CN114015902B - Method for producing vanadium-aluminum alloy by one-step method - Google Patents
Method for producing vanadium-aluminum alloy by one-step method Download PDFInfo
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- CN114015902B CN114015902B CN202111122718.4A CN202111122718A CN114015902B CN 114015902 B CN114015902 B CN 114015902B CN 202111122718 A CN202111122718 A CN 202111122718A CN 114015902 B CN114015902 B CN 114015902B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
- C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/04—Crucible or pot furnaces adapted for treating the charge in vacuum or special atmosphere
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details peculiar to crucible or pot furnaces
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details peculiar to crucible or pot furnaces
- F27B14/10—Crucibles
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Abstract
The invention relates to the field of vanadium metallurgy, and discloses a method for producing a vanadium-aluminum alloy by a one-step method. The method comprises the following steps: (1) providing a graphite crucible smelting furnace; (2) paving a lining material at the bottom of the furnace body of the graphite crucible smelting furnace, then placing an aluminum foil gasket in the middle of the furnace body of the smelting furnace, and then filling the lining material to obtain the vanadium-aluminum alloy smelting furnace; (3) evenly dividing vanadium pentoxide into N parts according to weight, and uniformly mixing N parts of vanadium pentoxide material, N parts of aluminum particles and N parts of heat regulating agent in sequence to obtain 1 st to N th mixed materials; (4) igniting the 1 st mixture, and sequentially adding the 2 nd to the Nth mixtures after the 1 st mixture starts aluminothermic reaction; (5) and standing, cooling, disassembling the furnace, crushing, polishing and selecting after the reaction is finished to obtain the finished product vanadium-aluminum alloy. The invention realizes the one-step smelting production of the vanadium-aluminum alloy, improves the product quality and reduces the production cost.
Description
Technical Field
The invention relates to the field of vanadium metallurgy, in particular to a method for producing a vanadium-aluminum alloy by a one-step method.
Background
The vanadium-aluminum alloy is an important additive of the titanium alloy, and can improve the properties of the titanium alloy, such as strength, toughness, formability, corrosion resistance, high temperature resistance and the like. The high-performance titanium alloy produced after the vanadium-aluminum alloy is added can be used for producing products such as jet engines, high-speed aircraft frameworks, rocket engine casings, gliders, automobile engine systems, automobile chassis parts, golf clubs, medical devices and the like. With the rapid development of the economy of China and the continuous improvement of the consumption level of people, the national defense strength and the space navigation strength of China are obviously enhanced, and the high-quality titanium alloy applied to the high-end fields of civil industry, aerospace and the like has a great growth momentum.
The main aluminothermic self-propagating process of the vanadium-aluminum alloy in China is used for production, a corundum dry sintering furnace, a magnesia sintering furnace, a graphite crucible and the like are usually adopted for smelting as reaction containers, materials such as vanadium oxide, aluminum particles, additives and the like are mixed and then added into the furnace, the mixture is ignited from the upper part for reaction, and after the reaction is finished, the furnace is disassembled, crushed and finished after being cooled in the air, so that the vanadium-aluminum alloy product is obtained. Patent application CN 201520341731.2 "a cooling device for aluminum alloy products" which can remove harmful fumes and collect waste water generated during cooling. The device takes away heat through cooling water, is simple to operate, is convenient to use, and is suitable for cooling in the processing process of aluminum alloy products. Patent application CN 201510075546.8 "vanadium-aluminum alloy and preparation method thereof" relates to a preparation method of vanadium-aluminum alloy, comprising the following steps: taking vanadium pentoxide and aluminum as raw materials, igniting and carrying out reduction reaction to obtain a vanadium-aluminum alloy; the graphite crucible with a cover with holes and the whole inner wall coated with the fused magnesia fire clay is used as a smelting furnace. Patent application CN 201710561632.9 "a method for preparing vanadium-aluminum alloy" relates to a method for preparing vanadium-aluminum alloy, and provides a method for preparing vanadium-aluminum alloy with simple process, low cost, easily controlled impurities and low content, which comprises the following steps: taking vanadium-containing oxide and aluminum powder with proper vanadium oxide molar ratio, placing the vanadium-containing oxide and the aluminum powder in a reaction furnace, igniting by an igniter to carry out aluminothermic reduction reaction, and obtaining the vanadium-aluminum alloy. Patent application CN 201810228430.7 "a method for producing vanadium-aluminum alloy" provides a method for improving the yield and quality of vanadium-aluminum alloy, reducing the impurity content of vanadium-aluminum alloy, enlarging the production scale and reducing the cost, which comprises: adding a first batch of vanadium pentoxide and aluminum into a graphite crucible with a drilling hole cover, igniting to perform an aluminothermic reduction reaction, after the reaction is completed, sequentially adding a subsequent batch of vanadium pentoxide and aluminum, respectively performing the aluminothermic reduction reaction until the vanadium pentoxide and the aluminum are completely added and react completely, and separating slag from gold to obtain the vanadium-aluminum alloy. Patent application CN 201911144319.0' preparation method of vanadium-aluminum alloyThe method and the reactor' provide a preparation method of vanadium-aluminum alloy and a reactor, and the preparation method comprises the following steps: 1) mixing a vanadium source, an aluminum source and a slag former to obtain a mixed material; 2) heating the mixed material to obtain a reaction product; 3) and cooling the reaction product under the condition of vacuumizing or introducing protective gas to obtain the vanadium-aluminum alloy. Patent CN110129595B "method for improving yield of AlV55 vanadium-aluminum alloy" provides a method for improving yield of vanadium-aluminum alloy and a reactor, comprising: a. will V2O5Weighing metal Al and AlV55 crushed alloy, and then filling the weighed metal Al and the crushed alloy into a charging bucket for mixing; b. pouring the mixed materials into a reactor for aluminothermic reduction smelting; c. and carrying out sand blasting and crushing treatment to obtain an AlV55 vanadium-aluminum alloy finished product. Patent application CN 201710364271.9 "a method for removing impurities from finished vanadium-aluminum alloy" provides a method for treating vanadium-aluminum alloy, which comprises: a. removing large blocky slag inclusions on the surface of the vanadium-aluminum alloy ingot; b. carrying out sand blasting treatment on the vanadium-aluminum alloy ingot; c. crushing a vanadium-aluminum alloy ingot; d. separating the alloy block containing the oxide film from the alloy block not containing the oxide film, and crushing the alloy block not containing the oxide film completely; e. the alloy block containing the oxide film is subjected to secondary sand blasting. Patent application CN 2013107420790 "a preparation method for preventing the segregation of vanadium-aluminum alloy" provides a preparation method of vanadium-aluminum alloy, comprising: 1) smelting an aluminum-vanadium intermediate alloy; 2) stirring the melt in the smelting furnace once every 20 minutes for more than 3 times; 3) sampling and analyzing the chemical composition of the melt; 4) after the analysis is qualified, the melt is led into a standing furnace while stirring, and the powder refining agent is blown into the melt by nitrogen for refining treatment; 5) and (4) standing after refining, and immediately casting.
The production of the vanadium-aluminum alloy has the following outstanding problems: 1) the corundum or magnesite knotting furnace has good heat preservation and slow cooling, and the oxidation and nitridation of the vanadium-aluminum alloy are serious because O in the corundum or magnesite diffuses into the reducing melt; 2) because the vanadium-aluminum alloy is an infinite mutual-soluble solid melt, the main species V, Al in the melt has density difference, the sedimentation velocity of V with higher density in the alloy melt is higher than that of Al with lower density under the action of gravity, so that the segregation phenomenon of' lower upper part of vanadium is higher than lower upper part of aluminum is presented in a vanadium-aluminum alloy ingot, the upper-lower difference of V content and Al content in the vanadium-aluminum alloy ingot is up to 2-4% due to gravity segregation, and the chemical composition segregation of the vanadium-aluminum alloy caused by gravity sedimentation difference cannot be effectively controlled under the existing smelting process condition; 3) the materials are added into the furnace body all at once and then are ignited at the upper part to smelt the vanadium-aluminum alloy, so that the splashing phenomenon exists, and the smelting yield is reduced.
