CN119194536B - A method for preparing niobium aluminum alloy by molten salt electrolysis of cerium niobium perovskite - Google Patents
A method for preparing niobium aluminum alloy by molten salt electrolysis of cerium niobium perovskite Download PDFInfo
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Abstract
本发明涉及电化学冶金技术领域，提及了一种熔盐电解铈铌钙钛矿制备铌铝合金的方法，包括：将原料铝放置于电解槽底部；将原料矿与熔盐混匀后放置于电解槽内；将电解槽底部进行加热，升温并保温后，使原料铝熔融至液态铝；保温结束后，将电解槽底部升温，液态铝作为阴极，石墨棒作为阳极，连接直流电源后，按照预设电源电压，进行恒电压电解，得到电解产物；将得到的电解产物进行破碎磨细，得到铌铝合金和残余的熔盐。本发明提及的方法，通过电化学条件的精准控制，实现铌、钛间的梯级电解和元素分离，在制备铌铝合金、铌钛铝合金的同时，实现了含稀土、铌、钛的共伴生矿或冶金渣中多种金属的综合提取利用。
The present invention relates to the field of electrochemical metallurgy technology, and mentions a method for preparing niobium aluminum alloy by electrolyzing cerium niobium perovskite in molten salt, comprising: placing raw aluminum at the bottom of an electrolytic cell; mixing the raw ore with molten salt and placing it in the electrolytic cell; heating the bottom of the electrolytic cell, heating and keeping the temperature, so that the raw aluminum melts into liquid aluminum; after the insulation is completed, heating the bottom of the electrolytic cell, using the liquid aluminum as the cathode and the graphite rod as the anode, connecting a DC power supply, and performing constant voltage electrolysis according to a preset power supply voltage to obtain an electrolysis product; crushing and grinding the obtained electrolysis product to obtain a niobium aluminum alloy and residual molten salt. The method mentioned in the present invention realizes the step electrolysis and element separation between niobium and titanium through the precise control of electrochemical conditions, and realizes the comprehensive extraction and utilization of multiple metals in the co-existing ore or metallurgical slag containing rare earth, niobium and titanium while preparing niobium aluminum alloy and niobium titanium aluminum alloy.
Description
Technical Field
The invention relates to the technical field of electrochemical metallurgy, in particular to a method for preparing niobium-aluminum alloy by electrolyzing cerium-niobium perovskite through molten salt.
Background
Niobium is a rare metal with great strategic significance for national security and development of emerging industries, and is widely applied to fields of steel, aviation, aerospace, navigation, chemical industry, construction, medicine and the like, and is indispensable in modern industry and sophisticated technology due to excellent physical, chemical and mechanical properties of niobium and related compounds thereof.
The bayan obo ore is a multi-metal intergrowth ore integrating important elements such as rare earth, iron, niobium, titanium and the like. The rare earth resource reserves are the first in the world, and the niobium resource reserves are the second in the world. However, in the past, the development and utilization of the baiyunebo mineral resources mainly comprise iron, the comprehensive utilization rate of rare earth resources is less than 10 percent, and the comprehensive utilization rate of niobium resources is almost zero. The niobium grade of the baiyunebo ore is about 0.10%, the number of the niobium-containing ore phases is up to 20, the particle size is generally not more than 20 mu m, and the baiyunebo ore phases are poor, mixed and fine, are symbiotic or packed with other ore phases, so that the separation and the extraction are extremely difficult. Especially, the chemical properties of niobium and titanium are similar, and the niobium and the titanium are widely symbiotic in various niobium-containing ore phases in the same class, and inherit to the process of dressing and smelting niobium resources, so that the concentrate grade and the product quality are seriously influenced.
