CN113249755A - Inert anode material and preparation method and application thereof - Google Patents
Inert anode material and preparation method and application thereof Download PDFInfo
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- CN113249755A CN113249755A CN202110516897.3A CN202110516897A CN113249755A CN 113249755 A CN113249755 A CN 113249755A CN 202110516897 A CN202110516897 A CN 202110516897A CN 113249755 A CN113249755 A CN 113249755A
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- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
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- B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
- B22F2009/0828—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
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- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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Abstract
The invention provides an inert anode material and a preparation method and application thereof, and relates to the technical field of molten salt electrolysis of nonferrous metals. The inert anode material provided by the invention comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, Co, Cr, Fe, Ni, Ti and Cu; the ceramic phase comprises CuAl2O4、NiAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、FeAl2O4、NiFe2O4And CuFe2O4One or more of (a). The inert anode material provided by the invention has stronger corrosion resistance, mechanical property and electrical conductivity in a cryolite molten salt system, can prolong the service life of the inert anode, and further solves the problems of high energy consumption, large discharge capacity and the like in the current aluminum electrolysis industry. The inert anode material provided by the invention is suitable for an electrolyte system at 800-1000 ℃, and realizes carbon-free aluminum electrolysis production.
Description
Technical Field
The invention relates to the technical field of molten salt electrolysis of nonferrous metals, in particular to an inert anode material and a preparation method and application thereof.
Background
Aluminum is the most important basic raw material in the non-ferrous metal industry, and is an important support for strengthening the country of manufacturing industry, promoting the growth of strategic emerging industries and guaranteeing the development of national defense military industry and aerospace. In 2020, the yield of the original aluminum in China is 3732 ten thousand tons, which accounts for 57.18 percent of the world yield. At present, the production process still adopts a Hall-Heroult high-temperature molten salt electrolysis method, 450-500 kg of carbon anode is consumed per ton of aluminum, and CO is mainly used2、CFnThe greenhouse gases escape in the form of equal amount, and the discharge amount of the greenhouse gases in the electrolysis process can reach more than 5180 ten thousand tons every year in China. The green aluminum electrolysis technology taking the inert anode as the core does not consume the carbon anode, and the oxygen escaping per ton of aluminum is over 800 kg; if the inert anode aluminum electrolysis is combined with the clean energy power generation technology, the near zero emission of the whole process of the aluminum electrolysis industry can be realized.
The inert anode material needs Na at high temperature3AlF6-AlF3-Al2O3The molten salt (cryolite molten salt system) must have good conductivity, mechanical and corrosion resistance for long-term service. As a result of extensive research, alloys and cermets are considered to be the two most promising materials, among which NiFe2O4The inert anode is the key point of domestic and foreign research in nearly thirty years due to good electric conduction and corrosion resistance. And troubles the NiFe2O4The main difficulty of the metal ceramic inert anode is that the formation and dissolution of a corrosion-resistant film on the surface of the anode cannot be balanced, and the core problem is that the service life of the inert anode under the electrolysis working condition cannot be ensured due to chain reactions such as metal phase looseness, matrix phase dissociation and the like caused by preferential dissolution of part of elements.
Although the inert anode material is researched by various colleges and enterprises in recent years, there is still no case of successful application in practical production, so that the problem to be solved in the prior art is to provide an anode material with good corrosion resistance, mechanical properties and electrical conductivity in a cryolite molten salt system.
Disclosure of Invention
The inert anode material provided by the invention has stronger corrosion resistance, mechanical property and electrical conductivity in a cryolite molten salt system, can prolong the service life of the inert anode, and further solves the problems of high energy consumption, large discharge capacity and the like in the current aluminum electrolysis industry.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an inert anode material, which comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, Co, Cr, Fe, Ni, Ti and Cu; the ceramic phase comprises CuAl2O4、NiAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、FeAl2O4、NiFe2O4And CuFe2O4One or more of (a).
Preferably, the proportion of each single element in the metal phase is 5 to 50 at%.
Preferably, the metal phase has a solid solution structure of no more than two phases.
The invention provides a preparation method of the inert anode material in the technical scheme, which comprises the following steps:
mixing the metal phase raw material and the ceramic phase raw material to obtain a mixed material;
cold pressing the mixed material to obtain a green body;
and sintering the green body to obtain the inert anode material.
Preferably, the metal phase raw material is prepared by a mechanical alloying method or an atomization method.
Preferably, the particle size of the metal phase raw material is 50-500 meshes.
Preferably, the mass ratio of the metal phase raw material to the ceramic phase raw material is 5-50: 50-95.
