CN109626970B - Refractory material for furnace wall below liquid line of non-ferrous smelting melting furnace and preparation method thereof - Google Patents

Refractory material for furnace wall below liquid line of non-ferrous smelting melting furnace and preparation method thereof Download PDF

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CN109626970B
CN109626970B CN201910127262.7A CN201910127262A CN109626970B CN 109626970 B CN109626970 B CN 109626970B CN 201910127262 A CN201910127262 A CN 201910127262A CN 109626970 B CN109626970 B CN 109626970B
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spinel
aluminum
magnesium
liquid line
wall below
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CN109626970A (en
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张利新
廖绍虎
王继宝
张全力
张瑜
李婉婉
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Sinosteel Luonai Technology Service Co ltd
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Abstract

A refractory material for a furnace wall below a liquid line of a nonferrous smelting and melting furnace is suitable for the position of the furnace wall below the liquid line of the nonferrous smelting and melting furnace, and comprises the following components: the aluminum-chromium eutectic, the magnesium-chromium spinel, the magnesium-aluminum spinel, the alpha alumina micropowder, the aluminum-magnesium spinel and the gel binder. The invention uses the ceramics fired by aluminum-chromium eutectic, magnesium-chromium spinel, magnesium-aluminum spinel, alpha alumina micropowder and aluminum-magnesium spinel which are easy to obtain and cheap as raw materials, and the raw materials are dry-mixed, pressed by adding water, dried, kiln-fired and heat-preserved, thus finally obtaining the refractory material for the furnace wall below the liquid line of the non-ferrous smelting and melting furnace. The ceramic co-fired by the magnesia-chrome spinel, the alpha alumina micro powder and the magnesia alumina spinel can reduce the porosity and pore diameter of the material, reduce the accumulation of slag in the refractory material and improve the impermeability of the material. Therefore, under the combined action of a plurality of materials, the refractory material for the furnace wall below the liquid line of the smelting furnace has good performance indexes.

Description

Refractory material for furnace wall below liquid line of non-ferrous smelting melting furnace and preparation method thereof
Technical Field
The invention relates to the technical field of refractory materials, in particular to a refractory material for a furnace wall below a liquid line of a non-ferrous smelting melting furnace.
Background
China is a large country for producing nonferrous metals, along with the rapid development of traffic, energy, construction, electromechanics, communication, automobiles, household appliances and the like in China and the need of importing a large amount of nonferrous metals in countries around China, such as Japan and Korean resource-poor countries, various types of composite materials, alloys, ultrathin copper plates, pipes and chemical products have wide domestic and foreign markets, the capacity is continuously expanded, and a series of the following products are: the problems of technology aging, equipment obsolescence, high energy consumption, high cost, serious environmental pollution, mine resource shortage, low recovery rate and the like need to be solved urgently. Particularly, along with the rapid iteration of electronic products, China is advancing the scrapping peak of the electronic products. In the face of the electronic waste scale expanding year by year, on one hand, the environmental pollution caused by the flooding of massive electronic waste erodes the living space of people day by day, on the other hand, the market of tourists blooms all the time, extensive workshop-type electronic waste treatment market grows wildly, the pollution of virulent, toxic and harmful components such as dioxin and the like to the atmosphere, soil, underground water and the like is serious, and the precious metal extraction process is a removal process prohibited by the state regulations, and the precious metal recovery rate is low. How to reasonably and effectively dispose and recycle electronic garbage, namely urban mineral products, realizes that the gray industry turns to green economy, and is a technical bottleneck restricting the development of the colored industry.
The most effective harmless treatment method in the world is that the regeneration enterprises in Japan, Belgium and other countries have advanced treatment technology and equipment, and the technology of the regeneration enterprises is advanced in the world. China still adopts the traditional method, is simple, original and laggard, and has no effective advanced pollution-free treatment technology in China. The smelting furnace is introduced into Japan and Belgium at home and abroad, and the service life of a furnace lining material is 1 or more than a month, and some furnace lining materials are even shorter. In order to promote the rapid development of the nonferrous industry, improve the nonferrous smelting process level and combine the requirement of the strengthening (strengthening the smelting proportion increasing) of the prior nonferrous smelting process on the service performance of refractory materials, the project mainly improves the material quality of special, key and harsh parts of the nonferrous smelting, prolongs the service life of the furnace lining of the high-temperature kiln, and develops technical research for realizing more environmental protection in the production process.