Chinese patent publication No. CN116240590a discloses a "method for preparing a niobium-titanium alloy by molten salt electrolysis", in which titanium tetrachloride and niobium pentachloride are dissolved in chloride molten salt to perform electrolysis to prepare a niobium-titanium alloy. Chinese patent publication No. CN115717254a discloses a "method for preparing high-purity metallic niobium by molten salt electrolysis", which uses the prepared niobium-carbon-based solid solution as a soluble anode and graphite as a cathode, and performs electrolysis in a chloride molten salt system to prepare metallic niobium. Chinese patent publication No. CN116463683a discloses a "method for separating metallic niobium and titanium by using soluble anode electrolysis", in which a prepared niobium-carbon-based solid solution and a titanium-carbon-based solid solution are used as anodes and are respectively placed in two chloride electrolyte systems for electrolysis, so as to achieve the separation of niobium and titanium. Chinese patent publication No. CN115305521a discloses a "method for preparing metallic niobium by molten salt electrolysis", which uses liquid niobium alloy to divide an electrolytic cell into a cathode cell and an anode cell, and then performs electrolysis to prepare metallic niobium.
The patent technologies all use molten salt electrolysis to achieve the purposes of preparing metal niobium or separating niobium and titanium. However, the problems of low current efficiency and poor electrolysis effect caused by low solubility of niobium and titanium in molten salt are not considered, the preparation process of adopting the niobium-titanium-carbon-based solid solution as a cathode is complex, and a large amount of carbon monoxide or carbon dioxide is released along with the deposition of a target product in the electrolysis process, so that large-scale production is difficult to realize, and the method does not carry out electrolysis separation on minerals with coexisting niobium and titanium, so that the effect in practical production and application is not considered.
Chinese patent publication No. CN105385866A discloses a preparation method and a system of a niobium-aluminum alloy, and the method utilizes aluminothermic reduction reaction to uniformly distribute metal niobium generated by the reaction in aluminum liquid and react with redundant aluminum to generate the niobium-aluminum alloy. Chinese patent publication No. CN115478200A discloses that the niobium-aluminum alloy is prepared by fully mixing a niobium source, an aluminum source, a slag former and a heat generator and then performing aluminothermic reaction. Chinese patent publication No. CN104674067a discloses a "production method of a niobium-aluminum alloy", which adopts pure principal element niobium, namely, a niobium-aluminum intermediate alloy with a melting point of about 1690 ℃ to perform smelting, so as to obtain the niobium-aluminum alloy.
The above methods all utilize thermite reduction reaction to prepare niobium-aluminum alloy, however, the above methods can not overcome the problem of co-reduction of other metals, so that the problem of separation of metal elements in complex co-associated ores can not be solved.
Disclosure of Invention
First, the technical problem to be solved
In view of the defects of various processes for extracting niobium from bayan obo mine tailings in the prior art, the technical problem of effective recycling is still not obtained.
(II) technical scheme
To this end, the invention provides a method for preparing niobium-aluminum alloy by molten salt electrolysis of cerium-niobium perovskite, comprising the following steps:
Step 1, placing raw material aluminum at the bottom of an electrolytic tank;
step 2, uniformly mixing the raw ore and the molten salt according to the mass ratio range of (1-10): 100, and then placing the mixture in an electrolytic tank;
Step 3, heating the bottom of the electrolytic tank, heating to a first preset temperature, and preserving heat for a first preset time to enable the raw material aluminum to be melted into liquid aluminum;
Step 4, after the heat preservation is finished, the temperature of the bottom of the electrolytic tank is raised to a second preset temperature, liquid aluminum is used as a cathode, a graphite rod is used as an anode, and after the direct current power supply is connected, constant-voltage electrolysis is performed according to a preset power supply voltage, so that an electrolysis product is obtained;
And 5, crushing and grinding the obtained electrolysis product to obtain the niobium-aluminum alloy and residual molten salt.
Further, in step4, the preset power supply voltage is lower than the decomposition voltage of the molten salt system, rare earth and titanium oxide, and higher than the decomposition voltage of niobium oxide.
Further, in step 2, the molten salt is formed by mixing Na 3AlF6 with at least one of NaF, liF, or KF.
Further, in the molten salt, na 3AlF6 and at least one of NaF, liF, or KF are mixed in a mass ratio of (7:3) - (5:5).
Further, the preset power supply voltage is 2-5V.