Preferably, the pressure of the cold pressing is 150-350 MPa, and the pressure maintaining time is 1-10 min.
Preferably, the sintering temperature is 1000-1650 ℃, and the heat preservation time is 2-24 h.
The invention provides an application of the inert anode material in the technical scheme or the inert anode material prepared by the preparation method in the technical scheme in aluminum electrolysis.
The invention provides an inert anode material, which comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, Co, Cr, Fe, Ni, Ti and Cu; the ceramic phase comprises CuAl2O4、NiAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、FeAl2O4、NiFe2O4And CuFe2O4One or more of (a). The AlCoCrFeNiTiCu-series high-entropy alloy is adopted as a metal phase, elements in the high-entropy alloy are complex and various, and the sizes of all atoms are different, so that atom migration is more difficult, and synergistic diffusion is difficult to perform; meanwhile, the serious distortion of the crystal lattice can also improve the diffusion activation energy of atoms, so that the effective diffusion rate of the atoms in the high-entropy alloy is limited, and the multielement high-entropy alloy can form stable compact oxide with a spinel phase structure after being oxidized, so that the internal diffusion of oxygen at high temperature can be effectively prevented, and the corrosion resistance and the mechanical property of the material are improved. The inert anode material provided by the invention has stronger corrosion resistance, mechanical property and electrical conductivity in a cryolite molten salt system, can prolong the service life of the inert anode, and further solves the problems of high energy consumption, large carbon emission and the like in the current aluminum electrolysis industry. The results of the examples show that the inert anode material provided by the invention is suitable for an electrolyte system at 800-1000 ℃, and carbon-free aluminum electrolysis production is realized.
Detailed Description
The invention provides an inert anode material, which comprises a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, Co, Cr, Fe, Ni, Ti and Cu; the ceramic phase comprises CuAl2O4、NiAl2O4、FeAl2O4、NiFe2O4And CuFe2O4One or more of (a).
The inert anode material provided by the invention comprises a metal phase. In the present invention, the metal phase includes five or more elements selected from Al, Co, Cr, Fe, Ni, Ti, and Cu, and particularly preferably a metal phase composed of Al, Co, Cr, Fe, and Ni, or a metal phase composed of Al, Co, Cr, Fe, Ni, Ti, and Cu. In the present invention, the ratio of each single element in the metal phase is preferably 5 to 50 at%, more preferably 20 to 35 at%. In the present invention, the metal phase preferably has a solid solution structure of not more than two phases, more preferably has a single-phase or two-phase solid solution structure. In the present invention, when the metal phase is a single-phase solid solution structure, it specifically refers to an FCC crystal phase structure or a BCC crystal structure; when the metal phase is a two-phase solid solution structure, it specifically refers to an FCC crystal phase structure and a BCC crystal structure.
The inert anode material provided by the invention comprises a ceramic phase. In the present invention, the ceramic phase includes CuAl2O4、NiAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、FeAl2O4、NiFe2O4And CuFe2O4One or more of (a).
In the invention, the mass ratio of the metal phase to the ceramic phase is preferably 5-50: 50-95, and more preferably 15-50: 50-85.
The invention also provides a preparation method of the inert anode material in the technical scheme, which comprises the following steps:
mixing the metal phase raw material and the ceramic phase raw material to obtain a mixed material;
cold pressing the mixed material to obtain a green body;
and sintering the green body to obtain the inert anode material.
The invention mixes the metal phase raw material and the ceramic phase raw material to obtain the mixed material. In the present invention, the composition of the metal phase raw material is the same as that of the metal phase in the above technical solution. In the present invention, the particle size of the metal phase raw material is preferably 50 to 500 mesh, and more preferably 100 to 300 mesh. In the present invention, the metal phase raw material is preferably prepared by a mechanical alloying method or an atomization method, which will be separately described below.
In the present invention, the preparation method of the metal phase raw material is preferably a mechanical alloying method, and preferably includes the steps of:
ball-milling and mixing the metal raw materials to obtain alloy powder;
and drying the alloy powder to obtain the metal phase raw material.
In the present invention, the purity of each of the metal raw materials is independently preferably 99.9 wt% or more. In the present invention, before ball milling and mixing, each of the metal raw materials preferably further comprises a pretreatment, and the pretreatment method preferably comprises: and (3) placing all the metal raw materials in ethanol for standing, and then carrying out ultrasonic cleaning and drying. In the standing process, the metal raw materials can be fully immersed in the ethanol, and the cleaning is more sufficient. In the present invention, the ethanol is preferably anhydrous ethanol; the standing time is preferably 1-2 h; the power of ultrasonic cleaning is preferably 180-300W, and more preferably 200-250W; the ultrasonic cleaning time is preferably 5-30 min; the drying temperature is preferably 70-90 ℃, and the drying time is preferably 15-24 h.