The NRTS furnace designed by a certain national colored institute is the first electronic waste melting-refining furnace in China, can effectively treat waste materials such as electronic waste, industrial waste residues, low-grade impure copper, anode mud and the like, has high recovery rate of rare and precious metals, and has a smelting technology exceeding the foreign level. However, because of the harsh smelting environment, the lining material is required to have strong acid and alkali resistance, high temperature resistance, strong erosion resistance of metal slag and the like, so the service life of the existing material is short, and the normal use cannot be met. Therefore, the development of a series of high-performance and long-life multi-composite spinel high-temperature furnace lining material for energy-saving and environment-friendly advanced electronic waste and non-ferrous solid waste smelting-refining furnace is urgently needed.
The furnace wall part below the liquid line of the non-ferrous smelting melting furnace has a large amount of materials to be melted, the materials are violently reacted at the furnace wall part below the liquid line, and various gases such as NO are generated along with the absorption and release of a large amount of reaction heatX、SO2、SO3And the furnace wall is easy to corrode, and the working conditions are complex. The traditional furnace lining material is mostly prepared into a magnesia-chromite furnace lining material and a magnesia-alumina furnace lining material by solid-phase sintering. The traditional magnesia-chrome refractory material has the characteristics of good slag resistance, erosion resistance and the like, but has weak thermal shock resistance and scouring resistance. The traditional magnesia-alumina furnace lining material has good thermal shock and anti-scouring performance, but cannot better deal with slag erosion. And the traditional magnesia-chromite and magnesia-alumina refractory material has high porosity and large pore diameter, so that the slag and the solution are easier to migrate into the refractory material and react with the constituent substances of the traditional magnesia-alumina or magnesia-chromite refractory material to generate MgSO4Etc. are filled in the pores of the refractory material. As a result of exposure to high temperature, MgSO4And the like can be decomposed again to form MgO, and the process is repeated, so that the physicochemical properties of the refractory material become discontinuous, and the service life of the refractory material is reduced. Therefore, new solutions to the problems of penetration resistance and erosion resistance of the conventional refractory materials are needed.
The invention patent with the patent application number of CN201611160536.5 discloses a low-porosity magnesia-chrome brick for non-ferrous smelting and a preparation method thereof. The method comprises the steps of mixing any one or any two of fused magnesia-chromite, chrome concentrate, magnesia, alumina and sulfurous acid pulp waste liquid, magnesium chloride solution and dextrin solution, preparing a brick blank by using a press, drying, firing and preserving heat, placing the magnesia-chromite brick in a pressure vessel, adding nano alumina suspension to completely submerge the magnesia-chromite brick under the condition that the vacuum degree is 1000-1500Pa, then carrying out pressure impregnation treatment, and carrying out microwave drying on the impregnated magnesia-chromite brick to obtain the low-porosity magnesia-chromite brick. The nano alumina is used for reducing the porosity and the pore diameter of the pores so as to reduce the permeation and the reaction of the solution and the slag on the refractory material, but the nano alumina is easy to react with the slag to generate FeO-Al2O3Spinel increases the viscosity of slag, accumulates unevenly in the refractory, destroys the structure of the refractory, and gradually reduces the high-temperature performance of the refractory.
The invention patent with the patent application number of CN201210257706.7 discloses a composite spinel zirconium refractory material for smelting nonferrous heavy metals. The composite spinel zirconium refractory material is prepared by mixing corundum sand, magnesia-chrome sand, magnesia-alumina spinel sand, magnesia sand, chromium green and zirconium dioxide, adding a bonding agent aluminum dihydrogen phosphate, forming by adopting a hydraulic press and sintering in a high-temperature tunnel kiln. However, the raw materials are many and zirconium dioxide is relatively expensive, so that the manufacturing cost is high.