Further, in the step2, the raw ore comprises, by mass percent, 38% -46% of REO, 13% -17% of Nb 2O5, 29% -37% of TiO and the balance of unavoidable impurities, wherein the sum of the mass percentages is 100%.
Further, in step 3, inert gas with preset flow rate is introduced to perform atmosphere protection.
Further, in step 4, the constant voltage electrolysis is performed for a second preset time, and the second preset time is 1-5 hours.
Further, in step 5, after the electrolysis is completed, the cathode, the anode and the molten salt are cooled under the protection of inert gas.
Further, in step 5, the residual molten salt contains rare earth and titanium for separation and extraction of rare earth and titanium.
(III) beneficial effects
The invention provides a method for preparing niobium-aluminum alloy by electrolyzing cerium-niobium perovskite through molten salt, which comprises the steps of placing raw material aluminum at the bottom of an electrolytic tank, uniformly mixing raw material ore and molten salt according to the mass ratio range of (1-10): 100, placing the mixture in the electrolytic tank, heating the bottom of the electrolytic tank, heating to a first preset temperature, preserving heat for a first preset time to enable the raw material aluminum to be melted into liquid aluminum, heating the bottom of the electrolytic tank to a second preset temperature after the heat preservation is finished, using the liquid aluminum as a cathode, using a graphite rod as an anode, connecting a direct-current power supply, carrying out constant-voltage electrolysis according to a preset power supply voltage to obtain an electrolytic product, and crushing and grinding the obtained electrolytic product to obtain the niobium-aluminum alloy and residual molten salt.
According to the method for preparing the niobium-aluminum alloy by the molten salt electrolysis cerium-niobium perovskite, the low-melting-point metal aluminum is used as a liquid cathode, so that the operation difficulty is low, the problem of dendrite growth of a niobium product is effectively avoided, the generation of niobium carbide and titanium carbide is avoided, and the related problems of low electrolysis efficiency and the like are solved. And (3) carrying out continuous electrolytic separation and extraction by supplementing raw materials, and successfully obtaining the niobium-aluminum alloy and the niobium-titanium-aluminum alloy. Through the accurate control of electrochemical conditions, the step electrolysis and element separation between niobium and titanium are realized. The selective reduction of niobium and titanium is realized by carrying out step electrolysis on the preset voltage according to the sequence of niobium, titanium and rare earth, and the niobium-aluminum alloy and the niobium-titanium-aluminum alloy are prepared. The phase separation of different key metals is realized by means of the diffusion of selectively precipitated metals between the molten salt and the liquid cathode. The method realizes the comprehensive extraction and utilization of various metals in the co-associated ore or metallurgical slag containing rare earth, niobium and titanium while preparing the niobium-aluminum alloy and the niobium-titanium-aluminum alloy while completing the separation of the niobium and the titanium.
Drawings
FIG. 1 is a theoretical decomposition voltage diagram of a method for preparing niobium-aluminum alloy by molten salt electrolysis of cerium-niobium perovskite according to the application;
FIG. 2 is a process flow diagram of a method for preparing a niobium-aluminum alloy by molten salt electrolysis of cerium-niobium perovskite according to the application;
fig. 3 is a crystal structure diagram of a raw material of a method for preparing a niobium-aluminum alloy by molten salt electrolysis of cerium-niobium perovskite according to the present application.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1-5" is disclosed, the described range should be interpreted to include the ranges of "1-4", "1-3", "1-2 and 4-5", "1-3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated. "parts by mass" refers to a basic unit of measurement representing the mass ratio of the components, and 1 part may represent an arbitrary unit mass, for example, 1 g or 3.527 g. If we say that the mass part of the A component is a part and the mass part of the B component is B part, the ratio a: B of the mass of the A component to the mass of the B component is expressed. Or the mass of the A component is aK, the mass of the B component is bK (K is any number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass. "and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The chemical properties of niobium and titanium are similar, the ionic radius is close, and the wide class of the same substances are formed in the bayan obo ore, so that the problems of difficult separation, insufficient purity of niobium products, limited application and the like are caused. And because of the complexity and the specificity of the composition of the bayan obo minerals, the treatment process is inevitably free from invalid circulation of repeated conversion of element occurrence forms, and the energy loading and unloading are switched for multiple times in the high-temperature and low-temperature process, and meanwhile, a large amount of high-pollution waste water and waste gas are discharged in the processes of decomposition, leaching, calcination and the like, so that the environment is polluted. Therefore, a new process is necessary to be developed, the deep separation of elements is realized by means of the difference of electrochemical behaviors of different key metals, and the cross fusion of metallurgical separation conversion and alloy material preparation is realized by following the design concept of metallurgical material integration.