In the invention, the ball milling and mixing are preferably carried out in a high-energy ball mill, and the material of the high-energy ball mill is preferably a vacuum stainless steel tank; the grinding balls adopted by ball milling mixing are preferably alloy balls, the alloy balls are preferably hard alloy balls or zirconia balls in composition, and the ball material ratio is preferably 4-20: 1, and more preferably 10: 1. In the invention, the rotation speed of the ball milling mixing is preferably 200-350 r/min, and more preferably 300-350 r/min; the time for ball milling and mixing is preferably 8-100 h, and more preferably 25-40 h. In the present invention, a process control agent is preferably added during the ball milling mixing process, and the process control agent preferably includes one of alcohol, stearic acid, paraffin wax, carbon tetrachloride and n-heptane; the addition amount of the process control agent is preferably 0.2 to 5 wt% based on the total mass of each metal raw material. The process control agent is added in the invention, so that cold welding and oxidation in the ball milling process can be prevented and reduced.
In the invention, the drying temperature of the alloy powder is preferably 70-90 ℃, and more preferably 80 ℃; the drying time is preferably 20-24 h. In the invention, the dried alloy powder is preferably sieved to obtain the metal phase raw material.
In the present invention, the preparation method of the metal phase raw material is preferably an atomization method, more preferably a vacuum induction melting atomization method, and particularly preferably includes the following steps:
carrying out induction melting on each metal raw material to obtain an alloy melt;
and spraying the alloy melt by using a high-pressure gas nozzle or a high-pressure water nozzle, and carrying out atomization treatment to obtain the metal phase raw material.
In the present invention, the purity of each of the metal raw materials is independently preferably 99.9 wt% or more. In the present invention, before the induction melting, each metal raw material preferably further includes a pretreatment, and the pretreatment method is the same as the pretreatment method in the mechanical alloying method described above, and is not described herein again.
In the present invention, the induction melting is preferably performed in an induction furnace, and in the present invention, before the induction melting is performed, the induction furnace is preferably vacuumized, and the degree of vacuum is preferably 0.1to 1 torr. In the present invention, the induction melting is preferably performed in a protective atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere; the induction melting temperature is preferably 1200-1700 ℃, and more preferably 1495 ℃; the induction melting time is preferably 80-150 min.
In the invention, when the alloy melt is sprayed by a high-pressure gas nozzle, high-purity nitrogen or high-purity argon is used as high-pressure gas; the purity of the high-purity nitrogen and the high-purity argon is preferably 99.999 percent; the pressure of the high-pressure gas is preferably 1.7 to 4.0MPa, and more preferably 2.0 MPa.
In the invention, when the alloy melt is sprayed by a high-pressure water nozzle, the pressure in the water atomization process is preferably 15-35 MPa, and the cooling rate of water in atomization is preferably controlled to be 1 x 105～1×104K/s。
In the invention, the atomized alloy powder is preferably sieved to obtain the metal phase raw material.
After the metal phase raw material is obtained, the metal phase raw material and the ceramic phase raw material are mixed to obtain a mixed material. In the invention, the particle size of the ceramic phase raw material is preferably 50-500 meshes, and more preferably 200-350 meshes. In the present invention, the ceramic phase raw material preferably includes CuAl2O4、NiAl2O4、FeAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、NiFe2O4And CuFe2O4One or more of (a). In the present invention, the ceramic phase raw material has a spinel structure, and can generate a corrosion-resistant layer phase in the electrolytic process to enhance the corrosion resistance of the inert anode.
In the invention, the mass ratio of the metal phase raw material to the ceramic phase raw material is preferably 5-50: 50-95, and more preferably 30-40: 60-70.
In the invention, the mixing method of the metal phase raw material and the ceramic phase raw material is preferably ball milling, and the rotating speed of the ball milling is preferably 100-350 r/min, more preferably 150-180 r/min; the ball milling time is preferably 4-8 h, and more preferably 7-8 h. In the invention, a binder and a dispersant are preferably added during the ball milling process; the binder is preferably polyvinyl alcohol or polyethylene glycol, and the dispersing agent is preferably deionized water or alcohol; the addition amount of the binder is preferably 0.5-3 wt% and the addition amount of the dispersant is preferably 0.5-4 wt% based on the total mass of the metal phase raw material and the ceramic phase raw material.