At present, the problems of high impurity content, large component segregation and the like generally exist in the vanadium-aluminum alloy industry in China, and extremely strict requirements on the component segregation and the impurity content of vanadium-aluminum are met in high-end fields.
Disclosure of Invention
The invention aims to solve the problems of high impurity content, large component segregation and the like of vanadium-aluminum alloy in the prior art, and provides a method for producing the vanadium-aluminum alloy by one step.
In order to achieve the above object, the present invention provides a method for producing a vanadium-aluminum alloy in a one-step method, comprising the steps of:
(1) providing a graphite crucible smelting furnace: the graphite crucible smelting furnace comprises a graphite crucible base, a first graphite crucible and a second graphite crucible which are detachably connected in sequence from bottom to top; the graphite crucible base is of a convex cylindrical structure; the first graphite crucible comprises two identical hollow semi-cylinders, two side edges of each hollow semi-cylinder are provided with stepped occlusion parts, and the two semi-cylinders can be occluded and spliced end to form a hollow cylinder structure through the stepped occlusion parts; the second graphite crucible is of a hollow cylinder structure;
(2) paving a lining material at the bottom of the graphite crucible smelting furnace body in the step (1), vibrating the lining material to be smooth and compact, then placing an aluminum foil gasket in the middle of the graphite crucible smelting furnace body, wherein the diameter of the aluminum foil gasket is 20-35mm smaller than the inner diameter of the graphite crucible smelting furnace body, and then filling the lining material in a gap formed by the graphite crucible smelting furnace body and the aluminum foil gasket to obtain the vanadium-aluminum alloy smelting furnace;
(3) evenly dividing vanadium pentoxide into N parts by weight, and sequentially weighing N parts of aluminum particles according to the following requirements, wherein the aluminum particles comprise the following components in parts by weight: the weight of the 1 st part of aluminum particles is q times of the theoretical value, the weight of the Nth part of aluminum particles is 2-q times of the theoretical value, and the weight of the kth part of aluminum particles is theoretical value
Multiple, k is more than 1 and less than N, k is an integer, and q is more than or equal to 1.14 and less than or equal to 1.18; mixing N parts of vanadium pentoxide material with N parts of aluminum particles and N parts of heat regulating agent in sequence to obtain 1 st part of mixture, 2 nd part of mixture, 3 rd part of mixture to N th part of mixture, and controlling the 1 st part of mixture, 2 nd part of mixture to the N th part of mixture
The heat quantity of the unit furnace charge of the part mixture is 3000-
Part mixture, first
Mixing the materials to the first
The heat of the unit furnace charge of the part mixture is 3200-
Part mixture, first
The unit charging heat from the part mixture to the Nth part mixture is 3300-;
(4) paving the 1 st part of mixture obtained in the step (3) at the bottom of the vanadium-aluminum alloy smelting furnace obtained in the step (2), then igniting and igniting the 1 st part of mixture, and after the 1 st part of mixture starts to carry out aluminothermic reaction, sequentially adding the 2 nd part of mixture, the 3 rd part of mixture to the Nth part of mixture in a continuous feeding mode;
(5) after the thermit reaction is finished, standing, pushing into a vacuum chamber, introducing argon into the vacuum chamber for cooling, and then sequentially disassembling, crushing, polishing and selecting to obtain a finished product vanadium-aluminum alloy;
wherein, in the step (2), the lining material contains vanadium-aluminum alloy powder, and the chemical composition of the vanadium-aluminum alloy powder comprises 43-76 wt% of V and 24-57 wt% of Al;
in the step (3), the heat quantity regulating agent is lime and/or potassium chlorate.
Preferably, in step (1), the stepped engaging portion of one side edge has an inner concave portion and an outer convex portion, and the stepped engaging portion of the other side edge has an inner convex portion and an outer concave portion.
Further preferably, the radius of the top surface of the graphite crucible base is the same as the inner radius of the first graphite crucible and the inner radius of the second graphite crucible, and the radius of the bottom surface of the graphite crucible base is the same as the outer radius of the first graphite crucible and the outer radius of the second graphite crucible.
Further preferably, the radius of the top surface of the graphite crucible base is 100-500 mm.
Further preferably, the radius of the top surface of the graphite crucible base is 150-400 mm.
Preferably, in the step (1), the difference between the radius of the bottom surface of the graphite crucible base and the radius of the top surface of the graphite crucible base is 40-100 mm.
Preferably, in the step (1), the height of the first graphite crucible is the same as the height of the second graphite crucible.
Further preferably, the ratio of the height of the first graphite crucible to the radius of the top surface of the graphite crucible base is 1-8: 1.
Further preferably, the height of the graphite crucible base is 40-100 mm.
Preferably, in the step (2), the height of the lining material laid at the bottom of the furnace body of the graphite crucible smelting furnace is 32-54 mm.
Further preferably, the thickness of the aluminum foil gasket is 0.45-0.55 mm.
Preferably, in the step (2), the chemical composition of the vanadium-aluminum alloy powder comprises 43-51 wt% of V and 49-57 wt% of Al.
Further preferably, the chemical composition of the vanadium-aluminum alloy powder comprises 50-62 wt% of V and 38-50 wt% of Al.
Further preferably, the chemical composition of the vanadium-aluminum alloy powder comprises 60-71 wt% of V and 29-40 wt% of Al.
Further preferably, the chemical composition of the vanadium-aluminum alloy powder comprises 63-76 wt% of V and 24-37 wt% of Al.
Preferably, in step (3), 3. ltoreq. N.ltoreq.10, and N is an integer.
Preferably, in the step (3), V in the vanadium pentoxide is2O5Content of >99 wt.%, content of Fe<0.09 wt%, content of Si<0.095 wt%, content of C<0.02 wt%, and the particle size of the vanadium pentoxide is 2-4 mm.
Further preferably, the content of Al in the aluminum particles is >99.8 wt.%, the content of Fe is <0.05 wt.%, the content of Si is <0.05 wt.%, the content of C is <0.01 wt.%, and the particle size of the aluminum particles is 2-4 mm.
Preferably, in step (4), the feeding speed of the continuous feeding is 200-500 kg/min.
Preferably, in the step (5), the standing time is 10 to 30 min.
Further preferably, the cooling time is 24-72 h.
The invention is provided with the graphite crucible special for vanadium-aluminum smelting, the lining material and complete technical methods of controlling segregation, regulating and controlling heat, continuously feeding, protecting and cooling and the like by adopting gradient aluminum distribution, realizes one-step smelting production of high-quality vanadium-aluminum alloy, improves the product quality and reduces the production cost.
Drawings
FIG. 1 is a schematic view of a graphite crucible furnace of the present invention;
FIG. 2 is a schematic view of a graphite crucible base;
FIG. 3 is a schematic view of a first graphite crucible;
FIG. 4 is a schematic view of a second graphite crucible;
FIG. 5 is a schematic view of a vanadium aluminum alloy smelting furnace made in accordance with the present invention;
FIG. 6 is a schematic view of a sampling position in test example 2 of the present invention.