Disclosure of Invention
In order to overcome the defects in the background art, the first technical problem to be solved by the invention is to provide a refractory material for the furnace wall below the liquid line of the non-ferrous smelting melting furnace.
The second technical problem to be solved by the invention is to provide a preparation method of the refractory material for the furnace wall below the liquid line of the non-ferrous smelting melting furnace.
In order to achieve the purpose, the invention adopts the following technical scheme:
a refractory material for a furnace wall below a liquid line of a nonferrous smelting and melting furnace is suitable for the position of the furnace wall below the liquid line of the nonferrous smelting and melting furnace, and comprises the following components: the aluminum-chromium eutectic, the magnesium-chromium spinel, the magnesium-aluminum spinel, the alpha alumina micropowder, the aluminum-magnesium spinel and the gel binder.
In order to further improve the technical scheme, the refractory material comprises the following components in parts by weight: 60-70 parts of an aluminum-chromium eutectic; 10-20 parts of magnesium chromium spinel; 10-20 parts of magnesium aluminate spinel; 5-15 parts of alpha alumina micro powder and aluminum-magnesium spinel; 5-8 parts of a gel binder.
In order to further improve the technical scheme, the invention provides Al in the aluminum-chromium eutectic2O3The content of (B) is 80-90%, Cr2O3The content of (A) is 10-15%.
In order to further improve the technical scheme, the alpha alumina micropowder and the aluminum-magnesium spinel are mixed in a ratio of 7: 3, the superfine powder is combined in a superfine powder combining mode, the granularity of the superfine powder is less than 1 mu, and the superfine powder is combined with aluminum-chromium eutectic, magnesium-chromium spinel and magnesium-aluminum spinel by high-temperature firing to form ceramic.
In order to further improve the technical scheme, the gel bonding agent is prepared by mixing aluminum dihydrogen phosphate and alpha alumina micro powder in a ratio of 1: 1.
In order to further improve the technical scheme, the magnesium aluminate spinel disclosed by the invention is aluminum-rich magnesium aluminate spinel.
In order to further improve the technical scheme, the particle size distribution intervals of the aluminum-chromium eutectic, the magnesium-chromium spinel and the magnesium-aluminum spinel are as follows: 5-3 mm, 3-1 mm, 1-0.1 mm, less than 180 meshes and less than 325 meshes.
In order to further improve the technical scheme, the particle sizes of the aluminum-chromium eutectic, the magnesium-chromium spinel and the magnesium-aluminum spinel are distributed according to the following particle sizes and mass ratios:
the particle size of 5-3 mm accounts for 25% of the total particle size mass ratio of the three components;
the granularity of 3-1 mm accounts for 30% of the total granularity mass ratio of the three components;
the particle size of 1-0.1 mm accounts for 10% of the total particle size mass ratio of the three components;
the fine powder with the granularity of less than 180 meshes accounts for 20 percent of the total granularity mass ratio of the three components;
the fine powder with the granularity of less than 325 meshes accounts for 15 percent of the total granularity mass ratio of the three components.
A preparation method of a refractory material for a furnace wall below a liquid line of a non-ferrous smelting melting furnace comprises the steps of dry mixing an aluminum-chromium eutectic, a magnesium-chromium spinel, a magnesium-aluminum spinel, alpha alumina micro powder and an aluminum-magnesium spinel according to the particle size composition according to the principle of firstly coarse and then fine, adding a gel binder after uniformly mixing particles and fine powder, pressing at the pressure of 630-1000T to form a green brick, placing the obtained green brick in a dryer, drying for 24 hours at the temperature of 100-150 ℃, then placing the dried green brick in a high-temperature tunnel kiln for firing, wherein the firing temperature is 1400-1500 ℃, and the heat preservation time is 6-8 hours under the firing temperature condition.
