CN109536751B - Method for producing magnesium-lithium alloy and by-product magnesium aluminate spinel by aluminothermic reduction - Google Patents

Method for producing magnesium-lithium alloy and by-product magnesium aluminate spinel by aluminothermic reduction Download PDF

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CN109536751B
CN109536751B CN201811471775.1A CN201811471775A CN109536751B CN 109536751 B CN109536751 B CN 109536751B CN 201811471775 A CN201811471775 A CN 201811471775A CN 109536751 B CN109536751 B CN 109536751B
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CN109536751A (en
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尤晶
王耀武
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Liaoning Institute of Science and Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C22B5/00—General methods of reducing to metals
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    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
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Abstract

A method for producing magnesium-lithium alloy and byproduct magnesium-aluminum spinel by aluminothermic reduction comprises the following steps: (1) calcining magnesite; (2) mixing lithium carbonate/lithium hydroxide and alumina to prepare pellets, and calcining to obtain lithium aluminate; (3) ball-milling and mixing calcined magnesite, lithium aluminate and aluminum powder to prepare pellets, and then carrying out vacuum reduction by using a reduction tank with a crystallizer; (4) taking out the crude magnesium-lithium alloy in the crystallizer, covering by a covering agent, and then re-melting and refining; (5) smelting the reducing slag in an electric arc furnace, and returning the generated flue gas to the step (2); (6) grinding the slag charge into small blocks, recovering the refining agent by vacuum distillation, and returning the distillation residue to the step (2). In the method, the lithium element can be utilized by 100 percent, and no waste residue is generated.

Description

Method for producing magnesium-lithium alloy and by-product magnesium aluminate spinel by aluminothermic reduction
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for producing magnesium-lithium alloy and by-product magnesium-aluminum spinel by aluminothermic reduction.
Background
The density of the metal magnesium is 1.74g/cm3Metallic lithium density 0.53g/cm3The magnesium-lithium alloy is an alloy material with the minimum density, and the specific gravity is generally 0.97-1.6 g/cm31/4-1/3 lighter than common magnesium alloy and 1/3-1/2 lighter than aluminum alloy, and the alloy is called ultra-light alloy; the magnesium-lithium alloy has high specific strength, high specific stiffness (from the material stiffness, if the stiffness of common steel is 1, the stiffness of titanium is 2.9, the stiffness of aluminum is 8.19, the stiffness of magnesium is 18.9, and the stiffness of the magnesium-lithium alloy is 22.68), excellent shock resistance and high-energy particle penetration resistance, and the density of the magnesium-lithium alloy is far lower than that of a novel aviation material aluminum-lithium alloy, so that the magnesium-lithium alloy is one of the most ideal structural materials with great development potential in the fields of aviation, aerospace, weapon industry, nuclear industry, automobile, 3C industry, medical instruments and the like.
At present, the magnesium-lithium alloy is basically produced by adopting a method of mixing metal magnesium and metal lithium; the metal magnesium is produced by adopting a Pidgeon method, and the metal lithium is produced by adopting a molten salt electrolysis method; the Pidgeon method for producing the metal magnesium is one of the non-ferrous industries with highest energy consumption and largest waste residue discharge amount, and is one of the national major regulation and control industries in recent years; the production of metal lithium by an electrolytic method is carried out in a molten salt system which takes lithium chloride and potassium chloride as main raw materials, wherein in the production process, 40000kWh of electricity is consumed for producing one ton of metal lithium, and more than 5 tons of toxic gas chlorine gas is generated; therefore, the smelting of metal lithium and metal magnesium belongs to the typical metallurgical industry with high energy consumption and high pollution; in addition, the process of producing the magnesium-lithium alloy by the mixing method is to melt magnesium firstly, then add solid or gaseous metal lithium into magnesium liquid, and then diffuse the metal lithium into the magnesium liquid to form the magnesium-lithium alloy, or put metal magnesium and metal aluminum into a vacuum furnace to be melted simultaneously to form the magnesium-lithium alloy, and because the saturated vapor pressure of the metal lithium is higher in the production process, the metal lithium is easy to oxidize and burn in the air to cause the loss of the metal lithium and is easy to generate danger; under the vacuum condition, magnesium and lithium (especially lithium) are easy to volatilize, so that the alloy composition is changed, and the energy consumption is high; the distribution of lithium in the magnesium-lithium alloy produced by adopting a blending method is not uniform; other methods for producing the magnesium-lithium alloy also have some problems which are difficult to solve, and the production cost of the magnesium-lithium alloy is very high due to the factors, namely dozens of thousands of yuan per ton, so that the further popularization and application of the magnesium-lithium alloy are limited.
