CN115322002A - Preparation method of low-carbon low-metal-content electrofusion chromium oxide - Google Patents
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Abstract
The invention relates to a preparation method of low-carbon low-metal content electrofused chromium oxide, which comprises the steps of laying a mixture of chromium sesquioxide particles and chromium sesquioxide dust collection dust generated in a chromium sesquioxide crushing process, using metallurgical coke particles and high-purity graphite strips as arc starting materials, and preparing a low-carbon low-metal content electrofused chromium oxide product through open arc smelting. The electric melting chromic oxide product prepared by the invention has low carbon and metal chromium content and has more excellent erosion resistance and shrinkage resistance.
Description
Technical Field
The invention relates to a chromic oxide raw material in the field of refractory materials and spraying materials, in particular to a preparation method of low-carbon low-metal-content electrofusion chromic oxide.
Background
The electrofused chromium oxide is widely applied to the fields of thermal spraying and high-end refractory materials, and shows unique wear resistance, temperature resistance and corrosion resistance compared with other materials. However, in the smelting process of the electrofusion chromium oxide, the strong activity of chromium leads to the reduction of carbon of the graphite electrode at the smelting temperature of over 2450 ℃, so that carbon elements enter the electrofusion chromium oxide product, part of trivalent chromium is reduced into metallic chromium, the metallic chromium content in the product reaches 1-5%, and the shrinkage is large and the wear resistance and corrosion resistance are poor when the product is applied.
In order to solve the problems, in chinese patent CN109592712A, a proper amount of titanium oxide powder is added around the graphite electrode to prevent chromium oxide around the graphite electrode from being reduced into elemental chromium, but the titanium oxide powder is high in price and can become an impurity in the electrofused chromium oxide product, although the content of metal (chromium) in the product is reduced, other performances are reduced, and the invention does not mention the problem of carburization in the electrofused chromium oxide product.
Disclosure of Invention
An object of the present invention is to solve at least one of the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the purpose of the invention, there is provided a method for preparing electrofused chromium oxide with low carbon and low metal content, comprising:
the mixture of chromium sesquioxide particles and chromium sesquioxide dust produced in the chromium sesquioxide crushing procedure is used for laying the bottom, coke particles for metallurgy and high-purity graphite strips are used as arc striking materials, and the electric melting chromium oxide product with low carbon and low metal content is prepared by open arc melting. The invention also provides a preparation method of the low-carbon low-metal content electrofusion chromium oxide, which comprises the following steps:
s1, mixing chromic oxide particles and chromic oxide dust generated in a chromic oxide crushing process, paving the mixture at the bottom, and covering the mixture with a to-be-melted chromic oxide raw material;
s2, placing metallurgical coke particles on a chromic oxide raw material into a star shape or a triangular shape at the position corresponding to an electrode, and placing three high-purity graphite strips on the coke, wherein the end points of the star shape or the triangular shape correspond to the graphite electrode;
s3, firstly, placing the graphite electrode to be just in contact with the end point of the high-purity graphite strip laid on the furnace bottom, then electrifying the graphite electrode, and smelting in a high-current and low-voltage mode;
s4, after the chromium sesquioxide laid at the bottom in the furnace is melted to form a molten pool and the metallurgical coke particles and the three high-purity graphite strips are combusted, starting to add the chromium sesquioxide raw material at a constant speed, and adopting open arc melting in the furnace;
s5, controlling the continuous feeding amount of the chromium sesquioxide according to the smelting condition in the furnace, and stopping feeding and smelting after the molten liquid reaches the expected feeding amount;
and S6, after the smelting is finished, the graphite electrode is powered off, and the materials in the furnace are naturally cooled, crystallized, crushed and screened to obtain the electro-fused chromium oxide product with low carbon and low metal content.
Preferably, the grain diameter of the electric melting chromic oxide particles for paving the bottom in the S1 is 0-3mm, the proportion of the particles to the dust collection ash is 1-5.
Preferably, in the first step, the thickness of the covering furnace bottom of the chromic oxide raw material is 5-20cm.
Preferably, the particle size of the metallurgical coke particles in S2 is 0.5-5cm.