From the theoretical decomposition voltage diagrams at different temperatures shown in fig. 1, it is found that the theoretical decomposition voltages of the titanium oxide and the rare earth oxide are above the theoretical decomposition voltages of the niobium oxide and the iron oxide, and the effect of preparing the niobium-aluminum alloy can be achieved by controlling the voltages to be a selective electrolysis between niobium and titanium to separate and precipitate the niobium and the titanium.
Referring to fig. 2, the invention provides a method for preparing niobium-aluminum alloy by molten salt electrolysis of cerium-niobium perovskite, which comprises the following steps:
and 1, placing raw material aluminum at the bottom of an electrolytic tank.
The metal aluminum is used as a liquid cathode, the operation is simple, the dendrite growth of a niobium product can be effectively avoided, and the niobium-aluminum alloy is directly prepared. The metal aluminum is used as a liquid cathode, and in the electrolysis process, the liquid cathode can provide a larger reaction area, so that the reaction is facilitated, and meanwhile, the dendrite growth is avoided, so that the quality and stability of the product can be improved.
Illustratively, the raw aluminum is metallic aluminum. 10-50 g of metallic aluminum can be placed at the bottom of the electrolytic cell.
And 2, uniformly mixing the raw ore and the molten salt according to the mass ratio range of (1-10): 100, and then placing the mixture in an electrolytic tank.
In a possible embodiment, in the step 2, the raw ore comprises, by mass percent, 38% -46% of REO, 29% -37% of Nb 2O5：13%-17%,TiO2 and the balance of unavoidable impurities, wherein the sum of the mass percentages is 100%. The raw ore contains cerium niobium perovskite and other components including REO (rare earth oxide), niobium oxide, titanium oxide and the like, has higher grade, and is used as a source of target metal. Because the solubility and the reactivity of different raw material ore components in molten salt are different, the mass ratio of the raw material ore to the molten salt is selected to be (1-10): 100, so that enough reactants participate in the reaction in the electrolysis process, and meanwhile, the phenomenon that the migration of ions and the reaction are influenced due to too thick molten salt system caused by too much raw materials is avoided.
The method for preparing the niobium-aluminum alloy by the molten salt electrolysis cerium-niobium perovskite adopts cerium-niobium perovskite with a similar crystal structure as the perovskite as an electrolysis raw material, and utilizes the characteristic that the cerium-niobium perovskite has higher solubility in a molten salt system due to the easily-dissociated crystal structure, so that the problem of low solubility of niobium and titanium oxides in the molten salt system is solved, and the current efficiency is improved. By utilizing the characteristic that certain difference exists in theoretical decomposition voltage required by reduction of oxides of niobium and titanium into metals, selective electrolytic reduction between different metals is realized through potential control, and phase-to-phase separation of different key metals is realized by virtue of diffusion of selectively separated metals between molten salt and liquid cathode.
Referring to fig. 3, fig. 3 shows a crystal structure of a raw material cerium niobium perovskite niobium, the crystal structure is ((Ca, ce) (Ni, ti) O 3), and the crystal structure has higher solubility and easy dissociation in a sodium fluoride-cryolite molten salt system, so that rapid migration and diffusion of alkali metal cations and oxyacid radical anions can be realized, and the problem of low solubility of niobium and titanium oxides in molten salt is solved.
In one possible embodiment, in step 2, the molten salt is Na 3AlF6 mixed with at least one of NaF, liF, or KF. In the molten salt, na 3AlF6 and at least one of NaF, liF or KF are mixed according to mass ratio (7:3) - (5:5).