Disclosure of Invention
In order to solve the problems, the invention provides a method for producing magnesium-lithium alloy by-product magnesium-aluminum spinel through aluminothermic reduction, which uses aluminum powder as a reducing agent, uses calcined magnesite and lithium aluminate as raw materials, directly produces crude magnesium-lithium alloy through vacuum thermic reduction, prepares industrial magnesium-lithium alloy through refining and component adjustment, and produces reducing slag to prepare magnesium-aluminum spinel and recycle lithium oxide; the production cost is reduced, and no waste is generated.
The method of the invention is carried out according to the following steps:
1. calcining magnesite at 800-1000 ℃ for 1-10 hours to obtain calcined magnesite;
2. mixing lithium carbonate and alumina, then pressing into pellets, and then calcining at 750-1000 ℃ for 1-10 hours to obtain lithium aluminate, wherein the molar ratio of the lithium carbonate to the alumina is (0.90-1.10) to 1; or mixing lithium hydroxide and alumina for batching, pressing to prepare pellets, and calcining at 750-1000 ℃ for 1-10 hours to obtain lithium aluminate, wherein the molar ratio of the lithium hydroxide to the alumina for batching is (1.90-2.10): 1;
3. ball-milling and mixing calcined magnesite, lithium aluminate and aluminum powder, pressing into pellets, putting the pellets into a vacuum reduction tank with a crystallizer, and reducing for 2-10 hours under the conditions of vacuum degree of 0.01-10 Pa and 900-1250 ℃; in the reduction process, magnesium oxide and lithium oxide are simultaneously reduced into metal magnesium and metal lithium by aluminum, and the metal magnesium and the metal lithium complete gaseous alloying under the gaseous condition and are crystallized on a crystallizer; after reduction is finished, forming a coarse magnesium-lithium alloy in the crystallizer, and taking the residual material at the bottom of the vacuum reduction tank as reducing slag; wherein the mass ratio of the lithium aluminate to the calcined magnesite is (0.60-60.0) to 1; the theoretical dosage of the aluminum powder is as follows:
2Al+4Li2O·Al2O3＝Li2O·5Al2O3+6Li
or
2Al+4MgO＝MgO·Al2O3+3Mg；
The actual dosage of the aluminum powder is 100-150% of the theoretical dosage of the reaction formula;
4. taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 400-700 ℃ to re-melt under the condition of covering by a covering agent to form a crude alloy melt; then, blowing a refining agent into the bottom of the crude alloy melt by taking argon as a carrier gas, refining the crude alloy melt to form refining slag and an alloy melt, wherein the refining slag floats to the surface of the alloy melt; finally, fishing out the slag on the upper layer, and pouring the residual alloy melt into a magnesium-lithium alloy ingot;
5. placing the reducing slag in an electric arc furnace, or adding alumina and/or calcined magnesite into the reducing slag and then placing the reducing slag in the electric arc furnace, smelting the reducing slag in the electric arc furnace at the electric melting temperature of 1800-2700 ℃, melting the magnesia and the alumina in the electric arc furnace to form an electric melting magnesia-alumina spinel melt, and cooling the electric melting magnesia-alumina spinel melt to the normal temperature along with the furnace to obtain magnesia-alumina spinel; wherein the addition amount of the alumina and the calcined magnesite is controlled according to the components of the magnesia-alumina spinel; recovering flue gas generated in the arc melting process, and then returning the flue gas to the step 2 to be used as a raw material for preparing pellets;
6. the fished slag mainly comprises a mixture of refining slag and a covering agent, and also comprises partial magnesium oxide and lithium oxide; grinding the slag until the granularity is 0.075-0.5 mm, and then pressing into pellets; putting the pellets into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation under the conditions that the vacuum degree is 0.01-10 Pa and the temperature is 900-1200 ℃; the chloride and fluoride obtained by distillation form crystals which are used as raw materials of a refining agent for recycling; the distillation residue formed by distillation, which is magnesium oxide and lithium oxide, is returned to step 2 as the raw material for pelletizing.
In the method, the reducing slag is divided into two parts, one part is returned to the step 2, and the reducing slag is mixed with lithium carbonate or lithium hydroxide according to the amount of alumina in the reducing slag to prepare lithium aluminate; the rest is made into magnesium aluminate spinel in the way of step 5.
In the method, when smoke is generated in the arc melting process, magnesium metal or lithium metal volatilizes from the fused magnesia-alumina spinel and is oxidized into oxide to enter the soot; the lithium aluminate in the reducing slag reacts with the magnesium oxide to release free lithium oxide, or the lithium aluminate is directly decomposed to release free lithium oxide, and the free lithium oxide is volatilized at high temperature to enter the soot.
In the method, the briquetting pressure when all the pellets are pressed into the pellets is 50-200 MPa.