According to the invention, preferably, after the ball milling, the obtained mixed powder is dried to obtain a mixed material. In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 70-80 ℃; the drying time is preferably 24-30 h.
After the mixed material is obtained, the mixed material is subjected to cold pressing to obtain a green body. In the invention, the pressure of the cold pressing is preferably 150-350 MPa, and more preferably 200-310 MPa; the dwell time is preferably 1-10 min, and more preferably 2 min. In the invention, the cold pressing temperature is preferably 15-25 ℃. In the present invention, the cold pressing is preferably carried out in a hydraulic press.
After a green body is obtained, the green body is sintered to obtain the inert anode material. In the present invention, the sintering is preferably performed in a sintering furnace; the sintering temperature is preferably 1000-1650 ℃, and more preferably 1200-1300 ℃; the heat preservation time is preferably 2-24 h, and more preferably 2-4 h. In the present invention, the atmosphere for the sintering is preferably a protective atmosphere, and more preferably an argon or nitrogen atmosphere.
The invention adopts the cold pressing-sintering technology to prepare the inert anode material, the obtained material has high density and is more uniform, and the mechanical property of the inert anode material is favorably improved.
The invention also provides the application of the inert anode material in the technical scheme or the inert anode material prepared by the preparation method in the technical scheme in aluminum electrolysis. In the invention, the aluminum electrolyte adopted by the electrolytic aluminum is preferably a cryolite molten salt system, and particularly preferably Na3AlF6-AlF3-Al2O3And (3) melting salt.
In the invention, the temperature of the electrolytic aluminum is preferably 800-1000 ℃, and the time of the electrolytic aluminum is preferably 10-20 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Selecting Al, Co, Cr, Fe and Ni as high-entropy alloy metal raw materials, respectively placing all the raw materials in absolute ethyl alcohol for standing for 1h, then placing the raw materials in an ultrasonic cleaning machine, carrying out ultrasonic cleaning for 10min at the power of 200W, drying after cleaning, and mixing the raw materials according to the atomic percentage of Al: co: cr: fe: ni is 1:1:1:1:1, and the purity of each metal raw material is not lower than 99.9 wt%; putting the weighed metal raw materials into a high-energy ball mill for mechanical alloying reaction, wherein the ball mill adopts a vacuum stainless steel tank and hard alloy balls, the ball milling and mixing are carried out for 8 hours at the speed of 200r/min, the ball-material ratio is 10:1, alcohol is added before the ball milling as a process control agent, and the adding amount of the alcohol is 1.0 wt% based on the total mass of the metal raw materials; and after the ball milling is finished, taking out the alloy powder, placing the alloy powder in a constant-temperature drying box, drying the alloy powder for 24 hours at the temperature of 80 ℃, sieving the alloy powder to obtain a metal phase raw material, and sieving the metal phase raw material to obtain the metal phase raw material with the granularity of 100-200 meshes.
Mixing 200-300 mesh NiFe2O4Powder is used as a ceramic phase raw material, the metal phase raw material and the ceramic phase raw material are mixed according to the mass fraction of 40 wt% and 60 wt%, polyvinyl alcohol is used as a binder, deionized water is used as a dispersing agent, ball milling is carried out for 8 hours at the speed of 150r/min in a ball milling tank, the materials are uniformly mixed, and a sample is dried for 24 hours in an oven at the temperature of 80 ℃ to obtain a mixed material;
pressing the mixed material into a green body by adopting a hydraulic press, keeping the pressure at 25 ℃ for 2min, wherein the pressure value is 200 MPa;
and (3) sintering the green body in a sintering furnace at the sintering temperature of 1200 ℃, keeping the temperature for 2 hours in the sintering atmosphere of argon, and preparing the inert anode material.
The inert anode material prepared in this example had a density of 5.8g/cm3The inert anode material is used for electrolyzing an aluminum electrolysis system at 800 ℃ for 15 hours, the aluminum electrolysis system is a cryolite molten salt system, and the weight of the inert anode is increased by 4.55mg/cm2The impurity content of the aluminum liquid is about 0.15 percent; after 20A electrolysis experiment, the average cell voltage is 3.431V, which is reduced compared with the voltage (3.8-4.0V) of the conventional carbon anode cell; after cooling, the oxide layer has no obvious phenomena of peeling, breaking and layering, and the size of the oxide layer is almost unchanged. The inert anode material prepared by the invention has better corrosion resistance, mechanical property and electrical conductivity.
The compression yield strength of the inert anode material prepared by the embodiment is 1309MPa, and the inert anode material has better mechanical property.