Preferably, in the second step, the carbon content in the medium-high purity graphite strip is more than or equal to 99.5%, and the cross-sectional area is 0.5-5cm 2 。
Preferably, the constant electrode current is 12000A and the electrode voltage is 60-100V during smelting;
compared with the existing preparation method of the electric melting chromium oxide, the preparation method of the electric melting chromium oxide with low carbon and low metal content provided by the invention at least has the following beneficial effects:
1. the safe operation of high-temperature smelting is ensured by innovative bottom laying and arc starting modes, the arc starting material can be quickly combusted and volatilized after a molten pool is formed in an auxiliary mode, the contact time with chromic oxide is reduced to the maximum extent, and the reduction and fusion of carbon to trivalent chromium at high temperature are reduced;
2. the open arc smelting is matched with the continuous feeding, so that the smelting arc length is increased, the distance between the graphite electrode and a molten pool is increased, the direct contact of materials and the graphite electrode is avoided, and simultaneously, the air guiding quantity can be controlled in the production process, so that the ultrafine carbon particles generated at the high temperature of the graphite electrode can be quickly pumped away and are not accumulated in the furnace;
3. the content of metallic chromium in the electric melting chromium oxide product can be lower than 0.5%, the content of carbon can be lower than 0.05%, compared with the content of metallic chromium in the common electric melting chromium oxide product which is 1-5% and the content of carbon is more than or equal to 0.1%, the electric melting chromium oxide product is used for manufacturing industries such as coal chemical industry, metallurgy, glass, thermal spraying and the like, and the product has more excellent erosion resistance and shrinkage resistance.
Additional features and advantages of the disclosure will be set forth in the description which follows, or in part may be learned by the practice of the above-described techniques of the disclosure, or may be learned by practice of the disclosure.
The specific implementation mode is as follows:
the invention is described in more detail below with reference to specific examples.
Example 1:
(1) At the bottom of an electric arc furnace, firstly paving a bottom by adopting a mixture of chromic oxide particles and chromic oxide dust-collecting ash generated in a chromic oxide crushing process, wherein the ratio of the chromic oxide particles to the chromic oxide dust-collecting ash is 2;
(2) On the chromium oxide raw material which is finished to be laid, adopting metallurgical coke with the grain size of 0.5-5cm at the position below the corresponding graphite electrode,placing the chromium oxide raw material into a triangle with the width of 5cm and the thickness of 3cm, and placing three high-purity graphite strips on the placed coke for metallurgy respectively, wherein the carbon content in the high-purity graphite strips is more than or equal to 99.5%, and the cross-sectional area is 3.5cm 2 ；
(3) Lowering the graphite electrode to the end point just corresponding to the laid high-purity graphite strip; electrifying and arcing, wherein the mixture laid at the bottom of the electric arc furnace and the chromic oxide raw material basically form a molten pool after 2min, and all coke and graphite blocks laid at the bottom of the electric arc furnace are completely combusted after 5 min;
(4) Continuously feeding a chromic oxide raw material into a molten pool at the bottom of an electric arc furnace at a feeding speed of 0.5 hour/ton, a constant electrode current of 12000A and a voltage of 60-100V, carefully observing the distance between a graphite electrode and the molten pool in the smelting process, observing whether the fed chromic oxide raw material is completely molten, timely adjusting the feeding amount, simultaneously controlling the air introduction amount in the electric arc furnace, and extracting ultrafine carbon particles generated by the graphite electrode at high temperature; after 10 tons of materials are fed, carefully observing whether the materials in the furnace are completely smelted, and after the materials are completely smelted, powering off the electrode to stop smelting;
(5) And naturally cooling, crystallizing, crushing and screening the materials in the furnace to obtain the fused chromium oxide product. The detection shows that the product contains 0.12 percent of metallic chromium, 0.03 percent of iron, 0.02 percent of silicon and Na 2 O and K 2 The sum of O content is 0.02%, the sum of CaO and MgO content is 0.03%, the content of carbon is 0.013%, cr 2 O 3 The content was 99.6%.