The molten salt serves as an electrolyte providing an ion conductive environment. The molten salt system formed by mixing Na 3AlF6 with at least one of NaF, liF or KF has the properties of proper melting point, viscosity, conductivity and the like, and can ensure smooth migration of ions and reaction in the electrolytic process.
The molten salt needs to be in sufficient quantity to dissolve a proportion of the raw ore to ionize it to form an ionic species available for electrolysis. At the same time, the molten salt also plays a role in transferring heat and maintaining the reaction temperature.
The raw material ores and the molten salt are uniformly mixed, so that the raw material ores are uniformly distributed in the molten salt, and the local concentration is prevented from being too high or too low, so that the uniformity of the reaction is improved.
In the electrolysis process, the migration speed and the reactivity of ions in molten salt are influenced by the concentration gradient, and the concentration gradient can be reduced by uniform distribution, so that the reaction can be carried out more smoothly.
The evenly distributed raw ore is also beneficial to heat transfer, avoids local overheating or supercooling, and maintains stable reaction temperature.
The ions in the molten salt interact with the components in the raw ore to promote ionization and dissolution of the raw ore. Illustratively, cations in the molten salt may react with oxides in the feed ore to form ionic metal and oxygen ions. The mixing process can increase the contact area of the raw ore and molten salt, accelerate the ionization and dissolution processes and improve the reaction efficiency.
According to the application, by selecting at least one of Na 3AlF6, naF, liF or KF and a molten salt system with the mass ratio of (7:3) - (5:5), the characteristic that certain difference exists in theoretical decomposition voltage required by reduction of oxides of niobium and titanium into metals can be utilized, so that selective electrolytic reduction among different metals can be realized. The concentration and activity of ions in the molten salt can be adjusted by the molten salt system and the mass ratio, so that the reduction potentials of different metal ions are influenced.
In one possible embodiment, the preset power supply voltage is lower than the decomposition voltage of the molten salt system, rare earth and titanium oxides, and higher than the decomposition voltage of niobium oxides. The electrolysis mode adopts constant voltage electrolysis, and the electrolysis range is 2-5V. Under the preset power supply voltage, only niobium oxide is reduced, but the molten salt system, rare earth and titanium oxide are not reduced, so that interphase separation can be realized. The current efficiency is improved, the selective electrolytic reduction and interphase separation of different metals are realized, the subsequent extraction of different metal components is facilitated, and the comprehensive utilization rate of resources is improved.
And 3, heating the bottom of the electrolytic tank, heating to a first preset temperature, and preserving heat for a first preset time to enable the raw material aluminum to be melted into liquid aluminum. The application changes the melting point of the aluminum raw material into liquid state by heating. The method is used for preparing the subsequent electrolytic reaction as a cathode, and the liquid aluminum can better react with cations, so that the reaction efficiency is improved.
The first preset temperature is 700-900 ℃ and the first preset time is 0.5-3 hours, so that the metal aluminum is completely melted to serve as a cathode.
In a possible implementation manner, in the step 3, the inert gas with a preset flow rate is introduced to perform atmosphere protection, and the inert gas may be high-purity argon, and the preset flow rate may be 0.5L/min-1.5L/min, for example.
Aluminum and metals that may be generated during electrolysis are easily reacted with oxygen in the air at high temperature and thus oxidized. The high-purity argon is introduced to form inert atmosphere in the electrolytic tank, so that contact between aluminum and other metals and oxygen is avoided, and oxidation reaction is prevented. The flow rate of the argon is controlled within the range of 0.5L/min-1.5L/min, so that the interference of excessive air flow to an electrolytic system can be avoided while the effective atmosphere protection is ensured. Too small flow rate can not sufficiently remove impurity gases such as oxygen, and too large flow rate can cause problems such as molten salt splashing and unstable temperature.
And 4, after the heat preservation is finished, raising the temperature of the bottom of the electrolytic tank to a second preset temperature, taking liquid aluminum as a cathode, taking a graphite rod as an anode, connecting a direct current power supply, and carrying out constant-voltage electrolysis according to a preset power supply voltage to obtain an electrolysis product.