In the method, the reaction formula of the calcination after the lithium carbonate and the alumina are batched is as follows:
Li2CO3+Al2O3＝Li2O·Al2O3+CO2；
the reaction formula of calcining after briquetting of lithium hydroxide and alumina ingredients is as follows:
2LiOH+Al2O3＝Li2O·Al2O3+H2O。
in the method, the covering agent comprises, by mass, 10-80% of LiCl, 10-80% of LiF, 0-50% of KCl and MgCl20～50％，MgF20-30% of the total amount of all the components is 100%; particle size of the ingredients in the covering agentAre all made of<1mm。
In the method, the refining agent comprises, by mass, 20-80% of LiCl, 20-80% of LiF, 0-50% of KCl and MgCl20～30％，MgF20-30% of the total amount of all the components is 100%; the particle sizes of all the components in the refining agent are equal<1mm, and the blowing amount of the refining agent is 2-10% of the total mass of the crude alloy melt.
And 4, fishing out the slag on the upper layer, adding metal or alloy into the alloy melt according to the grade of the magnesium-lithium alloy, and pouring to prepare the magnesium-lithium alloy with the required grade after the magnesium-lithium alloy is completely melted.
In the method, the main components of the reducing slag are MgO and Li2O and Al2O3The main phase is MgO. Al2O3、Li2O·5Al2O3And Al2O3In addition, the alloy also contains a small amount of unreacted metal aluminum powder, wherein the mass percent of MgO is 10-50%, and Li20.1-2% of O and Al2O3The mass percent of the Al is 40-90%, and the mass percent of the Al is 1-10%.
In the method, the reducing slag is blocky and has the granularity of 5-30 mm.
In the method, the granularity of calcined magnesite added into the reducing slag is 20-100 mm.
In the method, when the mixture is placed in an electric arc furnace for electric arc furnace smelting, the mixture is added in batches, and after electric melting, the magnesia-alumina spinel is discharged in batches.
In the above method, when the electric arc furnace smelting is performed, the reaction formula of the residual metallic aluminum and the residual magnesium oxide or lithium oxide is:
2Al+4MgO＝MgO·Al2O3+3Mg(g)
or
3(Li2O·5Al2O3)+2Al＝16Al2O3+6Li(g)。
In the above method, when the arc furnace smelting is performed, the reaction formula of the reaction between lithium aluminate and magnesium oxide to release free lithium oxide is:
Li2O·5Al2O3+5MgO＝5MgO·Al2O3+Li2O(g)。
in the above method, when the electric arc furnace smelting is carried out, the reaction formula for the direct decomposition of the lithium aluminate is:
Li2O·5Al2O3＝Li2O(g)+5Al2O3。
the vacuum reduction tank with the crystallizer is a reduction tank for smelting magnesium by a Pidgeon process, and during working, heating adopts gas heating or resistance heating.
The magnesite is more than three-level magnesite, and the mass content of magnesium oxide is more than 98%; in the step 2, the granularity of the calcined magnesite is 1-10 mm.
The lithium carbonate and the lithium hydroxide are industrial products, the purity is more than 98 percent, and the granularity is less than 1 mm.
The aluminum powder is industrial aluminum powder, the mass content of the aluminum is more than 99%, and the particle size is less than 1 mm.
The mass content of impurities in the magnesium-lithium alloy is less than or equal to 0.5 percent.
The integral method of the invention is mainly divided into two stages, wherein the first stage is a stage for preparing magnesium-lithium alloy by vacuum aluminothermic reduction, and the second stage is a stage for preparing magnesium-aluminum spinel by reducing slag through electric melting and recovering lithium oxide in the reducing slag; the main reactions that take place during the reduction can be illustrated by the following formula:
(c+a)MgO+(b+2d)Li2O·Al2O3+2(c+3d+e-b)Al＝aMg+bLi+cMgO·Al2O3+d(Li2O·5Al2O3)+eA l2O3；
wherein the specific values of a, b, c, d and e are related to the lithium content in the magnesium-lithium alloy to be prepared and the alumina content in the magnesium-aluminum spinel; in the recovery stage of preparing the electric smelting magnesia-alumina spinel from the reducing slag and the lithium oxide from the reducing slag, the main reaction can be expressed as follows:
Li2O·5Al2O3+5MgO＝MgO·Al2O3+Li2O、
3(Li2O·5Al2O3)+2Al＝16Al2O3+6Li
and
Li+O2＝Li2O；
the more the aluminum powder is added in the reduction process, the higher the reduction rate of magnesium and lithium in the reduction process is, the more the content of alumina in the reduction slag is, and the higher the content of alumina in the magnesia-alumina spinel obtained by electric melting is. Li in reduction process2O·Al2O3The higher the addition amount is, the higher the lithium content in the prepared magnesium-lithium alloy is; by the method, the magnesium-lithium alloy with 5-90% of lithium content can be prepared, and various magnesium-aluminum spinel refractory materials with 10-95% of alumina content are byproducts.