Description of the reference numerals
1 graphite crucible base 2 first graphite crucible
3 second graphite crucible 21 first hollow semi-cylinder
22 second hollow semi-cylinder
45 aluminium foil packing ring 6 inside linings of graphite crucible smelting furnace
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for producing vanadium-aluminum alloy by a one-step method, which comprises the following steps:
(1) providing a graphite crucible smelting furnace 4: the graphite crucible smelting furnace 4 comprises a graphite crucible base 1, a first graphite crucible 2 and a second graphite crucible 3 which are detachably connected in sequence from bottom to top; the graphite crucible base 1 is of a convex cylindrical structure; the first graphite crucible 2 comprises two identical hollow semi-cylinders, two side edges of each hollow semi-cylinder are provided with stepped occlusion parts, and the two semi-cylinders can be occluded and spliced end to form a hollow cylinder structure through the stepped occlusion parts; the second graphite crucible 3 is of a hollow cylinder structure;
(2) paving a lining material at the bottom of the furnace body of the graphite crucible smelting furnace 4 in the step (1), vibrating the lining material to be smooth and compact, then placing an aluminum foil gasket 5 in the middle of the furnace body of the graphite crucible smelting furnace 4, wherein the diameter of the aluminum foil gasket 5 is 20-35mm smaller than the inner diameter of the furnace body of the graphite crucible smelting furnace 4, and then filling the lining material in a gap formed by the furnace body of the graphite crucible smelting furnace 4 and the aluminum foil gasket 5 to obtain the vanadium-aluminum alloy smelting furnace;
(3) evenly dividing vanadium pentoxide into N parts by weight, and sequentially weighing N parts of aluminum particles according to the following requirements, wherein the aluminum particles comprise the following components in parts by weight: the weight of the 1 st part of aluminum particles is q times of the theoretical value, the weight of the Nth part of aluminum particles is 2-q times of the theoretical value, and the weight of the kth part of aluminum particles is theoretical value
Multiple, k is more than 1 and less than N, k is an integer, and q is more than or equal to 1.14 and less than or equal to 1.18; mixing N parts of vanadium pentoxide material with N parts of aluminum particles and N parts of heat regulating agent in sequence to obtain 1 st part of mixture, 2 nd part of mixture, 3 rd part of mixture to N th part of mixture, and controlling the 1 st part of mixture, 2 nd part of mixture to the N th part of mixture
The heat quantity of the unit furnace charge of the part mixture is 3000-
Part mixture, first
Mixing the materials to the first
Portion mixtureThe heat per unit charge is 3200-3300kJ/kg
Part mixture, first
The unit charging heat from the part mixture to the Nth part mixture is 3300-;
(4) paving the 1 st part of mixture obtained in the step (3) at the bottom of the vanadium-aluminum alloy smelting furnace obtained in the step (2), then igniting and igniting the 1 st part of mixture, and after the 1 st part of mixture starts to carry out aluminothermic reaction, sequentially adding the 2 nd part of mixture, the 3 rd part of mixture to the Nth part of mixture in a continuous feeding mode;
(5) after the thermit reaction is finished, standing, pushing into a vacuum chamber, introducing argon into the vacuum chamber for cooling, and then sequentially disassembling, crushing, polishing and selecting to obtain a finished product vanadium-aluminum alloy;
wherein, in the step (2), the lining material contains vanadium-aluminum alloy powder, and the chemical composition of the vanadium-aluminum alloy powder comprises 43-76 wt% of V and 24-57 wt% of Al;
in the step (3), the heat quantity regulating agent is lime and/or potassium chlorate.
In the present invention, the graphite crucible smelting furnace 4 is schematically shown in FIG. 1, in which 1A is a front view and 1B is a sectional view.
In the present invention, the graphite crucible base 1 is a convex cylindrical structure, and the schematic view of the graphite crucible base 1 is shown in fig. 2, in which the front view is shown in fig. 2A, and the top view is shown in fig. 2B. The convex cylinder structure is composed of a cylinder bottom with a larger radius and a cylinder convex part with a smaller radius.
In a preferred embodiment, the radius (R1) of the top surface of the graphite crucible base 1 is 100-500 mm;
in a preferred embodiment, the radius of the top surface of the graphite crucible base 1 is 150-400 mm.
Further preferably, the difference between the radius of the bottom surface of the graphite crucible base 1 (R2) and the radius of the top surface of the graphite crucible base 1 is 40-100 mm.
In the present invention, a schematic view of the first graphite crucible 2 is shown in fig. 3, wherein fig. 3A is a front view and fig. 3B is a top view, and the first graphite crucible 2 includes a first hollow semi-cylinder 21 and a second hollow semi-cylinder 22.
In the invention, the first graphite crucible 2 comprises two identical hollow semi-cylinders, and because the two hollow semi-cylinders have the same structure, if one hollow semi-cylinder is damaged in the industrial smelting process, a new hollow semi-cylinder can be assembled with the other hollow semi-cylinder which is not damaged, the whole first graphite crucible does not need to be replaced, and the cost can be saved.
In a preferred embodiment, the stepped bite of one side of each of the hollow semi-cylinders has an inner concave portion and an outer convex portion, and the stepped bite of the other side has an inner convex portion and an outer concave portion.
In a preferred embodiment, the projections and depressions of the medial depression, lateral projection, medial projection and lateral depression are the same size. Further preferably, the length and width of the convex and concave portions are the same as the thickness (D) of the hollow semi-cylindrical body, that is, the same as the difference between the outer radius and the inner radius of the first graphite crucible 2.
In a specific embodiment, the installation can be completed by inserting the outer protrusion of the first hollow semi-cylinder 21 into the outer recess of the second hollow semi-cylinder, inserting the inner protrusion of the second hollow semi-cylinder 22 into the inner recess of the first hollow semi-cylinder 21, inserting the inner protrusion of the first hollow semi-cylinder 21 into the inner recess of the second hollow semi-cylinder 22, inserting the outer protrusion of the second hollow semi-cylinder 22 into the outer recess of the first hollow semi-cylinder 21 so that the two semi-cylinders are engaged and spliced into a hollow cylindrical structure. Because the two hollow semi-cylinders are installed in an inserting and meshing mode, compared with the traditional simple splicing mode, the invention reduces gaps, and can prevent the leakage and the loss of materials in the smelting process on the premise of ensuring the convenience of disassembling the furnace.
In a preferred embodiment, the first graphite crucible 2 further has "ears" connected to the outer protrusions and the outer depressions. Further preferably, the length of the ear is twice the thickness of the hollow semi-cylinder.
In a preferred embodiment, the top radius (R1) of the graphite crucible base 1 is the same as the inner radius (R3) of the first graphite crucible 2 and the inner radius (R5) of the second graphite crucible 3, and the bottom radius (R2) of the graphite crucible base 1 is the same as the outer radius (R4) of the first graphite crucible 2 and the outer radius (R6) of the second graphite crucible 3.
In a preferred embodiment, the height (H3) of the first graphite crucible 2 is the same as the height (H4) of the second graphite crucible 3;
further preferably, the ratio of the height (H3) of the first graphite crucible 2 to the radius of the top surface of the graphite crucible base 1 is 1-8: 1;
preferably, the height (H2) of the graphite crucible base (1) is 40-100mm, wherein the height H1 of the bottom of the cylinder with larger radius is 10-30 mm.
In the present invention, a schematic view of the second graphite crucible 3 is shown in FIG. 4, in which FIG. 4A is a front view and FIG. 4B is a plan view.
In the invention, the graphite crucible smelting furnace 4 for producing the vanadium-aluminum alloy by the one-step method can be sequentially installed from bottom to top when in use. Specifically, the specific process of the installation of the graphite crucible smelting furnace 4 for producing the vanadium-aluminum alloy by the one-step method is as follows: a first graphite crucible 2 is placed on a graphite crucible base 1, two identical semi-cylinders of the first graphite crucible 2 are meshed and spliced into a hollow cylinder structure head and tail through stepped meshing parts, and then a second graphite crucible 3 is placed on the first graphite crucible 2.
In the method for manufacturing the vanadium-aluminum alloy smelting furnace in the step (2), a layer of lining material with a specific chemical composition is firstly paved at the bottom of the furnace body of the graphite crucible smelting furnace 4 in the step (1), then an aluminum foil gasket 5 is placed, finally the lining material with the specific chemical composition is filled in a gap formed between the aluminum foil gasket 5 and the periphery of the furnace body of the graphite crucible smelting furnace 4, and linings 6 are formed at the periphery and the bottom of the furnace body of the graphite crucible smelting furnace 4 (as shown in fig. 5).