It should be noted that the second preset temperature is an electrolysis temperature, and the electrolysis temperature is 700-1100 ℃ by way of example, and the increase of the temperature can increase the migration speed and the reactivity of ions so that the electrolysis reaction can be performed more quickly. The elevated temperature ensures that the molten salt maintains good fluidity during electrolysis so that ions can migrate smoothly therein. If the temperature is too low, the molten salt becomes too viscous, affecting the conduction of ions and the progress of the reaction.
Under the action of direct current, the anode performs oxidation reaction, and the graphite rod loses electrons. The cathode undergoes a reduction reaction, and the cations are reduced to metal at the liquid aluminum cathode by electrons. The preset power supply voltage is lower than the decomposition voltage of the molten salt system, rare earth and titanium oxide and higher than the decomposition voltage of niobium oxide, so that only the niobium oxide is reduced, and selective electrolytic reduction is realized. The preset power supply voltage is set to selectively reduce the niobium oxide to prepare the niobium-aluminum alloy, so that other unnecessary metals are prevented from being reduced, and the purity and pertinence of the product are improved.
In a possible embodiment, in step 4, the constant voltage electrolysis is performed for a second preset time, the second preset time being 1-5 hours.
And 5, crushing and grinding the obtained electrolysis product to obtain the niobium-aluminum alloy and residual molten salt. In one possible embodiment, after the electrolysis is completed in step 5, the cathode, anode and molten salt are cooled under the protection of inert gas.
In one possible embodiment, in step 5, the residual molten salt contains rare earth and titanium for the separation and extraction of rare earth and titanium.
Illustratively, the electrolysis product may be separated into the niobium-aluminum alloy and the residual molten salt by means of physical disruption. The crushing and grinding can facilitate the subsequent further processing and utilization of the niobium-aluminum alloy, and the residual molten salt contains rare earth and titanium, so that the method can be used for separating and extracting the rare earth and the titanium, and the comprehensive utilization rate of resources is improved. In addition, inert gas is introduced in the step 3 for atmosphere protection, so that aluminum and other metals can be prevented from being oxidized at high temperature, and smooth reaction is ensured. After the electrolysis in the step 5 is finished, the cathode, the anode and the molten salt are cooled under the protection of inert gas, so that the oxidation of metal is prevented, and the quality of the product is maintained.
The application solves the problem of low solubility of niobium and titanium oxides in molten salt by means of the oxyacid salt structure of cerium niobium perovskite. Cerium niobium perovskite has a space structure with higher solubility and dissociation degree in a molten salt system, can realize rapid migration and diffusion of alkali metal cations and oxyacid radical anions, and meets the industrial requirements of limiting current diffusion density and current efficiency.
The invention is matched with the use of a liquid metal cathode, and solves the difficult problem of dendrite growth of refractory metal electrolysis products. The niobium-containing ion groups are promoted to be electrochemically converted and diffused into the cathode in situ on the surface of the liquid cathode, so that dendrite growth of niobium products is avoided, and direct preparation of products such as Nb-Al alloy, nb-Ti-Al alloy and the like is realized.
The invention realizes the step electrolysis and element separation between niobium and titanium through the accurate control of electrochemical conditions. The voltage of the electrolytic tank can be regulated and controlled to carry out step electrolysis according to the sequence of niobium, titanium and rare earth, and the interphase separation of different key metals is realized by virtue of the diffusion of selectively separated metals between molten salt and liquid cathode.
For a better understanding of the technical solution, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
And 1, placing metal aluminum at the bottom of the electrolytic tank.
And 2, compounding NaF-Na 3AlF6 according to the mass percentages of 42% and 58%, adding 8% of cerium-niobium perovskite, wherein the components comprise w (REO) 46% and w (Nb 2O5)：13%,w(TiO2) 35%, and placing the uniformly mixed molten salt in a high-purity graphite electrolytic tank.