By applying the technology of the invention, in the process of producing the magnesium-lithium alloy, magnesium ore and lithium oxide are directly used as raw materials for vacuum thermal reduction, the obtained magnesium metal and lithium metal are subjected to gas-phase alloying under the vacuum condition and are cooled together to be crystallized on a crystallizer to form the magnesium-lithium alloy, the components of the prepared magnesium-lithium alloy are relatively uniform, the magnesium-lithium alloy is stable and is not easy to burn and lose in the remelting and refining process, lithium oxide in reducing slag can be completely recovered, lithium element can be utilized by 100 percent, no waste slag is generated in the whole production process, and the magnesium-lithium alloy is a green production process.
Drawings
FIG. 1 is a schematic flow chart of the method for producing magnesium-lithium alloy and by-producing magnesium aluminate spinel by aluminothermic reduction of the present invention.
Detailed Description
The vacuum reduction tank with the crystallizer adopted in the embodiment of the invention is a reduction tank for smelting magnesium by a Pidgeon method, and during working, heating adopts gas heating or resistance heating.
The magnesite adopted in the embodiment of the invention is more than three-grade magnesite, and the mass content of magnesium oxide is more than 98%.
In the embodiment of the invention, the calcined magnesite with the granularity of 1-10 mm is used for ball-milling and mixing with lithium aluminate and aluminum powder.
In the embodiment of the invention, the part with the granularity of 20-100 mm in the calcined magnesite is used for mixing with the reducing slag.
In the embodiment of the invention, the lithium carbonate and the lithium hydroxide are industrial products, the purity is more than 98%, and the granularity is less than 1 mm.
The aluminum powder in the embodiment of the invention is industrial aluminum powder, the mass content of the aluminum is more than 99%, and the particle size is less than 1 mm.
In the embodiment of the invention, the mass content of impurities in the magnesium-lithium alloy is less than or equal to 0.5 percent.
In the embodiment of the invention, the mass percentage of lithium in the magnesium-lithium alloy is 5-90%.
In the embodiment of the invention, the mass percentage of the alumina in the magnesium aluminate spinel is 10-95%.
In the embodiment of the invention, when the mixture is placed in an electric arc furnace for electric arc furnace smelting, the mixture is added in batches, and after electric melting, the magnesia-alumina spinel is discharged in batches.
In the embodiment of the invention, the flow speed of argon is 10-500L/min when the refining agent is blown.
In the embodiment of the invention, the main components of the reducing slag are MgO and Li2O and Al2O3The main phase is MgO. Al2O3、Li2O·5Al2O3And Al2O3In addition, the alloy also contains a small amount of unreacted metal aluminum powder, wherein the mass percent of MgO is 10-50%, and Li20.1-2% of O and Al2O3The mass percent of the Al is 40-90%, and the mass percent of the Al is 1-10%.
In the embodiment of the invention, when the soot returns to the step 2 to be used as the raw material for preparing the pellets, the soot is added without changing the proportioning ratio of the lithium carbonate/lithium hydroxide and the alumina.
The following are preferred embodiments of the present invention.
Example 1
The flow is shown in figure 1;
step 1: calcining magnesite at 800 ℃ for 10 hours to obtain calcined magnesite;
step 2: mixing lithium carbonate and alumina, pressing into pellets, and calcining at 750 ℃ for 10 hours to obtain lithium aluminate, wherein the molar ratio of the lithium carbonate to the alumina is 0.9: 1;
and step 3: ball-milling and mixing calcined magnesite, lithium aluminate and aluminum powder, pressing into pellets, putting the pellets into a vacuum reduction tank with a crystallizer, and reducing for 2 hours under the conditions of vacuum degree of 0.01-10 Pa and 1250 ℃; in the reduction process, magnesium oxide and lithium oxide are simultaneously reduced into metal magnesium and metal lithium by aluminum, and the metal magnesium and the metal lithium complete gaseous alloying under the gaseous condition and are crystallized on a crystallizer; after reduction is finished, forming a coarse magnesium-lithium alloy in the crystallizer, and taking the residual material at the bottom of the vacuum reduction tank as reducing slag; wherein the mass ratio of the lithium aluminate to the calcined magnesite is 6: 1; the theoretical dosage of the aluminum powder is as follows:
2Al+4Li2O·Al2O3＝Li2O·5Al2O3+6Li；
the actual dosage of the aluminum powder is 150% of the theoretical dosage;
and 4, step 4: taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 400 ℃ to re-melt under the condition of covering by a covering agent to form a crude alloy melt; then, blowing a refining agent into the bottom of the crude alloy melt by taking argon as a carrier gas, refining the crude alloy melt to form refining slag and an alloy melt, wherein the refining slag floats to the surface of the alloy melt; finally, fishing out the slag on the upper layer, and pouring the residual alloy melt into a magnesium-lithium alloy ingot; the covering agent comprises 50% of LiCl and 50% of LiF according to mass percentage; the particle size of each component in the covering agent is less than 1 mm; the dosage of the covering agent is based on the complete covering of the crude alloy melt; the refining agent comprises 80 mass percent of LiCl and 20 mass percent of LiF; the particle size of each component in the refining agent is less than 1mm, and the blowing amount of the refining agent is 9% of the total mass of the coarse alloy melt;