In the method of the invention, the V, Al content of the vanadium-aluminum alloy powder contained in the lining material is determined according to the grade of smelting vanadium-aluminum alloy. The lining material provided by the invention has the following two functions: 1) preventing C in the graphite smelting crucible furnace 4 or O in the magnesia knotting furnace from diffusing into the alloy melt to influence the components of the vanadium-aluminum alloy product; 2) during cooling, the lining material can prevent O and N from diffusing into the alloy by absorbing O and N by itself, and further reduce O, N content in the vanadium-aluminum alloy product. To achieve both of the above effects, the liner material needs to have the following properties: 1) the lining material is in a reflow state in the vanadium-aluminum smelting process; 2) the lining material can not be converted into alloy liquid with better flow and enters the vanadium-aluminum alloy melt. In order to achieve the purpose, the inventor researches the melting properties of vanadium-aluminum alloys with different grades and different V, Al contents, and finds that the melting point of the alloy is gradually increased along with the increase of the V content in the vanadium-aluminum alloy. In the smelting process of each grade of vanadium-aluminum alloy, aluminum and vanadium pentoxide in furnace burden are subjected to oxidation-reduction reaction, the reaction releases heat to enable the reduced alloy and slag phase to be in a liquid state, the reaction process belongs to self-propagating reaction heat release, and the reaction duration is 1-5 min. The lining material does not emit heat in the vanadium-aluminum smelting process, and the temperature of the lining material is increased through the heat conduction of the vanadium-aluminum alloy liquid and the molten slag. Research results show that in the reaction process of smelting AlV55, V-aluminum alloy powder with 43-51 wt% of V and 49-57 wt% of Al is used as a lining material, so that the V-aluminum alloy powder can be subjected to in-situ reflow without entering alloy liquid, and O or C in a furnace body material is prevented from entering the alloy; after the vanadium-aluminum smelting reaction is finished, the temperature of the lining material soft melt and the vanadium-aluminum alloy liquid in the furnace begins to be reduced, the melting point of the lining material is lower than that of the vanadium-aluminum alloy liquid because the content of V in the lining material is lower than that of V in the vanadium-aluminum alloy, the lining material is always in a soft melting state within 0-30min in the temperature reduction process, the vanadium-aluminum alloy liquid begins to solidify after the temperature of the vanadium-aluminum alloy liquid is lower than that of the alloy liquid, and in the process, external gas is absorbed and blocked by the lining material in the soft melting state and cannot enter the vanadium-aluminum alloy liquid, so that the effective control of O, N in the vanadium-aluminum alloy is realized; and further cooling, completely solidifying the vanadium-aluminum alloy liquid, and when the temperature is lower than the melting point of the lining material, solidifying the soft melt of the lining material again, and completely wrapping the vanadium-aluminum alloy which is solidified firstly by the solidified lining material, so that the outside O, N is prevented from entering. In the process of disassembling the furnace and finishing, the lining material and the vanadium-aluminum alloy can be efficiently separated and removed, so that the O, N content in the vanadium-aluminum alloy is effectively controlled. The lining materials adopted in the smelting process of other grades of vanadium-aluminum alloys can be determined according to the principle.
In a specific embodiment, when AlV55 is smelted, the chemical composition of the vanadium-aluminum alloy powder comprises 43-51 wt% of V and 49-57 wt% of Al.
In a specific embodiment, when AlV65 is smelted, the chemical composition of the vanadium-aluminum alloy powder comprises 50-62 wt% of V and 38-50 wt% of Al.
In a specific embodiment, when AlV75 is smelted, the chemical composition of the vanadium-aluminum alloy powder comprises 60-71 wt% of V and 29-40 wt% of Al.
In a specific embodiment, when AlV85 is smelted, the chemical composition of the vanadium-aluminum alloy powder comprises 63-76 wt% of V and 24-37 wt% of Al.
In the method of the present invention, in a preferred embodiment, it is necessary to control the particle size of the vanadium-aluminum alloy powder within a suitable range.
In a specific embodiment, the particle size of the vanadium-aluminum alloy powder can be in any range of 0.1 to 3mm, such as 0.1 to 1mm, 0.1 to 2mm, 0.1 to 3mm, 1 to 2mm, 1 to 3mm, or 2 to 3 mm.
On one hand, the melting state of the vanadium-aluminum alloy powder needs to be controlled to be subjected to in-situ reflow, the melting state of the vanadium-aluminum alloy powder is not only related to V, Al content, but also related to the particle size of the vanadium-aluminum alloy powder, the larger the particle size is, the higher the reflow temperature is, the smaller the particle size is, the lower the reflow temperature is, when the particle size of the vanadium-aluminum alloy powder is smaller than 0.1mm, the heat produced by smelting the vanadium-aluminum alloy can completely melt the lining material into a liquid state with a better flowing state through heat conduction and is fused with the vanadium-aluminum alloy liquid, the effect of controlling C, O, N cannot be realized, when the particle size of the vanadium-aluminum alloy powder is larger than 3mm, the heat produced by smelting the vanadium-aluminum alloy cannot cause the lining material to be subjected to reflow through heat conduction, at the moment, the lining material exists in the form of solid particles, and cannot wrap the vanadium-aluminum alloy in the cooling process, so that the effect of controlling the content of the vanadium-aluminum alloy O, N is poor; on the other hand, when the particle size is less than 0.1mm, the amount of dust in the operation site increases rapidly during the use, which deteriorates the site operation environment, and when the particle size is more than 3mm, a large amount of air is present between the solid particles, which cannot be discharged by the tapping operation, and the reaction process of absorption O, N is slow because the particles of the lining material are large and have a small specific surface area during the cooling process, so that the outside air diffuses and penetrates through the protective layer of the lining material and enters the vanadium-aluminum alloy, and therefore, the particle size of the vanadium-aluminum alloy powder needs to be controlled within a suitable range.
In a preferred embodiment, in the step (2), the height of the lining material laid in the furnace body bottom of the graphite crucible smelting furnace 4 may be 32 to 54mm, for example, 32mm, 34mm, 36mm, 38mm, 40mm, 42mm, 44mm, 46mm, 48mm, 50mm, 51mm, 52mm, 53mm or 54 mm. The thickness of the lining material paved at the bottom of the furnace body of the graphite crucible smelting furnace 4 is controlled within the range, because in the cooling process, the outside O, N gas simultaneously generates the oxidative nitridation reaction with the lining material in the process of diffusing in the lining material, the larger the height of the lining material is, the longer the gas diffusion time is, the more O, N the lining material absorbs through the oxidative nitridation reaction, and the lower the O, N concentration is, and research results show that after the height of the lining material is more than 32mm, the O, N concentration of the interface between the lining material and the vanadium-aluminum alloy liquid is already reduced to 0, and after the value is less than the value, the interface O, N concentration is increased, so that the O, N content of the vanadium-aluminum alloy is influenced. Meanwhile, after the height is larger than 54mm, the heat conduction in the vanadium-aluminum alloy smelting process cannot enable all lining materials to be in a reflow state, the function of absorbing and isolating O, N cannot be achieved, the required lining materials are increased, the production cost of the vanadium-aluminum alloy is increased, and in conclusion, the proper height of the lining materials paved at the bottom is 32-54 mm.
In the manufacturing method of the vanadium-aluminum alloy smelting furnace, the thickness of the aluminum foil gasket 5 can be 0.45-0.55 mm; specifically, for example, it may be 0.45mm, 0.46mm, 0.47mm, 0.48mm, 0.49mm, 0.5mm, 0.51mm, 0.52mm, 0.53mm, 0.54mm or 0.55 mm.
In the present invention, in step (3), in a preferred embodiment, 3. ltoreq. N.ltoreq.10, and N is an integer. In particular embodiments, N may be 3, 4, 5, 6, 7, 8, 9, or 10.
In the invention, in the step (3), when N is a multiple of 3,
and
taking a calculated value; when N does not take a multiple of 3,
and
integer values are rounded off.
In a preferred embodiment, in step (3), 1.15. ltoreq. q.ltoreq.1.16.
In a preferred embodiment, in step (3), V in the vanadium pentoxide is2O5Content of >99 wt.%, content of Fe<0.09 wt%, content of Si<0.095 wt%, content of C<0.02 wt%, and the particle size of the vanadium pentoxide is 2-4 mm.
In a preferred embodiment, in step (3), the content of Al in the aluminum particles is >99.8 wt.%, the content of Fe is <0.05 wt.%, the content of Si is <0.05 wt.%, the content of C is <0.01 wt.%, and the particle size of the aluminum particles is 2-4 mm.