And 3, heating the electrolytic tank to 700 ℃ and preserving heat for 2 hours to enable the metal aluminum to be completely melted into a liquid state to serve as an aluminum cathode, and continuously introducing inert gas in the process.
And 4, taking liquid aluminum as a cathode, taking high-purity graphite as an anode, keeping the temperature, and then raising the temperature to 800 ℃ for electrolysis, setting the cell voltage to 2.5V for constant-voltage electrolysis for 2 hours.
And 5, after the electrolysis is finished, cooling the electrode and the molten salt in an inert gas atmosphere, taking out, transferring niobium ions to the surface of the liquid metal aluminum at the bottom in the electrolysis process to obtain electrons, reducing the electrons into metal niobium, continuously diffusing the separated niobium into the liquid metal aluminum, and rapidly wrapping the separated niobium to form the niobium-aluminum alloy. After the alloy is fully crushed and ground, distilled water is washed for a plurality of times, components are detected after low-temperature drying, the content of Nb and Al in the alloy is respectively 13% and 75%, and the rest components are impurities, so that the effect of separating niobium from titanium is successfully achieved, selective electrolytic precipitation is realized, and the niobium-aluminum alloy is directly prepared.
Example 2
And 1, placing metal aluminum at the bottom of the electrolytic tank.
And 2, preparing NaF-Na3AlF6 according to the mass percentages of 42% and 58%, adding 8% of cerium-niobium perovskite, wherein the components comprise w (REO) 38%, w (Nb 2O 5) 16% and w (TiO 2) 29%, and placing the uniformly mixed molten salt in a high-purity graphite electrolytic tank.
And 3, heating the electrolytic tank to 700 ℃ and preserving heat for 2 hours to enable the metal aluminum to be completely melted into a liquid state to serve as an aluminum cathode, and continuously introducing inert gas in the process.
And 4, taking liquid aluminum as a cathode, taking high-purity graphite as an anode, keeping the temperature, and then raising the temperature to 850 ℃ for electrolysis, and setting the cell voltage to 3.0V for constant-voltage electrolysis for 2 hours.
And 5, after the electrolysis is finished, cooling the electrode and the molten salt in an inert gas atmosphere, taking out, transferring niobium ions to the surface of the liquid metal aluminum at the bottom in the electrolysis process to obtain electrons, reducing the electrons into metal niobium, continuously diffusing the separated niobium into the liquid metal aluminum, and rapidly wrapping the separated niobium to form the niobium-aluminum alloy. After the alloy is fully crushed and ground, distilled water is used for washing for a plurality of times, components are detected after low-temperature drying, the content of Nb and Al in the alloy is respectively 18 percent and 71 percent, and the rest components are impurities, so that the effect of separating niobium from titanium is successfully achieved, selective electrolytic precipitation is realized, and the niobium-aluminum alloy is directly prepared.
Example 3
And 1, placing metal aluminum at the bottom of the electrolytic tank.
And 2, preparing 38% and 62% of NaF-Na3AlF6 by mass percent respectively, adding 10% of cerium-niobium perovskite, wherein the components comprise w (REO) 43%, w (Nb 2O 5) 17% and w (TiO 2) 37%, and placing the uniformly mixed molten salt in a high-purity graphite electrolytic tank.
And 3, heating the graphite electrolytic tank to 700 ℃ and preserving heat for 2 hours to enable the metal aluminum to be completely melted into a liquid state to serve as an aluminum cathode, and continuously introducing inert gas in the process.
And 4, taking liquid aluminum as a cathode, taking high-purity graphite as an anode, keeping the temperature, raising the temperature to 900 ℃ for electrolysis, and setting the cell voltage to 4V for constant-voltage electrolysis for 4 hours.
And 5, after the electrolysis is finished, cooling the electrode and the molten salt in an inert gas atmosphere, taking out, transferring niobium and titanium ions to the surface of the liquid metal aluminum at the bottom in the electrolysis process to obtain electrons, reducing the electrons into metal niobium and metal titanium, continuously diffusing the separated metal into the liquid metal aluminum, and rapidly wrapping the metal to form niobium-aluminum alloy and niobium-titanium-aluminum alloy. After the alloy is fully crushed and ground, distilled water is used for washing for a plurality of times, components are detected after low-temperature drying, and the contents of Nb, ti and Al in the alloy are respectively 14%, 27% and 48%, so that selective electrolytic precipitation is realized, and the niobium titanium aluminum alloy is directly prepared.