Example 2
Selecting Al, Co, Cr, Fe, Ni, Ti and Cu as high-entropy alloy metal raw materials, respectively placing all the raw materials in absolute ethyl alcohol for standing for 2 hours, then placing the raw materials in an ultrasonic cleaning machine, ultrasonically cleaning for 25min at the power of 250W, drying after cleaning, and mixing the raw materials according to the atomic percentage of Al: co: cr: fe: ni: ti: cu is 0.6:1:1:1:1:1, and the purity of each metal raw material is not lower than 99.9 wt%; putting the weighed metal raw materials into a copper crucible for induction melting, vacuumizing an induction furnace before melting, controlling the vacuum degree to be 0.1torr, performing induction melting under the condition of taking argon as protective gas, controlling the working temperature to be 1495 ℃, spraying a melt through a high-pressure gas nozzle after the working temperature is reached for atomization treatment, selecting high-purity argon with the purity of 99.999% from high-pressure gas, controlling the pressure to be 2.0MPa, and cooling and sieving the prepared alloy powder to obtain the metal phase raw materials with the particle size of 200-300 meshes.
Mixing 200-300 mesh CuAl2O4Powder is used as a ceramic phase raw material, the metal phase raw material and the ceramic phase raw material are mixed according to the mass fractions of 30 wt% and 70 wt%, polyvinyl alcohol is used as a binder, deionized water is used as a dispersing agent, ball milling is carried out for 7 hours at a speed of 160r/min in a ball milling tank, the materials are uniformly mixed, a sample is dried for 30 hours in a 70 ℃ oven, and a mixed material is obtained
Pressing the mixed material into a green body by adopting a hydraulic press, keeping the pressure at 20 ℃ for 2min, wherein the pressure value is 310 MPa;
and sintering the green body in a sintering furnace at the sintering temperature of 1300 ℃, keeping the temperature for 4 hours in the sintering atmosphere of nitrogen, and preparing the inert anode material.
The inert anode material prepared in this example had a density of 5.7g/cm3The inert anode material is used for electrolyzing an aluminum electrolysis system at 800 ℃ for 20 hours, the aluminum electrolysis system is a cryolite molten salt system, and the weight of the inert anode is increased by 4.63mg/cm2The impurity content of the aluminum liquid is about 0.26 percent; the average cell voltage of 3.479V after 20A electrolysis experiment is reduced compared with the voltage (3.8-4.0V) of the conventional carbon anode cell; after cooling, the oxide layer has no obvious phenomena of peeling, breaking and layering, and the size of the oxide layer is almost unchanged. The inert anode prepared by the invention has better corrosion resistance, mechanical property and electrical conductivity.
Comparative example 1
The Ni-Fe alloy inert anode is used for electrolyzing an aluminum electrolysis system at 860 ℃ for 20 hours, the aluminum electrolysis system is a cryolite molten salt system, after 20 hours of electrolysis, anode fluorination is serious, the voltage is increased from 3.426V to more than 6V, and the resistance of electron transmission is large, so that the voltage is large, and the conductivity is poor.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An inert anode material comprising a metal phase and a ceramic phase; the metal phase comprises more than five elements of Al, Co, Cr, Fe, Ni, Ti and Cu; the ceramic phase comprises CuAl2O4、NiAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、FeAl2O4、NiFe2O4And CuFe2O4One or more of (a).
2. The inert anode material according to claim 1, wherein the proportion of each single element in the metal phase is 5 to 50 at%.
3. Inert anode material according to claim 1 or 2, characterized in that the metal phase has a solid solution structure of not more than two phases.
4. A method for preparing an inert anode material as claimed in any one of claims 1to 3, comprising the steps of:
mixing the metal phase raw material and the ceramic phase raw material to obtain a mixed material;
cold pressing the mixed material to obtain a green body;
and sintering the green body to obtain the inert anode material.
5. The preparation method according to claim 4, wherein the metal phase raw material is prepared by a mechanical alloying method or an atomization method.
6. The production method according to claim 4 or 5, wherein the particle size of the metal phase raw material is 50 to 500 mesh.
7. The preparation method according to claim 4, wherein the mass ratio of the metal phase raw material to the ceramic phase raw material is 5-50: 50-95.
8. The preparation method according to claim 4, wherein the pressure of the cold pressing is 150 to 350MPa, and the dwell time is 1to 10 min.
9. The preparation method according to claim 4, wherein the sintering temperature is 1000-1650 ℃, and the heat preservation time is 2-24 h.
10. Use of the inert anode material according to any one of claims 1to 3 or the inert anode material prepared by the preparation method according to any one of claims 4 to 9 in aluminum electrolysis.
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