In a specific embodiment, the specific operations of step (3) and step (4) are as follows:
(3) the vanadium pentoxide material is divided into 5 parts according to the weight average, and the following components are addedWeighing 5 parts of aluminum particles in sequence, wherein the aluminum particles comprise the following components in parts by weight: the weight of the 1 st part of aluminum particles is q times of the theoretical value, and the weight of the 2 nd part of aluminum particles is the theoretical value
The weight of the 3 rd part of aluminum particles is 1 time of the theoretical value, and the weight of the 4 th part of aluminum particles is the theoretical value
Mixing 5 parts of vanadium pentoxide materials with 5 parts of aluminum particles and 5 parts of heat regulating agent in sequence to obtain a 1 st part of mixture, a 2 nd part of mixture, a 3 rd part of mixture, a 4 th part of mixture and a 5 th part of mixture, controlling the unit furnace charge heat of the 1 st part of mixture and the 2 nd part of mixture to be 3000-;
(4) and (3) paving the 1 st mixture obtained in the step (3) at the bottom of the vanadium-aluminum alloy smelting furnace obtained in the step (2), then igniting and igniting the 1 st mixture, and after the 1 st mixture starts to carry out aluminothermic reaction, sequentially adding the 2 nd mixture, the 3 rd mixture, the 4 th mixture and the 5 th mixture in a continuous feeding mode.
In the present invention, in step (3), the raw aluminum particles have two functions: firstly, participate in the reduction of V2O5Formation of V and Al2O3(ii) a Second, Al and V produce Al8V5、AlV3The compound or solid solution enters the alloy phase. In the present invention, the theoretical value is the theoretical value of the amount of aluminum used in the process of producing the vanadium-aluminum alloy, that is, V2O5The sum of the theoretical addition of Al required for reduction to V and the theoretical addition of Al required in the vanadium-aluminum alloy.
In a preferred embodiment, in the step (3), when the grade of the vanadium-aluminum alloy is AlV55, the theoretical value of aluminum particles is V2O50.87 to 1.06 times of the weight; when the mark of the vanadium-aluminum alloy is AlV65, the theoretical value of aluminum particles is V2O50.74-0.87 times of the weight; when the mark of the vanadium-aluminum alloy is AlV75, the theoretical value of aluminum particles is V2O50.64-0.74 times of the weight; when the mark of the vanadium-aluminum alloy is AlV85, the theoretical value of aluminum particles is V2O50.56 to 0.64 times the weight of the composition.
In the invention, in the step (3), no special requirement is imposed on the dosage of the heat regulator, and the unit charge heat of the mixed material is controlled within the range described in the application.
In a preferred embodiment, in step (4), the feeding rate of the continuous feeding is 200-500 kg/min. Specifically, the feeding speed can be 200kg/min, 250kg/min, 300kg/min, 350kg/min, 400kg/min, 450kg/min or 500 kg/min.
In the present invention, in the step (5), the standing time is 10 to 30 min. Specifically, the standing time can be 10min, 12min, 15min, 17min, 20min, 22min, 25min, 27min or 30 min.
In the invention, in the step (5), the cooling time is 24-72 h. Specifically, the cooling time can be 24h, 28h, 32h, 36h, 40h, 44h, 48h, 52h, 56h, 60h, 64h, 68h or 72 h.
The method of the invention has the advantages that the graphite crucible smelting furnace is simple and easy to maintain, has the characteristics of good smelting effect and convenient furnace disassembly, the device meets the production requirements of factories, is simple and convenient to operate, can adapt to the existing vanadium-aluminum alloy process, can shorten the cooling time, reduce the loss caused by the damage of furnace disassembly, can reduce the O, N content in alloy products by adding lining materials, improve the product quality, realize continuous and accurate compensation regulation and control on chemical segregation caused by gravity sedimentation in the longitudinal direction of alloy ingots by adopting gradient batching, effectively control the chemical composition segregation caused by gravity sedimentation in the vanadium-aluminum alloy smelting process, improve the quality of vanadium-aluminum alloy, thereby improving the economic benefit of vanadium-aluminum alloy, has obvious social benefit and economic benefit, can enlarge the production scale by adopting a continuous feeding mode, and ensure that the alloy ingots are kept in a molten state for a long time, the yield of vanadium is improved. The obtained vanadium-aluminum alloy has wide application range, can be applied to the high-end technical field and even the aerospace technical field, and has great popularization value and application prospect.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
The following examples were all carried out using the following graphite crucible smelting furnace 4. The graphite crucible smelting furnace 4 (shown in figure 1) comprises a graphite crucible base 1, a first graphite crucible 2 and a second graphite crucible 3 which are detachably connected in sequence from bottom to top;
the graphite crucible base 1 is of a convex cylindrical structure, the schematic diagram is shown in fig. 2, the convex cylindrical structure is composed of a cylindrical bottom with a larger radius and a cylindrical convex part with a smaller radius, the radius of the top surface (R1) of the graphite crucible base 1 is 300mm, the radius of the bottom surface (R2) of the graphite crucible base 1 is 400mm, the height H2 of the graphite crucible base is 100mm, and the height H1 of the bottom of the cylindrical body with a larger radius is 20 mm;
the first graphite crucible 2 comprises two identical hollow semi-cylinders, a schematic view is shown in figure 3, the height H3 of the first graphite crucible 2 is 600mm, the inner radius R3 is 300mm and the outer radius R4 is 400mm, the first hollow semi-cylinder 21 and the second hollow semi-cylinder 22 are respectively, two side edges of each hollow semi-cylinder are provided with step-shaped occlusion parts, the step-shaped occlusion part of one side edge of each hollow semi-cylinder is provided with an inner side depressed part and an outer side protruded part, the step-shaped occlusion part of the other side edge is provided with an inner side protruded part and an outer side depressed part, the sizes of the bulges and the depressions of the inner side depressed part, the outer side raised part, the inner side raised part and the outer side depressed part are the same, the length and width of the convex part and the concave part are the same as the thickness of the hollow semi-cylinders, and the two semi-cylinders can be meshed and spliced end to end through the convex part and the concave part of the stepped meshing part to form a hollow cylinder structure; in the first graphite crucible 2, the outer convex part and the outer concave part are also connected with ears, and the length of the ears is 200 mm;
the second graphite crucible 3 is a hollow cylindrical structure, as shown in fig. 4, the inner radius R5 of the second graphite crucible 3 is 300mm, the outer radius R6 of the second graphite crucible is 400mm, and the height H4 of the second graphite crucible 3 is 600 mm;
the installation process of the graphite crucible smelting furnace 4 is as follows: arrange graphite crucible base 1 in on the smelting platform, then place first graphite crucible 2 on the graphite crucible base 1, and will the outside bellying of first hollow half cylinder 21 inserts the hollow half cylinder outside depressed part of second, will the inboard bellying of the hollow half cylinder 22 of second inserts the inboard depressed part of first hollow half cylinder 21, will the inboard bellying of first hollow half cylinder 21 inserts the inboard depressed part of the hollow half cylinder 22 of second, will the outside bellying of the hollow half cylinder 22 of second inserts the outside depressed part of first hollow half cylinder 21 makes two thereby the halfcylinder interlock splices into a hollow cylinder structure and accomplishes the installation, then place second graphite crucible 3 on the first graphite crucible 2.