and 5: placing the reducing slag in an electric arc furnace, carrying out electric arc furnace smelting at the electric melting temperature of 1800-2700 ℃, melting magnesium oxide and aluminum oxide in the electric arc furnace to form an electric melting magnesia-alumina spinel melt, and cooling the electric melting magnesia-alumina spinel melt to normal temperature along with the furnace to obtain magnesia-alumina spinel; wherein the addition amount of the alumina and the calcined magnesite is controlled according to the components of the magnesia-alumina spinel; recovering flue gas generated in the arc melting process, and then returning the flue gas to the step 2 to be used as a raw material for preparing pellets; when smoke is generated in the arc melting process, magnesium metal or lithium metal volatilizes from the electric melting magnesia-alumina spinel and is oxidized into oxide to enter the soot; reacting lithium aluminate with magnesium oxide in the reducing slag to release free lithium oxide, or directly decomposing the lithium aluminate to release free lithium oxide, and volatilizing the free lithium oxide at high temperature to enter soot;
step 6: the fished slag mainly comprises a mixture of refining slag and a covering agent, and also comprises partial magnesium oxide and lithium oxide; grinding the slag until the granularity is 0.075-0.5 mm, and then pressing into pellets; putting the pellets into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation under the conditions of vacuum degree of 0.01-10 Pa and 900 ℃; the chloride and fluoride obtained by distillation form crystals which are used as raw materials of a refining agent for recycling; distilling to form distillation residues of magnesium oxide and lithium oxide, and returning the distillation residues to the step 2 to be used as raw materials for preparing pellets;
the briquetting pressure for pressing into pellets is 50 MPa.
Example 2
The flow is shown in figure 1; the method is the same as example 1, except that:
(1) calcining magnesite at 850 ℃ for 8 hours;
(2) mixing lithium carbonate and alumina, pressing into pellets, and calcining at 800 ℃ for 6 hours to obtain lithium aluminate, wherein the molar ratio of the lithium carbonate to the alumina is 0.95: 1;
(3) reducing the pellets for 9 hours at 1200 ℃; the mass ratio of the lithium aluminate to the calcined magnesite is 5: 1;
the actual dosage of the aluminum powder is 140 percent of the theoretical dosage;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 500 ℃ to re-melt under the condition of covering by a covering agent; the covering agent comprises, by mass, LiCl 10%, LiF 10%, and MgCl250％，MgF230 percent; the refining agent comprises 20% of LiCl and 80% of LiF according to mass percentage; the blowing amount of the refining agent is 8 percent of the total mass of the crude alloy melt;
(5) adding calcined magnesite into the reducing slag, placing the reducing slag into an electric arc furnace, and smelting the reducing slag in the electric arc furnace at the electric melting temperature of 1800-2700 ℃;
(6) grinding the slag charge, pressing into pellets, putting into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation at 950 ℃;
the briquetting pressure during the pressing into pellets is 80 MPa.
Example 3
The flow is shown in figure 1; the method is the same as example 1, except that:
(1) calcining magnesite at 900 ℃ for 6 hours;
(2) mixing lithium carbonate and alumina, pressing into pellets, and calcining at 900 ℃ for 3 hours to obtain lithium aluminate, wherein the molar ratio of the lithium carbonate to the alumina is 1: 1;
(3) reducing the pellets for 8 hours at 1100 ℃; the mass ratio of the lithium aluminate to the calcined magnesite is 4: 1;
the actual dosage of the aluminum powder is 130 percent of the theoretical dosage;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 500 ℃ to re-melt under the condition of covering by a covering agent; the covering agent comprises, by mass, LiCl 20%, LiF 20%, KCl 50%, and MgCl25％，MgF25 percent; the refining agent comprises, by mass, LiCl 20%, LiF 20%, and MgCl230％，MgF230 percent; the blowing amount of the refining agent is 2 percent of the total mass of the crude alloy melt;
(5) returning 50% of the reducing slag to the step 2, and mixing the reducing slag with lithium carbonate or lithium hydroxide according to the amount of the alumina in the reducing slag to prepare lithium aluminate; adding calcined magnesite into the rest part, placing the mixture into an electric arc furnace, and smelting the mixture in the electric arc furnace at the electric melting temperature of 1800-2700 ℃;
(6) grinding the slag charge, pressing into pellets, putting into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation at 950 ℃;
the briquetting pressure during the pressing into pellets is 100 MPa.