Compared with the prior art, the invention has the beneficial effects that: the invention uses the ceramics fired by aluminum-chromium eutectic, magnesium-chromium spinel, magnesium-aluminum spinel, alpha alumina micropowder and aluminum-magnesium spinel which are easy to obtain and cheap as raw materials, and the raw materials are dry-mixed, pressed by adding water, dried, kiln-fired and heat-preserved, thus finally obtaining the refractory material for the furnace wall below the liquid line of the non-ferrous smelting and melting furnace. The ceramic co-fired by the magnesia-chrome spinel, the alpha alumina micro powder and the magnesia alumina spinel can reduce the porosity and pore diameter of the material, reduce the accumulation of slag in the refractory material and improve the impermeability of the material. Therefore, under the combined action of a plurality of materials, the refractory material for the furnace wall below the liquid line of the non-ferrous smelting melting furnace has good performance indexes.
Through the test method given in GB/T2997 test method for bulk density, apparent porosity and true porosity of compact and shaped refractory products, the apparent porosity of the refractory material for the furnace wall below the liquid line of the non-ferrous smelting and melting furnace prepared by the technical scheme is found to be less than or equal to 14%, and the use requirement of the refractory material for the furnace wall below the liquid line of the non-ferrous smelting and melting furnace is well met. The refractory material prepared by the technical scheme has longer service life, avoids frequently repairing and replacing the furnace lining, saves a large amount of manpower and financial resources, and has great significance for treating electronic waste and promoting the development of nonferrous smelting.
Detailed Description
The present invention will be explained in detail by the following examples, which are disclosed for the purpose of protecting all technical improvements within the scope of the present invention.
Example one
60 parts of aluminum-chromium eutectic, 20 parts of magnesium-chromium spinel, 10 parts of magnesium-aluminum spinel, 15 parts of alpha alumina micro powder and aluminum-magnesium spinel are composed according to granularity, dry-mixed in a wet mill according to the principle of firstly coarse and then fine, 5 parts of gel bonding agent prepared by aluminum dihydrogen phosphate and alpha alumina micro powder in the mass ratio of 1:1 is added after particles and fine powder are uniformly mixed, the mixture is pressed at the pressure of 1000T to form a green brick, the obtained green brick is placed in a dryer and dried for 24 hours at the temperature of 150 ℃, and then the dried green brick is placed in a high-temperature tunnel kiln to be fired at the firing temperature of 1400 ℃ for 8 hours at the firing temperature.
Example two
70 parts of aluminum-chromium eutectic, 10 parts of magnesium-chromium spinel, 20 parts of magnesium-aluminum spinel, 5 parts of alpha alumina micro powder and aluminum-magnesium spinel are composed according to granularity, dry-mixed in a wet mill according to the principle of firstly coarse and then fine, 8 parts of gel bonding agent prepared by aluminum dihydrogen phosphate and alpha alumina micro powder in the mass ratio of 1:1 is added after the particles and fine powder are uniformly mixed, the mixture is pressed at the pressure of 1000T to form a green brick, the obtained green brick is placed in a dryer and dried for 24 hours at the temperature of 130 ℃, and then the dried green brick is placed in a high-temperature tunnel kiln to be fired at the firing temperature of 1500 ℃ for 7 hours at the firing temperature.
EXAMPLE III
62 parts of aluminum-chromium eutectic, 18 parts of magnesium-chromium spinel, 12 parts of magnesium-aluminum spinel, 13 parts of alpha alumina micro powder and aluminum-magnesium spinel are composed according to granularity, dry-mixed in a wet mill according to the principle of firstly coarse and then fine, 6 parts of gel binder prepared by mixing aluminum dihydrogen phosphate and alpha alumina micro powder in a mass ratio of 1:1 is added after particles and fine powder are uniformly mixed, the mixture is pressed at the pressure of 800T and is molded into a green brick, the obtained green brick is placed in a dryer and is dried for 24 hours at the temperature of 150 ℃, and then the dried green brick is placed in a high-temperature tunnel kiln for firing at the firing temperature of 1400 ℃ for 8 hours.