Example 2:
(1) At the bottom of an electric arc furnace, firstly paving a bottom by adopting a chromium trioxide particle and chromium trioxide dust collection ash mixture generated in a chromium trioxide crushing process, wherein the ratio of the chromium trioxide particle to the chromium trioxide dust collection ash is 1, the particle size of the chromium trioxide particle is 0-3mm, the paving height of the mixture is 20cm, then paving a chromium trioxide raw material on the basis of the mixture base material, and the paving height is 20cm, wherein the purity of the chromium trioxide in the chromium trioxide particle, the chromium trioxide dust collection ash and the chromium trioxide raw material is more than 99%;
(2) After finishingPlacing metallurgical coke with particle size of 1-3cm under corresponding graphite electrode to form a triangle, placing the metallurgical coke with width of 5cm and thickness of 3cm, and placing three high-purity graphite strips on the placed metallurgical coke, wherein the carbon content in the high-purity graphite strips is not less than 99.5%, and the transverse cutting area is 0.5cm 2 ；
(3) Lowering the graphite electrode to the end point just corresponding to the laid high-purity graphite strip; electrifying and arcing, wherein the mixture laid at the bottom of the electric arc furnace and the chromic oxide raw material basically form a molten pool after 2min, and all coke and graphite blocks laid at the bottom of the electric arc furnace are completely combusted after 5 min;
(4) Continuously feeding materials at a feeding speed of 0.5 hour/ton, a constant electrode current of 12000A and a voltage of 60-100V, carefully observing the distance between a graphite electrode and a molten pool in the smelting process, timely adjusting the feeding amount, simultaneously controlling the air guiding amount in an electric arc furnace, and extracting ultra-fine carbon particles generated by the graphite electrode at a high temperature; after 15 tons of materials are fed, carefully observing whether all materials in the furnace are completely smelted, and after all materials are completely smelted, powering off the electrode to stop smelting;
(5) And naturally cooling, crystallizing, crushing and screening the materials in the furnace to obtain the fused chromium oxide product. The detection shows that the product contains 0.15 percent of metallic chromium, 0.03 percent of iron, 0.02 percent of silicon and Na 2 O and K 2 The sum of the O content is 0.03 percent, the sum of the CaO content and the MgO content is 0.04 percent, the carbon content is 0.021 percent, and the Cr content is 2 O 3 The content is 99.5%.
Example 3:
(1) At the bottom of an electric arc furnace, firstly paving a bottom by adopting a mixture of chromic oxide particles and chromic oxide dust-collecting ash generated in a chromic oxide crushing process, wherein the ratio of the chromic oxide particles to the chromic oxide dust-collecting ash is 5, the particle size of the chromic oxide particles is 0-3mm, the paving height of the mixture is 60cm, then paving a chromic oxide raw material on the basis of the mixture base material, and the paving height is 10cm, wherein the purities of the chromic oxide particles, the chromic oxide dust-collecting ash and the chromic oxide in the chromic oxide raw material are all more than 99%;
(2) After completion of layingOn a chromic oxide raw material, adopting metallurgical coke with the particle size of 0.5-5cm at the position below a corresponding graphite electrode, placing the metallurgical coke in a star shape on the chromic oxide raw material, wherein the placing width is 5cm, the placing thickness is 3cm, and then respectively placing three high-purity graphite strips on the placed metallurgical coke, wherein the carbon content in the high-purity graphite strips is more than or equal to 99.5%, and the cross-sectional area is 5cm 2 ；
(3) Lowering the graphite electrode to the end point just corresponding to the laid high-purity graphite strip; electrifying for arcing, wherein after 3min, the mixture paved at the bottom of the electric arc furnace and the chromic oxide raw material basically form a molten pool, and after 5min, coke and graphite blocks paved at the bottom of the electric arc furnace are all burnt;
(4) Continuously feeding a chromic oxide raw material into a molten pool at the bottom of an electric arc furnace at a feeding speed of 0.5 hour/ton, a constant electrode current of 12000A and a voltage of 60-100V, carefully observing the distance between a graphite electrode and the molten pool in the smelting process, observing whether the fed chromic oxide raw material is completely molten, timely adjusting the feeding amount, simultaneously controlling the air introduction amount in the electric arc furnace, and extracting ultrafine carbon particles generated by the graphite electrode at high temperature; after 10 tons of materials are fed, carefully observing whether all materials in the furnace are completely smelted, and after all materials are completely smelted, powering off the electrode to stop smelting;
(5) And naturally cooling, crystallizing, crushing and screening the materials in the furnace to obtain the fused chromium oxide product. Through detection, the carbon content of the product is 0.015 percent, the metal chromium content is 0.14 percent, the iron content is 0.03 percent, the silicon content is 0.03 percent, and Na 2 O and K 2 The sum of the O content is 0.02 percent, the sum of the CaO content and the MgO content is 0.04 percent, and the Cr content 2 O 3 The content was 99.5%.