Example 1
(1) Laying 38kg of lining material with the height of 35mm at the bottom of a furnace body of a graphite crucible smelting furnace 4, vibrating the lining material to be smooth and compact, wherein the lining material contains vanadium-aluminum alloy powder, the chemical composition of the vanadium-aluminum alloy powder comprises 45 wt% of V and 55 wt% of Al, the granularity of the vanadium-aluminum alloy powder is 0.1-1 mm, placing an aluminum foil gasket 5 with the thickness of 0.48mm in the middle of the furnace body of the graphite crucible smelting furnace 4, and the diameter of the aluminum foil gasket 5 is 30mm smaller than the inner diameter of the furnace body of the graphite crucible smelting furnace 4;
(2) filling 22kg of the lining material in the step (1) in a gap formed by the furnace body of the graphite crucible smelting furnace 4 and the aluminum foil gasket 5 to obtain a vanadium-aluminum alloy smelting furnace;
(3) the method comprises the following steps of averagely dividing 700kg of vanadium pentoxide into 6 parts by weight, and sequentially weighing 6 parts of aluminum particles according to the following requirements, wherein the aluminum particle weight requirements comprise: the weight of the 1 st part of aluminum particles is a theoretical value (V)2O50.90 times of the weight) of the vanadium pentoxide compound, and respectively accounting for 1.084 times, 1.028 times, 0.972 times, 0.916 times and 0.86 times of theoretical values of the aluminum particles from the 2 nd part to the 6 th part, wherein the vanadium pentoxide compound accounts for 6 partsThe materials are sequentially and uniformly mixed with 1 st to 6 th aluminum particles and 1 st to 6 th heat regulating agents (potassium chlorate) to obtain 1 st mixture, 2 nd mixture, 3 rd mixture, 4 th mixture, 5 th mixture and 6 th mixture, and the unit furnace charge heat of the 1 st mixture and the 2 nd mixture is controlled to be 3050kJ/kg, the unit furnace charge heat of the 3 rd mixture and the 4 th mixture is 3250kJ/kg, and the unit furnace charge heat of the 5 th mixture and the 6 th mixture is controlled to be 3370 kJ/kg;
(4) paving the 1 st part of mixture obtained in the step (3) at the bottom of the vanadium-aluminum alloy smelting furnace obtained in the step (2), then igniting and igniting the 1 st part of mixture, and after the 1 st part of mixture starts to carry out aluminothermic reaction, sequentially adding the 2 nd part of mixture, the 3 rd part of mixture to the 6 th part of mixture in a continuous feeding mode, wherein the feeding speed of continuous feeding is 260 kg/min;
(5) standing for 20min after the thermit reaction is finished, then pushing the reaction product into a vacuum chamber, introducing argon into the vacuum chamber for cooling for 50h, then disassembling the furnace to obtain 701.8kg of vanadium-aluminum alloy cakes, and then crushing, polishing and selecting to obtain a finished product vanadium-aluminum alloy;
wherein, in the step (3), V in the vanadium pentoxide is2O599.20 wt%, Fe 0.070 wt%, Si 0.090 wt%, C0.01 wt%, and particle size 2-3 mm;
the aluminum particles used had an Al content of 99.85 wt.%, an Fe content of 0.02 wt.%, an Si content of 0.01 wt.%, a C content of 0.007 wt.% and a particle size of 2-3 mm.
The vanadium-aluminum alloy obtained after cooling is smelted by the method, the yield of the smelted vanadium is 99.1%, and the furnace is smoothly removed in the smelting process. The smelting is carried out for a plurality of times according to the mode, wherein the inner wall of the first graphite crucible 2 is gradually corroded after the 10 th smelting, the first graphite crucible 2 is discarded due to the increase of alloy carburization after being used for 28 times, and the furnace can be smoothly disassembled in the smelting process for a plurality of times.
Example 2
(1) Laying 46kg of lining material with the height of 42mm at the bottom of a furnace body of a graphite crucible smelting furnace 4, and vibrating the lining material to be smooth and compact, wherein the lining material contains vanadium-aluminum alloy powder, the chemical composition of the vanadium-aluminum alloy powder comprises 57 wt% of V and 43 wt% of Al, the granularity of the vanadium-aluminum alloy powder is 1-2 mm, an aluminum foil gasket 5 with the thickness of 0.5mm is arranged in the middle of the furnace body of the graphite crucible smelting furnace 4, and the diameter of the aluminum foil gasket 5 is 28mm smaller than the inner diameter of the furnace body of the graphite crucible smelting furnace 4;
(2) filling 27kg of the lining material in the step (1) into a gap formed by the furnace body of the graphite crucible smelting furnace 4 and the aluminum foil gasket 5 to obtain a vanadium-aluminum alloy smelting furnace;
(3) the 708kg of vanadium pentoxide material is averagely divided into 3 parts by weight, 3 parts of aluminum particles are sequentially weighed according to the following requirements, and the weight requirements of the aluminum particles comprise: the weight of the 1 st part of aluminum particles is a theoretical value (V)2O50.80 times of the weight) of the vanadium pentoxide powder, wherein the weight of the 2 nd to 3 rd aluminum particles is 1.00 times and 0.82 times of the theoretical value respectively, 3 parts of vanadium pentoxide materials are sequentially and uniformly mixed with the 1 st to 3 rd aluminum particles and the 1 st to 3 rd heat regulating agents (lime) to obtain the 1 st mixture, the 2 nd mixture and the 3 rd mixture, and the unit furnace charge heat of the 1 st mixture is controlled to be 3150kJ/kg, the unit furnace charge heat of the 2 nd mixture is controlled to be 3290kJ/kg, and the unit furnace charge heat of the 3 rd mixture is controlled to be 3365 kJ/kg;
(4) paving the 1 st part of mixture obtained in the step (3) at the bottom of the vanadium-aluminum alloy smelting furnace obtained in the step (2), then igniting and igniting the 1 st part of mixture, and after the 1 st part of mixture starts to carry out aluminothermic reaction, sequentially adding the 2 nd part of mixture and the 3 rd part of mixture in a continuous feeding mode, wherein the feeding speed of continuous feeding is 320 kg/min;
(5) standing for 18min after the thermit reaction is finished, then pushing the reaction product into a vacuum chamber, introducing argon into the vacuum chamber for cooling for 64h, then removing the furnace to obtain 660.5kg of vanadium-aluminum alloy cakes, and then sequentially crushing, polishing and selecting to obtain a finished product vanadium-aluminum alloy;
wherein, in the step (3), V in the vanadium pentoxide is2O599.50 wt%, Fe 0.032 wt%, Si 0.037 wt%, and C0.012 wt%, particle size 2-4 mm;
the aluminum particles used had an Al content of 99.90 wt.%, an Fe content of 0.032 wt.%, an Si content of 0.04 wt.%, a C content of 0.008 wt.%, and a particle size of 3-4 mm.
The vanadium-aluminum alloy obtained after cooling is smelted by the method, the yield of the smelted vanadium is 99.3%, and the furnace is smoothly removed in the smelting process. The smelting is carried out for a plurality of times according to the mode, wherein the inner wall of the first graphite crucible 2 is gradually corroded after the 12 th smelting, the first graphite crucible 2 is discarded due to the increase of alloy carburization after being used for 33 times, and the furnace can be smoothly disassembled in the smelting process for a plurality of times.
Example 3
(1) Laying 53kg of lining material with the height of 51mm at the bottom of a furnace body of a graphite crucible smelting furnace 4, and vibrating the lining material to be smooth and compact, wherein the lining material contains vanadium-aluminum alloy powder, the chemical composition of the vanadium-aluminum alloy powder comprises 56 weight percent of V and 44 weight percent of Al, the granularity of the vanadium-aluminum alloy powder is 1-3 mm, an aluminum foil gasket 5 with the thickness of 0.47mm is arranged in the middle of the furnace body of the graphite crucible smelting furnace 4, and the diameter of the aluminum foil gasket 5 is 24mm smaller than the inner diameter of the furnace body of the graphite crucible smelting furnace 4;
(2) filling 25kg of the lining material in the step (1) in a gap formed by the furnace body of the graphite crucible smelting furnace 4 and the aluminum foil gasket 5 to obtain a vanadium-aluminum alloy smelting furnace;
(3) the method comprises the following steps of averagely dividing 705kg of vanadium pentoxide into 9 parts by weight, and sequentially weighing 9 parts of aluminum particles according to the following requirements, wherein the aluminum particle weight requirements comprise: the weight of the 1 st part of aluminum particles is a theoretical value (V)2O50.80 times of the weight) of the mixture, wherein the weights of the 2 nd to 9 th aluminum particles are 1.1125 times, 1.075 times, 1.0375 times, 1.000 times, 0.9625 times, 0.9250 times, 0.8875 times and 0.8500 times of theoretical values respectively, and 9 parts of vanadium pentoxide materials are sequentially and uniformly mixed with the 1 st to 9 th aluminum particles and the 1 st to 9 th heat regulating agent (potassium chlorate) to obtain the 1 st mixture, the 2 nd mixture, the 3 rd mixture, the 4 th mixture, the 5 th mixture, the 6 th mixture, the 7 th mixture, the 8 th mixture and the 9 th mixture, and the mixture is mixedControlling the unit furnace charge heat of the 1 st part of mixture, the 2 nd part of mixture and the 3 rd part of mixture to be 3160kJ/kg, the unit furnace charge heat of the 4 th part of mixture, the 5 th part of mixture and the 6 th part of mixture to be 3240kJ/kg, and the unit furnace charge heat of the 7 th part of mixture, the 8 th part of mixture and the 9 th part of mixture to be 3380 kJ/kg;
(4) paving the 1 st mixture obtained in the step (3) at the bottom of the vanadium-aluminum alloy smelting furnace obtained in the step (2), then igniting and igniting the 1 st mixture, and after the 1 st mixture starts to carry out aluminothermic reaction, sequentially adding the 2 nd mixture, the 3 rd mixture and the 9 th mixture in a continuous feeding manner, wherein the feeding speed of continuous feeding is 420 kg/min;
(5) standing for 24min after the thermit reaction is finished, then pushing the reaction product into a vacuum chamber, introducing argon into the vacuum chamber for cooling for 70h, then removing the furnace to obtain 664.5kg of vanadium-aluminum alloy cakes, and then sequentially crushing, polishing and selecting to obtain a finished product vanadium-aluminum alloy;
wherein, in the step (3), V in the vanadium pentoxide is2O599.78 wt%, 0.040 wt% Fe, 0.050 wt% Si, 0.01 wt% C, 2-4mm grain size;
the aluminum particles used had an Al content of 99.94 wt.%, an Fe content of 0.02 wt.%, an Si content of 0.03 wt.%, an C content of 0.004 wt.%, and a particle size of 2-4 mm.