Example 4
The flow is shown in figure 1; the method is the same as example 1, except that:
(1) calcining magnesite at 950 ℃ for 5 hours;
(2) mixing lithium carbonate and alumina, pressing into pellets, and calcining at 1000 ℃ for 1 hour to obtain lithium aluminate, wherein the molar ratio of the lithium carbonate to the alumina is 1.1: 1;
(3) reducing the pellets for 6 hours at 1050 ℃; the mass ratio of the lithium aluminate to the calcined magnesite is 3: 1;
the actual dosage of the aluminum powder is 125 percent of the theoretical dosage;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 550 ℃ to re-melt under the condition of covering by a covering agent; the covering agent comprises 30 mass percent of LiCl, 40 mass percent of LiF, 10 mass percent of KCl and MgCl210％，MgF210 percent; the refining agent comprises 25% of LiCl, 25% of LiF and 50% of KCl by mass percent; the blowing amount of the refining agent is 3 percent of the total mass of the crude alloy melt;
(5) returning 50% of the reducing slag to the step 2, and mixing the reducing slag with lithium carbonate or lithium hydroxide according to the amount of the alumina in the reducing slag to prepare lithium aluminate; adding alumina and calcined magnesite into the rest part, placing the mixture into an electric arc furnace, and smelting the mixture in the electric arc furnace at the electric melting temperature of 1800-2700 ℃;
(6) grinding the slag charge, pressing into pellets, putting into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation at 1000 ℃;
the briquetting pressure during the pressing into pellets is 120 MPa.
Example 5
The flow is shown in figure 1; the method is the same as example 1, except that:
(1) calcining magnesite at 950 ℃ for 4 hours;
(2) mixing lithium hydroxide and alumina for batching, pressing to prepare pellets, and calcining at 750 ℃ for 10 hours to obtain lithium aluminate, wherein the molar ratio of the lithium hydroxide to the alumina for batching is 1.9: 1;
(3) reducing the pellets for 4 hours at 1000 ℃; the mass ratio of the lithium aluminate to the calcined magnesite is 2: 1; the theoretical dosage of the aluminum powder is as follows:
2Al+4MgO＝MgO·Al2O3+3Mg；
the actual dosage of the aluminum powder is 120 percent of the theoretical dosage;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 600 ℃ to be remelted under the condition of covering by a covering agent; the covering agent comprises 30 mass percent of LiCl, 25 mass percent of LiF, 15 mass percent of KCl and MgCl215％，MgF215 percent; the refining agent comprises, by mass, LiCl 20%, LiF 20%, KCl 20%, and MgCl220％，MgF220 percent; the blowing amount of the refining agent is 4 percent of the total mass of the crude alloy melt;
(5) adding alumina and calcined magnesite into the reducing slag, placing the reducing slag into an electric arc furnace, and smelting the reducing slag in the electric arc furnace at the electric melting temperature of 1800-2700 ℃;
(6) grinding the slag charge, pressing into pellets, putting into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation at 1000 ℃;
the briquetting pressure during the pressing into pellets is 130 MPa.
Example 6
The flow is shown in figure 1; the method is the same as example 1, except that:
(1) calcining magnesite at 950 ℃ for 3 hours;
(2) mixing lithium hydroxide and alumina, pressing to prepare pellets, and calcining at 800 ℃ for 6 hours to obtain lithium aluminate, wherein the molar ratio of the lithium hydroxide to the alumina is 1.95: 1;
(3) reducing the pellets for 3 hours at 950 ℃; the mass ratio of the lithium aluminate to the calcined magnesite is 1.5: 1; the theoretical dosage of the aluminum powder is as follows:
2Al+4MgO＝MgO·Al2O3+3Mg；
the actual dosage of the aluminum powder is 115 percent of the theoretical dosage;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and heating to 600 ℃ under the condition of covering by a covering agentMelting; the covering agent comprises, by mass, LiCl 40%, LiF 40%, KCl 10%, and 4MgF240 percent; the refining agent comprises 30 mass percent of LiCl, 30 mass percent of LiF, 20 mass percent of KCl and MgCl210％，MgF210 percent; the blowing amount of the refining agent is 5 percent of the total mass of the crude alloy melt;
(5) adding alumina and calcined magnesite into the reducing slag, placing the reducing slag into an electric arc furnace, and smelting the reducing slag in the electric arc furnace at the electric melting temperature of 1800-2700 ℃;
(6) grinding the slag charge, pressing into pellets, putting into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation at 1050 ℃;
the briquetting pressure during the pressing into pellets is 150 MPa.