Example 4:
(1) At the bottom of an electric arc furnace, firstly paving a bottom by adopting a chromium trioxide particle and chromium trioxide dust collection ash mixture generated in a chromium trioxide crushing process, wherein the ratio of the chromium trioxide particle to the chromium trioxide dust collection ash is 5, the particle size of the chromium trioxide particle is 0-3mm, the paving height of the mixture is 70cm, then paving a chromium trioxide raw material on the basis of a mixture base material, and the paving height is 5cm, wherein the purity of the chromium trioxide in the chromium trioxide particle, the chromium trioxide dust collection ash and the chromium trioxide raw material is more than 99%;
(2) On the laid chromic oxide raw material, adopting metallurgical coke with the particle size of 0.5-5cm at the position below the corresponding graphite electrode, placing the metallurgical coke on the chromic oxide raw material into a triangle with the width of 5cm and the thickness of 3cm, and placing three high-purity graphite strips on the placed metallurgical coke respectively, wherein the carbon content in the high-purity graphite strips is more than or equal to 99.5 percent, and the cross-sectional area is 5cm 2 ；
(3) Lowering the graphite electrode to the end point just corresponding to the laid high-purity graphite strip; electrifying and arcing, wherein the mixture laid at the bottom of the electric arc furnace and the chromic oxide raw material basically form a molten pool after 3min, and all coke and graphite blocks laid at the bottom of the electric arc furnace are completely combusted after 5 min;
(4) Continuously feeding a chromic oxide raw material into a molten pool at the bottom of an electric arc furnace at a feeding speed of 0.5 hour/ton, a constant electrode current of 12000A and a voltage of 60-100V, carefully observing the distance between a graphite electrode and the molten pool in a smelting process, observing whether the fed chromic oxide raw material is completely molten, timely adjusting the feeding amount, simultaneously controlling the air induction amount in the electric arc furnace, and extracting ultrafine carbon particles generated by the graphite electrode at high temperature; after 15 tons of materials are fed, carefully observing whether the materials in the furnace are completely smelted, and after the materials are completely smelted, powering off the electrode to stop smelting;
(5) And naturally cooling, crystallizing, crushing and screening the materials in the furnace to obtain the fused chromium oxide product. The detection proves that the carbon content of the product is 0.014%, the chromium content of the product is 0.13%, the iron content of the product is 0.04%, the silicon content of the product is 0.02%, and the Na content of the product is 2 O and K 2 The sum of the O content is 0.03 percent, the sum of the CaO content and the MgO content is 0.05 percent, and the Cr content 2 O 3 The content was 99.6%.
As can be seen from the above examples 1-4, the electrofused chromium oxide product of the present invention has a carbon content of 0.05% or less, a chromium metal content of 0.5% or less, an iron content of 0.05% or less, a silicon content of 0.05% or less, na 2 O and K 2 O content is less than or equal to 0.05 percent, caO and MgO content is less than or equal to 0.05 percent, and compared with the common electric melting chromium oxide, the content of metal chromium is 1 to 5 percent, the content of carbon is more than or equal to 0.1 percent, the content of iron is 0.1 to 0.3 percent, the content of silicon is 0.1 to 0.3 percent, and Na 2 O and K 2 The content of O is 0.1-0.5%, the content of CaO and MgO is less than or equal to 0.1-0.5%, the carbon content of the product is lower, the content of impurities is less, and the product has excellent anti-erosion and anti-shrinkage capabilities;
as can be seen from the above examples 1-4, in the present application, metallurgical coke and high purity graphite strips are used as arc starting materials, chromium sesquioxide particles and chromium sesquioxide dust generated in a chromium sesquioxide crushing process are used as bottom laying materials, the arc starting materials can be rapidly combusted and volatilized after a molten pool is formed in an auxiliary manner, contact time with the chromium sesquioxide is reduced to the maximum extent, reduction and fusion of trivalent chromium by carbon at a high temperature are reduced, the content of chromium metal in a product is reduced, and the problem of increase of the content of chromium metal in common electrofused chromium oxide is solved;
it can be known from the above embodiments 1-4 that, this application adopts open arc melting to cooperate with continuous feeding, has increased and smelts the arc length, has increased the distance of graphite electrode and molten bath, controls the induced air volume in the electric arc furnace simultaneously, takes out the superfine carbon particle that produces at high temperature apart from the graphite electrode, compares the submerged arc operation of ordinary electrofusion chromic oxide production, has stopped the direct contact of material with graphite electrode, has solved the problem that carbon content increases in the electrofusion chromic oxide product among the prior art scheme.