Example four
67 parts of aluminum-chromium eutectic, 13 parts of magnesium-chromium spinel, 16 parts of magnesium-aluminum spinel, 9 parts of alpha alumina micro powder and aluminum-magnesium spinel are composed according to granularity, dry-mixed in a wet mill according to the principle of firstly coarse and then fine, 7 parts of gel binder prepared by mixing aluminum dihydrogen phosphate and alpha alumina micro powder in a mass ratio of 1:1 is added after particles and fine powder are uniformly mixed, the mixture is pressed at the pressure of 630T to form a green brick, the obtained green brick is placed in a dryer and dried for 24 hours at the temperature of 150 ℃, and then the dried green brick is placed in a high-temperature tunnel kiln to be fired at the temperature of 1500 ℃ for 8 hours at the firing temperature.
The weight parts of the components of the first to fourth embodiments are shown in table 1:
TABLE 1 parts by weight of the components in examples one to four
Components Example one Example two EXAMPLE III Example four
Al-Cr eutectic 60 70 62 67
Magnesium chromium spinel 20 10 18 13
Magnesium aluminate spinel 10 20 12 16
Alpha alumina micropowder and aluminum magnesium spinel 15 5 13 9
Gel binder 5 8 6 7
The main technical indexes of the refractories for the furnace wall below the melting line of the nonferrous smelting melting furnace in the first to fourth embodiments are shown in Table 2:
TABLE 2 physicochemical indices of the first to fourth examples
Figure BDA0001974026760000081
The present invention is not described in detail in the prior art.

Claims (6)

1. A refractory material for a furnace wall below a liquid line of a non-ferrous smelting and melting furnace is suitable for the position of the furnace wall below the liquid line of the non-ferrous smelting and melting furnace, and is characterized in that: the refractory material comprises the following components in parts by weight: 60-70 parts of an aluminum-chromium eutectic; 10-20 parts of magnesium chromium spinel; 10-20 parts of magnesium aluminate spinel; 5-15 parts of alpha alumina micro powder and aluminum-magnesium spinel; 5-8 parts of a gel binder.
2. The refractory for the furnace wall below the liquid line of a nonferrous smelting melting furnace according to claim 1, wherein: the content of Al2O3 in the aluminum-chromium eutectic is 80-90%, and the content of Cr2O3 is 10-15%.
3. The refractory for the furnace wall below the liquid line of a nonferrous smelting melting furnace according to claim 1, wherein: the alpha alumina micro powder and the aluminum-magnesium spinel are mixed in a ratio of 7: 3, the superfine powder is combined in a superfine powder combining mode, the granularity of the superfine powder is less than 1 mu m, and the superfine powder is combined with aluminum-chromium eutectic, magnesium-chromium spinel and magnesium-aluminum spinel by high-temperature firing to form ceramic.
4. The refractory for the furnace wall below the liquid line of a nonferrous smelting melting furnace according to claim 1, wherein: the magnesium aluminate spinel is rich in aluminum.
5. The refractory for the furnace wall below the liquid line of a nonferrous smelting melting furnace according to claim 1, wherein: the gel binder is prepared by mixing aluminum dihydrogen phosphate and alpha alumina micro powder in a ratio of 1: 1.
6. A method for producing the refractory for the furnace wall below the liquid line of the nonferrous smelting melting furnace according to any one of claims 1 to 5, characterized by comprising: the preparation method comprises the steps of mixing aluminum-chromium eutectic, magnesium-chromium spinel, magnesium aluminate spinel, alpha alumina micro powder and aluminum-magnesium spinel according to particle size, dry-mixing the aluminum-chromium eutectic, magnesium aluminate spinel, alpha alumina micro powder and aluminum-magnesium spinel according to the principle of firstly coarse particles and secondly fine particles, adding a gel binder after the particles and the fine powder are uniformly mixed, pressing the mixture at the pressure of 630-1000T to form a green brick, placing the obtained green brick in a dryer, drying the green brick for 24 hours at the temperature of 100-150 ℃, then placing the dried green brick in a high-temperature tunnel kiln for firing at the firing temperature of 1400-1500 ℃, and keeping the temperature for 6-8 hours at the firing temperature.
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