The vanadium-aluminum alloy obtained after cooling is smelted by the method, the yield of the smelted vanadium is 99.5%, and the furnace is smoothly removed in the smelting process. The smelting is carried out for a plurality of times according to the mode, wherein the inner wall of the first graphite crucible 2 is gradually corroded after the 9 th smelting, the first graphite crucible 2 is abandoned due to the increase of alloy carburization after being used for 26 times, and the furnace can be smoothly disassembled in the smelting process for a plurality of times.
Comparative example 1
The same raw materials as in example 1 were used for smelting under the same conditions, except that the first graphite crucible was not included in the smelting apparatus and the second graphite crucible was directly connected to the graphite crucible base.
The smelting is carried out by the method, wherein 701.2kg of vanadium-aluminum alloy cakes are obtained by normally disassembling the furnace after the smelting. The smelting is carried out for a plurality of times in the above manner, wherein the inner wall of the second graphite crucible is gradually corroded and the furnace disassembly difficulty occurs after the 6 th smelting, and the second graphite crucible is used for the 19 th time and is mechanically damaged due to the furnace disassembly.
Comparative example 2
Carried out according to the method of example 1, except that, in step (2), the chemical composition of the vanadium-aluminum alloy powder comprises 40% by weight of V and 60% by weight of Al;
in this comparative example, the furnace was removed to obtain 721.3kg of a vanadium-aluminum alloy cake.
Comparative example 3
Carried out according to the method of example 3, except that, in step (2), the chemical composition of the vanadium-aluminum alloy powder comprises 77% by weight of V and 23% by weight of Al;
in this comparative example, the furnace was removed to obtain 676.1kg of vanadium-aluminum alloy cake.
Comparative example 4
The method is implemented according to the method of the embodiment 1, except that the vanadium pentoxide, the aluminum particles and the heat regulating agent which are from the same sources as those in the embodiment 1 are directly used as raw materials, the raw materials are the same in weight, the raw materials are put into a smelting furnace for smelting at one time, and the smelting conditions, the standing, the cooling, the furnace dismantling, the crushing, the grinding and the selecting conditions are the same as those in the embodiment 1;
in this comparative example 678.9kg of vanadium-aluminium alloy cake was obtained after dismantling the furnace.
Comparative example 5
The procedure described in example 1 was followed, except that in step (3), q was 1.12;
in this comparative example 699.2kg of vanadium-aluminium alloy cake was obtained after dismantling the furnace.
Comparative example 6
The procedure described in example 2 was followed, except that in step (3), q was 1.2;
in this comparative example 652.3kg of vanadium-aluminium alloy cake was obtained after dismantling the furnace.
Comparative example 7
The process of example 2 was followed except that in step (3), the heat per charge of the 3 rd batch was 3200 kJ/kg;
in this comparative example 627.6kg of vanadium-aluminium alloy cake was obtained after dismantling the furnace.
Comparative example 8
The process of example 3 was followed except that in step (3), the heat per charge of 4 th to 6 th mixes was 3000 kJ/kg;
589.2kg of vanadium-aluminium alloy cake is obtained after dismantling the furnace in this comparative example.
Comparative example 9
The process of example 1 was followed except that in step (3), the heat per charge of the 1 st part of the mix and the 2 nd part of the mix was 3300 kJ/kg;
in this comparative example 664.0kg of vanadium-aluminium alloy cake was obtained after dismantling the furnace.
Test example 1
The contents of O and N in the vanadium-aluminum alloys prepared in examples 1 to 3 and comparative examples 1 to 9 were measured, and the contents of O and N were measured using an oxygen-nitrogen-hydrogen analyzer.
TABLE 1
It can be seen from the results in table 1 that, from comparative examples 2 and 3, too high or too low V content in the vanadium-aluminum alloy powder can cause the O and N content in the vanadium-aluminum alloy to increase, when the V content is too low, the lining material is completely melted and fused with the alloy liquid in the smelting process, when the V content is too high, the vanadium-aluminum alloy powder cannot be reflowed in the smelting process, the vanadium-aluminum alloy fine powder with proper composition can be reflowed in situ without entering the alloy liquid as the lining material, and the O and N are prevented from entering the alloy in the cooling process, so that the O, N content in the alloy is reduced. Comparative example 4 adopts a one-time feeding method, because the reaction speed is high, the protection time of the slag on the alloy is shortened, and O and N in the alloy are increased to a certain extent. In comparative examples 5 and 6, too large or too small a q value significantly increases the O content in the alloy impurities during the reduction reaction. In comparative examples 7, 8 and 9, when the heat is too low, the slag and gold separation is not complete due to the low temperature of the system, part of products cannot float sufficiently, so that the O content is increased, and when the heat is too high, the protection effect of the interior material is weakened, so that O and N are increased. The content of O in the vanadium-aluminum alloy prepared according to the technical scheme of the invention is less than or equal to 0.06 percent, and the content of N in the vanadium-aluminum alloy prepared according to the technical scheme of the invention is less than or equal to 0.03 percent.
Test example 2
The vanadium content of the vanadium-aluminum alloy obtained in the examples and the comparative examples at different positions is detected, sampling is carried out at the upper, middle and lower parts along the center line of the alloy ingot, sampling is carried out at the upper, middle and lower parts along the side line, the vanadium content is detected by adopting the method YB/T4908.1-2021, the schematic diagram of the sampling positions is shown in FIG. 6, and the detection results are shown in Table 2.
TABLE 2
Further, the maximum deviation of the measured vanadium content of 6 of each vanadium-aluminum alloy was calculated, and the results are shown in table 3.
TABLE 3
As can be seen from the results in tables 2 and 3, in comparative examples 2 and 3, the vanadium content of the side line of the alloy cake is obviously increased or reduced due to the change of the components of the vanadium-aluminum alloy powder of the lining material, so that the segregation between the side line and the central line is increased; compared with the prior art, when the one-time feeding smelting is adopted in the comparative example 4, the reaction time is short, so that the alloy sedimentation is insufficient, the vanadium content at the lower part of the alloy cake is lower than that at the upper part, and the up-and-down segregation of the alloy cake is increased; in comparative examples 5 and 6, since the q value is too large or too small, overcompensation and undercompensation occur in chemical segregation control caused by gravity settling in the longitudinal direction of the alloy ingot, and the up-and-down segregation of the vanadium-aluminum alloy cake increases. In comparative examples 7, 8 and 9, the alloy sedimentation rate is changed due to the change of heat, so that the alloy segregation is increased, which shows that the method of the invention can effectively overcome the component segregation of the vanadium-aluminum alloy.
Test example 3
The composition and vanadium yield of the vanadium-aluminum alloy finished products obtained in examples 1 to 3 and comparative examples 1 to 9 were measured by the following test methods:
and (3) vanadium content determination: YB/T4908.1-2021 vanadium-aluminum alloy vanadium content determination ammonium persulfate oxidation-ferrous ammonium sulfate titration method;
and (3) measuring the aluminum content: YB/T4908.3-2021 vanadium-aluminum alloy determination of aluminum content barium salt alkali decomposition-EDTA titration method;
measuring Fe and Si by adopting ICP; c is measured by a carbon-sulfur analyzer; o and N are measured by adopting an oxygen nitrogen hydrogen analyzer;
the test results are shown in table 4.