Example 7
The flow is shown in figure 1; the method is the same as example 1, except that:
(1) calcining magnesite at 1000 ℃ for 2 hours;
(2) mixing lithium hydroxide and alumina, pressing to prepare pellets, and calcining at 900 ℃ for 3 hours to obtain lithium aluminate, wherein the molar ratio of the lithium hydroxide to the alumina is 2: 1;
(3) reducing the pellets for 2 hours at 900 ℃; the mass ratio of the lithium aluminate to the calcined magnesite is 1: 1; the theoretical dosage of the aluminum powder is as follows:
2Al+4MgO＝MgO·Al2O3+3Mg；
the actual dosage of the aluminum powder is 110 percent of the theoretical dosage;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 650 ℃ to re-melt under the condition of covering by a covering agent; the covering agent comprises 25 percent of LiCl, 25 percent of LiF, 25 percent of KCl and MgCl according to mass percentage225 percent; the refining agent comprises, by mass, 35% of LiCl, 35% of LiF, 10% of KCl and MgCl210％，MgF210 percent; the blowing amount of the refining agent is 6 percent of the total mass of the crude alloy melt; taking out the slag, adding cast ingots of zinc and other elements, melting, and casting to prepare an LZ91 magnesium-lithium alloy;
(5) returning 50% of the reducing slag to the step 2, and mixing the reducing slag with lithium carbonate or lithium hydroxide according to the amount of the alumina in the reducing slag to prepare lithium aluminate; adding alumina into the rest part, putting the mixture into an electric arc furnace, and smelting the mixture in the electric arc furnace at the electric melting temperature of 1800-2700 ℃;
(6) grinding the slag charge, pressing into pellets, putting into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation at 1100 ℃;
the briquetting pressure during the pressing into pellets is 180 MPa.
Example 8
The flow is shown in figure 1; the method is the same as example 1, except that:
(1) calcining magnesite at 1000 ℃ for 1 hour;
(2) mixing lithium hydroxide and alumina for batching, pressing to prepare pellets, and calcining at 1000 ℃ for 1 hour to obtain lithium aluminate, wherein the molar ratio of the lithium hydroxide to the alumina for batching is 2.1: 1;
(3) reducing the pellets for 2 hours at 900 ℃; the mass ratio of the lithium aluminate to the calcined magnesite is 0.6: 1; the theoretical dosage of the aluminum powder is as follows:
2Al+4MgO＝MgO·Al2O3+3Mg；
the actual dosage of the aluminum powder is 105 percent of the theoretical dosage;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 700 ℃ to re-melt under the condition of covering by a covering agent; the covering agent comprises, by mass, LiCl 20%, LiF 20%, KCl 20%, and MgCl220％，MgF220 percent; the refining agent comprises, by mass, LiCl 40%, LiF 40%, KCl 20%, and MgCl210％，MgF210 percent; the blowing amount of the refining agent is 10 percent of the total mass of the crude alloy melt;
(5) returning 50% of the reducing slag to the step 2, and mixing the reducing slag with lithium carbonate or lithium hydroxide according to the amount of the alumina in the reducing slag to prepare lithium aluminate; adding alumina into the rest part, putting the mixture into an electric arc furnace, and smelting the mixture in the electric arc furnace at the electric melting temperature of 1800-2700 ℃;
(6) grinding the slag charge, pressing into pellets, putting into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation at 1200 ℃;
the briquetting pressure during the pressing into pellets is 200 MPa.

