown corundum, 8-12% of Indian chromium concentrate, 10-15% of chromium oxide green and alpha-Al2O35-8% and 3-4% of binding agent.
2. The aluminum-chromium solid solution brick for the copper smelting furnace according to the claim 1, characterized in that the dense white corundum is composed of four kinds of grain size particles of 5mm-3mm, 3mm-1mm, 1mm-0.1mm and 0.088 mm.
3. The aluminum-chromium solid solution brick for the copper smelting furnace according to claim 2, wherein the mol percentages of the four kinds of particle size particles are respectively 5mm-3 mm: 18% -23%, 3mm-1 mm: 10% -15%, 1mm-0.1 mm: 15% -20% and 0.088 mm: 5 to 10 percent.
4. The aluminum-chromium solid solution brick for the copper smelting furnace according to the claim 1, wherein the brown corundum is composed of two grain sizes of 3mm-1mm and 1mm-0.1 mm.
5. The aluminum-chromium solid solution brick for the copper smelting furnace according to claim 4, characterized in that the mol percentages of the two kinds of grain size particles are respectively 3mm-1 mm: 10% -15% and 1mm-0.1 mm: 10 to 15 percent.
6. The aluminum-chromium solid solution brick for the copper smelting furnace according to any one of the claims 1 to 5, characterized in that the binding agent is at least one of pulp or phosphoric acid.
7. A manufacturing method of an aluminum-chromium solid solution brick for a copper smelting furnace is characterized by comprising the following steps:
mixing the raw materials of any one of claims 1 to 5;
sending the mixed raw materials to a press machine for pressing to obtain a green brick;
and (5) firing the green brick in a kiln to obtain a finished product.
8. The method of claim 7, wherein the kiln firing of the green bricks comprises:
preheating the green bricks to 240 ℃ and then putting the green bricks into a kiln;
raising the temperature in the kiln to 1630 ℃, stopping raising the temperature, and keeping the temperature for 16 hours;
cooling to 300 ℃ and then taking out of the kiln.
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Cited By (2)
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| CN113999029A (en) * | 2021-11-17 | 2022-02-01 | 江苏国豪耐火科技有限公司 | Low apparent porosity anti-chloride ion brick and preparation method thereof |
| CN114292094A (en) * | 2021-12-28 | 2022-04-08 | 郑州荣盛窑炉耐火材料有限公司 | Acid-corrosion-resistant long-life refractory brick for Osmant furnace and preparation method thereof |
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| CN113999029A (en) * | 2021-11-17 | 2022-02-01 | 江苏国豪耐火科技有限公司 | Low apparent porosity anti-chloride ion brick and preparation method thereof |
| CN114292094A (en) * | 2021-12-28 | 2022-04-08 | 郑州荣盛窑炉耐火材料有限公司 | Acid-corrosion-resistant long-life refractory brick for Osmant furnace and preparation method thereof |
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