The foregoing has outlined the basic principles, features, and advantages of the present invention. However, the foregoing is merely specific examples of the present invention, and the technical features of the present invention are not limited thereto, and any other embodiments that are derived by those skilled in the art without departing from the technical solution of the present invention are included in the scope of the present invention.
In the description of the present invention, each embodiment focuses on the differences from other embodiments, and the same similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
In the description of the present invention, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
In the present invention, unless expressly stated or limited otherwise, a first feature is "on" or "under" a second feature, which may be in direct contact with the first and second features, or in indirect contact with the first and second features via an intervening medium. Moreover, a first feature "above," "over" and "on" a second feature may be a first feature directly above or obliquely above the second feature, or simply indicate that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is level lower than the second feature.
In the description of the present specification, the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., refer to particular features, structures, materials, or characteristics described in connection with the embodiment or example as being included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that alterations, modifications, substitutions and variations may be made in the above embodiments by those skilled in the art within the scope of the invention.
Claims (6)
1. The method for preparing the niobium-aluminum alloy by the molten salt electrolysis of cerium-niobium perovskite is characterized by comprising the following steps:
Step 1, placing raw material aluminum at the bottom of an electrolytic tank;
step 2, uniformly mixing the raw ore and the molten salt according to the mass ratio range of (1-10): 100, and then placing the mixture in an electrolytic tank;
step 3, heating the bottom of the electrolytic tank, heating to a first preset temperature, and preserving heat for a first preset time to enable the raw material aluminum to be melted into liquid aluminum;
step 4, after heat preservation is finished, the temperature of the bottom of the electrolytic tank is raised to a second preset temperature, liquid aluminum is used as a cathode, a graphite rod is used as an anode, and after a direct current power supply is connected, constant-voltage electrolysis is performed according to a preset power supply voltage, so that an electrolysis product is obtained;
step 5, crushing and grinding the obtained electrolysis product to obtain niobium-aluminum alloy and residual molten salt;
In step 4, the preset power supply voltage is lower than the decomposition voltage of the molten salt system, rare earth and titanium oxide and higher than the decomposition voltage of niobium oxide;
In the step 2, the molten salt is formed by mixing Na 3AlF6 with at least one of NaF, liF or KF;
In the molten salt, na 3AlF6 and at least one of NaF, liF or KF are mixed according to mass ratio, wherein the mass ratio is (7:3) - (5:5);
The preset power supply voltage is 2-3V.
2. The method for preparing the niobium-aluminum alloy by the molten salt electrolysis of cerium-niobium perovskite according to claim 1, wherein,
In the step 2, the raw ore comprises, by mass, 38% -46% of REO, 13% -17% of Nb 2O5, 29% -37% of TiO and the balance of unavoidable impurities, wherein the sum of the mass percentages is 100%.
3. The method for preparing the niobium-aluminum alloy by the molten salt electrolysis of cerium-niobium perovskite according to claim 1, wherein,
In the step 3, inert gas with preset flow rate is introduced to perform atmosphere protection.
4. The method for preparing the niobium-aluminum alloy by the molten salt electrolysis of cerium-niobium perovskite according to claim 1, wherein,
In the step 4, the constant voltage electrolysis is carried out for a second preset time, and the second preset time is 1-5h.
5. The method for preparing the niobium-aluminum alloy by the molten salt electrolysis of cerium-niobium perovskite according to claim 1, wherein,
In step 5, after the electrolysis is completed, the cathode, anode and molten salt are cooled under the protection of inert gas.
6. The method for preparing the niobium-aluminum alloy by the molten salt electrolysis of cerium-niobium perovskite according to claim 1, wherein,
In the step 5, the residual molten salt contains rare earth and titanium and is used for separating and extracting the rare earth and the titanium.
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