Claims (9)

1. A method for producing magnesium-lithium alloy and by-product magnesium aluminate spinel by aluminothermic reduction is characterized by comprising the following steps:
(1) calcining magnesite at 800-1000 ℃ for 1-10 hours to obtain calcined magnesite;
(2) mixing lithium carbonate and alumina, then pressing into pellets, and then calcining at 750-1000 ℃ for 1-10 hours to obtain lithium aluminate, wherein the molar ratio of the lithium carbonate to the alumina is (0.90-1.10) to 1; or mixing lithium hydroxide and alumina for batching, pressing to prepare pellets, and calcining at 750-1000 ℃ for 1-10 hours to obtain lithium aluminate, wherein the molar ratio of the lithium hydroxide to the alumina for batching is (1.90-2.10): 1;
(3) ball-milling and mixing calcined magnesite, lithium aluminate and aluminum powder, pressing into pellets, putting the pellets into a vacuum reduction tank with a crystallizer, and reducing for 2-10 hours under the conditions of vacuum degree of 0.01-10 Pa and 900-1250 ℃; in the reduction process, magnesium oxide and lithium oxide are simultaneously reduced into metal magnesium and metal lithium by aluminum, and the metal magnesium and the metal lithium complete gaseous alloying under the gaseous condition and are crystallized on a crystallizer; after reduction is finished, forming a coarse magnesium-lithium alloy in the crystallizer, and taking the residual material at the bottom of the vacuum reduction tank as reducing slag; wherein the mass ratio of the lithium aluminate to the calcined magnesite is (0.60-60.0) to 1; the theoretical dosage of the aluminum powder is as follows:
2Al +4 Li2O•Al2O3= Li2O•5Al2O3+6Li
or
2Al+4MgO=MgO•Al2O3+3Mg；
The actual dosage of the aluminum powder is 100-150% of the theoretical dosage of the reaction formula;
(4) taking out the crude magnesium-lithium alloy in the crystallizer, and then heating to 400-700 ℃ to re-melt under the condition of covering by a covering agent to form a crude alloy melt; then, blowing a refining agent into the bottom of the crude alloy melt by taking argon as a carrier gas, refining the crude alloy melt to form refining slag and an alloy melt, wherein the refining slag floats to the surface of the alloy melt; finally, fishing out the slag on the upper layer, and pouring the residual alloy melt into a magnesium-lithium alloy ingot;
(5) placing the reducing slag in an electric arc furnace, or adding alumina and/or calcined magnesite into the reducing slag and then placing the reducing slag in the electric arc furnace, smelting the reducing slag in the electric arc furnace at the electric melting temperature of 1800-2700 ℃, melting the magnesia and the alumina in the electric arc furnace to form an electric melting magnesia-alumina spinel melt, and cooling the electric melting magnesia-alumina spinel melt to the normal temperature along with the furnace to obtain magnesia-alumina spinel; wherein the addition amount of the alumina and the calcined magnesite is controlled according to the components of the magnesia-alumina spinel; recovering flue gas generated in the arc melting process, and then returning the flue gas to the step (2) to be used as a raw material for preparing pellets;
(6) the fished slag mainly comprises a mixture of refining slag and a covering agent, and also comprises partial magnesium oxide and lithium oxide; grinding the slag until the granularity is 0.075-0.5 mm, and then pressing into pellets; putting the pellets into a vacuum reduction tank with a crystallizer, and carrying out vacuum distillation under the conditions that the vacuum degree is 0.01-10 Pa and the temperature is 900-1200 ℃; the chloride and fluoride obtained by distillation form crystals which are used as raw materials of a refining agent for recycling; and (3) distilling to form distillation residues of magnesium oxide and lithium oxide, and returning the distillation residues to the step (2) to be used as raw materials for pelletizing.
2. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel as a byproduct by aluminothermic reduction according to claim 1, wherein the reducing slag is divided into two parts, one part is returned to the step (2), and the mixture is mixed with lithium carbonate or lithium hydroxide according to the amount of alumina in the reducing slag to prepare lithium aluminate; and (5) preparing the magnesium aluminate spinel from the rest part in the step (5).
3. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel as a byproduct by aluminothermic reduction according to claim 1, wherein briquetting pressure in the process of briquetting pellets in steps (2), (3) and (6) is 50-200 MPa.
4. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel as the byproduct by aluminothermic reduction according to claim 1, wherein the covering agent comprises, by mass, 10-80% of LiCl, 10-80% of LiF, 0-50% of KCl, and MgCl20~50%，MgF20-30% of the total amount of all the components is 100%; the particle size of each component in the covering agent is the same<1mm。
5. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel as a byproduct by aluminothermic reduction according to claim 1, wherein the refining agent comprises, by mass, 20-80% of LiCl, 20-80% of LiF, 0-50% of KCl, and MgCl20~30%，MgF20-30% of the total amount of all the components is 100%; the particle sizes of all the components in the refining agent are equal<1mm, and the blowing amount of the refining agent is 2-10% of the total mass of the crude alloy melt.
6. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel as a byproduct by aluminothermic reduction according to claim 1, wherein in the step (4), after the slag on the upper layer is fished out, metal or alloy is added into the alloy melt according to the grade of the magnesium-lithium alloy, and the magnesium-lithium alloy with the required grade is cast after the metal or alloy is completely melted.
7. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel as a byproduct by aluminothermic reduction according to claim 1, wherein the particle size of the calcined magnesite added into the reducing slag in the step (5) is 20-100 mm.
8. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel as byproduct by aluminothermic reduction according to claim 1, wherein the magnesite is more than three-grade magnesite, and the mass content of magnesium oxide is more than 98%; the granularity of the calcined magnesite in the step (2) is 1-10 mm.
9. The method for producing magnesium-lithium alloy and magnesium-aluminum spinel by aluminothermic reduction according to claim 1, wherein the mass content of impurities in the magnesium-lithium alloy is less than or equal to 0.5%.
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