Finally, it should be noted that: the above-mentioned embodiments are only specific embodiments of the present invention, which are used for illustrating the technical solutions of the present invention and not for limiting the same, and the protection scope of the present invention is not limited thereto, although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention should be defined by the appended claims.
Claims (7)
1. A preparation method of low-carbon low-metal-content electrofused chromium oxide is characterized in that a mixture of chromium sesquioxide particles and chromium sesquioxide dust collection dust generated in a chromium sesquioxide crushing procedure is paved, metallurgical coke particles and high-purity graphite strips are used as arcing materials, and the low-carbon low-metal-content electrofused chromium oxide product is prepared through open arc smelting.
2. A preparation method of low-carbon low-metal content electrofusion chromium oxide is characterized by comprising the following steps:
s1, mixing chromic oxide particles and chromic oxide dust generated in a chromic oxide crushing process, paving the mixture at the bottom, and covering the mixture with a to-be-melted chromic oxide raw material;
s2, placing metallurgical coke particles on a chromic oxide raw material into a star shape or a triangular shape at the position corresponding to an electrode, and placing three high-purity graphite strips on the coke, wherein the end points of the star shape or the triangular shape correspond to the graphite electrode;
s3, firstly, placing the graphite electrode to be just in contact with the end point of the high-purity graphite strip laid on the furnace bottom, then electrifying the graphite electrode, and smelting in a high-current and low-voltage mode;
s4, after the chromium sesquioxide laid at the bottom in the furnace is melted to form a molten pool and the metallurgical coke particles and the three high-purity graphite strips are combusted, starting to add the chromium sesquioxide raw material at a constant speed, and adopting open arc melting in the furnace;
s5, controlling the continuous feeding amount of the chromium sesquioxide according to the smelting condition in the furnace, and stopping feeding and smelting after the molten liquid reaches the expected feeding amount;
and S6, after the smelting is finished, the graphite electrode is powered off, and the materials in the furnace are naturally cooled, crystallized, crushed and screened to obtain the low-carbon low-metal-content electrofusion chromium oxide product.
3. The method for preparing low-carbon low-metal content electrofused chromium oxide according to claim 2, wherein the grain size of electrofused chromium oxide particles for bedding in S1 is 0-3mm, the ratio of the particles to dust collecting ash is 1-5, and the bedding thickness is 20-70cm.
4. The method for preparing low-carbon low-metal content electrofused chromium oxide according to claim 2, wherein the thickness of the furnace bottom covered with the raw material of chromium oxide in S1 is 5-20cm.
5. The method for preparing low-carbon low-metal content electrofused chromium oxide according to claim 2, wherein the particle size of the metallurgical coke particles in S2 is 0.5-5cm.
6. The method for preparing the electrofusion chromium oxide with low carbon and low metal content as claimed in claim 2, wherein the carbon content in the high-purity graphite strips in S2 is more than or equal to 99.5%, and the cross-sectional area is 0.5-5cm 2 。
7. The method for preparing low-carbon low-metal content electrofused chromium oxide according to claim 2, wherein the constant electrode current is 12000A and the electrode voltage is 60-100V during smelting.
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| Title |
|---|
| 顾立德, 冶金工业出版社 * |
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