TABLE 4
As shown in tables 1 to 4, the vanadium-aluminum alloy obtained in comparative examples 2 to 3 has a high O, N content, the vanadium-aluminum alloy obtained in comparative example 4 has a high vanadium-aluminum content due to the use of one-time feeding and the use of comparative example 9 for increasing heat, so that the spattering during the smelting process is increased, the smelting yield is reduced, the content of oxygen and nitrogen impurities is increased, the vanadium and aluminum segregation in the vanadium-aluminum alloy obtained in comparative examples 5 to 6 is large, and the vanadium-aluminum alloy obtained in comparative example 7 and comparative example 8 have a low heat, so that the slag-gold separation during the smelting process is incomplete, and part of the alloy is not sufficiently settled and exists in the slag phase as fine particles, so that the smelting yield is reduced. The vanadium-aluminum alloy prepared by the scheme of the invention meets the production requirements of factories, is convenient to disassemble, is convenient to operate, can reduce the loss caused by disassembling the furnace, has low O, N content in the prepared vanadium-aluminum alloy, has small chemical segregation, meets the requirements of the vanadium-aluminum alloy, and has a vanadium smelting yield of more than 98%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (20)
1. A method for producing vanadium-aluminum alloy by one-step method is characterized by comprising the following steps:
(1) providing a graphite crucible smelting furnace (4): the graphite crucible smelting furnace (4) comprises a graphite crucible base (1), a first graphite crucible (2) and a second graphite crucible (3) which are detachably connected in sequence from bottom to top; the graphite crucible base (1) is of a convex cylindrical structure; the first graphite crucible (2) comprises two identical hollow semi-cylinders, two side edges of each hollow semi-cylinder are provided with stepped occlusion parts, and the two semi-cylinders can be occluded and spliced end to form a hollow cylinder structure through the stepped occlusion parts; the second graphite crucible (3) is of a hollow cylinder structure;
(2) paving a lining material at the bottom of the furnace body of the graphite crucible smelting furnace (4) in the step (1), vibrating the lining material to be smooth and compact, then placing an aluminum foil gasket (5) in the middle of the furnace body of the graphite crucible smelting furnace (4), wherein the diameter of the aluminum foil gasket (5) is 20-35mm smaller than the inner diameter of the furnace body of the graphite crucible smelting furnace (4), and then filling the lining material in a gap formed by the furnace body of the graphite crucible smelting furnace (4) and the aluminum foil gasket (5) to obtain the vanadium-aluminum alloy smelting furnace;
(3) evenly dividing vanadium pentoxide into N parts by weight, and sequentially weighing N parts of aluminum particles according to the following requirements, wherein the aluminum particles comprise the following components in parts by weight: the weight of the 1 st part of aluminum particles is q times of the theoretical value, the weight of the Nth part of aluminum particles is 2-q times of the theoretical value, and the weight of the kth part of aluminum particles is theoretical value
Multiple, k is more than 1 and less than N, k is an integer, and q is more than or equal to 1.14 and less than or equal to 1.18; mixing N parts of vanadium pentoxide material with N parts of aluminum particles and N parts of heat regulating agent in sequence to obtain 1 st part of mixture, 2 nd part of mixture, 3 rd part of mixture to N th part of mixture, and controlling the 1 st part of mixture, 2 nd part of mixture to the N th part of mixture
The heat quantity of the unit furnace charge of the part mixture is 3000-
Part mixture, first
Mixing the materials to the first
The heat of the unit furnace charge of the part mixture is 3200-
Part mixture, first
The unit charging heat from the mixture to the Nth mixture is 3300-;
(4) paving the 1 st part of mixture obtained in the step (3) at the bottom of the vanadium-aluminum alloy smelting furnace obtained in the step (2), then igniting and igniting the 1 st part of mixture, and after the 1 st part of mixture starts to carry out aluminothermic reaction, sequentially adding the 2 nd part of mixture, the 3 rd part of mixture to the Nth part of mixture in a continuous feeding mode;
(5) after the thermit reaction is finished, standing, pushing into a vacuum chamber, introducing argon into the vacuum chamber for cooling, and then sequentially disassembling, crushing, polishing and selecting to obtain a finished product vanadium-aluminum alloy;
wherein, in the step (2), the lining material contains vanadium-aluminum alloy powder, and the chemical composition of the vanadium-aluminum alloy powder comprises 43-76 wt% of V and 24-57 wt% of Al;
in the step (3), the heat regulator is lime and/or potassium chlorate;
in the step (3), N is more than or equal to 3 and less than or equal to 10, and N is an integer; when N is a multiple of 3,
and
taking a calculated value; when N does not take a multiple of 3,
and
integer values are rounded off.
2. The method of claim 1 wherein in step (1) the stepped occlusion of one side edge has an inboard recess and an outboard projection and the stepped occlusion of the other side edge has an inboard projection and an outboard recess.
3. The method according to claim 2, characterized in that in step (1), the top radius of the graphite crucible base (1) is the same as the inner radius of the first graphite crucible (2) and the inner radius of the second graphite crucible (3), and the bottom radius of the graphite crucible base (1) is the same as the outer radius of the first graphite crucible (2) and the outer radius of the second graphite crucible (3).
4. The method as claimed in claim 2, wherein in step (1), the radius of the top surface of the graphite crucible base (1) is 100-500 mm.
5. The method as claimed in claim 2, wherein, in step (1), the radius of the top surface of the graphite crucible base (1) is 150-400 mm.
6. The method according to claim 1 or 2, characterized in that in step (1), the difference between the radius of the bottom surface of the graphite crucible base (1) and the radius of the top surface of the graphite crucible base (1) is 40-100 mm.
7. The method according to claim 1, characterized in that in step (1), the height of the first graphite crucible (2) is the same as the height of the second graphite crucible (3).
8. The method according to claim 7, characterized in that in step (1), the ratio of the height of the first graphite crucible (2) to the radius of the top surface of the graphite crucible base (1) is 1-8: 1.
9. The method according to claim 7, wherein in step (1), the height of the graphite crucible base (1) is 40-100 mm.
10. The method according to claim 1, wherein in the step (2), the height of the lining material laid in the furnace body bottom of the graphite crucible smelting furnace (4) is 32-54 mm.
11. The method according to claim 10, wherein in step (2), the aluminum foil gasket (5) has a thickness of 0.45-0.55 mm.
12. The method according to claim 1 or 10, wherein in the step (2), the chemical composition of the vanadium-aluminum alloy powder comprises 43 to 51 wt% of V and 49 to 57 wt% of Al.
13. The method according to claim 12, wherein in the step (2), the chemical composition of the vanadium-aluminum alloy powder includes 50 to 62 wt% of V and 38 to 50 wt% of Al.
14. The method according to claim 12, wherein in the step (2), the chemical composition of the vanadium-aluminum alloy powder comprises 60 to 71 wt% of V and 29 to 40 wt% of Al.
15. The method according to claim 12, wherein in the step (2), the chemical composition of the vanadium-aluminum alloy powder includes 63 to 76 wt% of V and 24 to 37 wt% of Al.
16. The method according to claim 1, wherein in step (3), V is contained in the vanadium pentoxide2O5Content of >99 wt.%, content of Fe<0.09 wt%, content of Si<0.095 wt%, content of C<0.02 wt%, and the particle size of the vanadium pentoxide is 2-4 mm.
17. The method according to claim 16, wherein in step (3), the content of Al in the aluminum particles is >99.8 wt.%, the content of Fe is <0.05 wt.%, the content of Si is <0.05 wt.%, the content of C is <0.01 wt.%, and the particle size of the aluminum particles is 2-4 mm.
18. The method as claimed in claim 1, wherein in step (4), the feeding rate of the continuous feeding is 200-500 kg/min.
19. The method according to claim 1, wherein in the step (5), the standing time is 10 to 30 min.
20. The method of claim 19, wherein in step (5), the cooling time is 24-72 hours.
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