CN108456897B

CN108456897B - Aluminum source for preparing aluminum-containing alloy through electrolysis, preparation method and method for preparing aluminum-containing alloy through aluminum source

Info

Publication number: CN108456897B
Application number: CN201710087088.9A
Authority: CN
Inventors: 卢旭晨; 刘洋; 张志敏
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2017-02-17
Filing date: 2017-02-17
Publication date: 2020-11-20
Anticipated expiration: 2037-02-17
Also published as: CN108456897A

Abstract

The present invention provides an aluminum source for the electrolytic preparation of aluminum-containing alloys comprising a double salt formed from an aluminum halide and an alkali metal halide. The problem that aluminum halide is easy to absorb water at normal temperature and sublimate at high temperature, and the actual adding amount of the aluminum source is difficult to control is solved, the harm to the environment caused by aluminum halide aluminum source sublimation is solved, the problem that the aluminum hydroxide sediment is generated by water absorption of the aluminum halide aluminum source is solved, and the deslagging period of the electrolytic cell and the service life of the electrolytic cell are prolonged. When the aluminum-containing alloy is used for preparing aluminum-containing alloy, the content of aluminum element entering an electrolyte can be controlled, the controllable proportion of the aluminum-containing alloy element is further realized, the stability of the proportion of elements in aluminum-containing alloys in different batches is realized, and the secondary melting during the preparation of workpieces by aluminum-containing alloy materials is omitted; in addition, the aluminum source provided by the invention can reduce the sublimation of aluminum element and reduce the environmental hazard.

Description

Aluminum source for preparing aluminum-containing alloy through electrolysis, preparation method and method for preparing aluminum-containing alloy through aluminum source

Technical Field

The invention belongs to the field of metallurgy and materials, and particularly relates to an aluminum source for preparing an aluminum-containing alloy through electrolysis and a method for preparing the aluminum-containing alloy by using the aluminum source.

Background

Aluminum-containing alloys such as magnesium aluminum alloy, lithium aluminum alloy, beryllium aluminum, manganese aluminum, silicon aluminum, tin aluminum, scandium aluminum, yttrium aluminum, zirconium aluminum, rare earth aluminum alloy and the like have unique excellent properties, and are widely applied to the preparation of new materials or the application of the new materials in the fields of aerospace, aviation, military industry, transportation vehicles, electronics, 3C and the like. In recent years, the miniaturization, intelligentization and lightweight of products are developed more and more rapidly, and the demand of new materials is more and more urgent. For example, magnesium-aluminum alloy has the characteristics of light weight, high specific strength, electromagnetic interference resistance, good shock absorption, easy recovery and the like, and is known as the metal material in the 21 st century. The secondary molten salt lithium battery made of the lithium-aluminum alloy has high power density, high energy density and long cycle life.

The traditional alloy preparation adopts a smelting method (also called a symmetric doping method), which is to place alloy metal in a smelting furnace, keep the high temperature for enough time under the protection of gas and flux to melt, diffuse and mix the materials uniformly, and then prepare the target alloy. The method has the following defects: the alloy production process is complicated: the required alloying metal is obtained through respective metallurgical process, and then the target alloy can be obtained through two or even multiple times of smelting; secondly, the product has poor uniformity: due to the large difference of the densities of different metals participating in alloying (such as the magnesium metal with the density of 1.74 g/cm)³Is thin and thinThe density of the earth metal neodymium is 7.00g/cm³) Even if mechanical stirring is adopted in high-temperature liquid phase, the alloy elements can be hardly ensured to be fully mixed, so that the obtained magnesium alloy has certain component segregation; poor stability: the performance difference of different batches of alloys is large due to reasons such as burning loss in the alloy smelting process; fourthly, the environmental hazard is large: some metals, such as magnesium, do not form a dense oxide film at high temperatures to isolate the metal from oxygen, so that good protection measures must be taken during smelting, while SF is still used in large quantities today₆The protective gas of (2) can cause great threat to the environment; severe burnout: the oxidation burning loss of the active metal is serious in the heating and smelting process.

In order to solve the above problems, in recent years, attention has been paid to alloy preparation by a molten salt electrolysis method, in which a direct current is applied to a cathode to deposit an alloy or an alloy element in a halide (such as chloride or fluoride) molten salt system, thereby finally obtaining the alloy.

The molten salt electrolysis method for preparing the alloy comprises the following two methods:

one is an electrolytic diffusion process. This method uses a metal or alloy in a solid or liquid state as a cathode, on which other alloying elements are deposited and diffusion alloyed to obtain an alloy of the desired composition. When the method is used for electrolyzing the magnesium-aluminum alloy, liquid aluminum or liquid aluminum alloy is used as a cathode to electrolytically deposit active metal magnesium, and then diffusion alloying is carried out, wherein the aluminum or aluminum alloy cathode is prepared by another metallurgical process.

The other is an electrolytic co-deposition method. The method is to co-deposit and alloy ions of various alloying elements at a cathode. The electrolytic codeposition method has the following advantages: the process is short: each alloyed metal is not required to be prepared independently, and the whole production flow is short; good alloy uniformity: various alloy elements are mixed at an atomic level under the electrolysis condition, and the obtained alloy has good component uniformity; good alloy stability: the electrolysis process can realize automatic control, the electrolysis parameters can be accurately controlled, and the human interference factors are small, so that the stability of the product is good.

The problems of the smelting method are well solved by fused salt electrolysis codeposition, the cost is greatly reduced, the environment is protected, the energy is saved, and high-quality alloy is obtained.

The research on the electrolytic preparation of aluminum-containing alloys has received much attention, and most of them use anhydrous aluminum halide as an aluminum source. When the aluminum-containing alloy is prepared by electrolysis by taking anhydrous aluminum halide as an aluminum source, the anhydrous aluminum halide is added into a molten salt electrolyte by two methods: one is directly added by anhydrous aluminum halide powder; the other method is to add the anhydrous aluminum halide in a granular form after tabletting.

The method for preparing the aluminum-containing alloy by electrolyzing the aluminum halide powder without water or the aluminum halide tablet which is added into an electrolyte system in a granular form has the following problems:

(1) the anhydrous aluminum halide, especially the anhydrous aluminum chloride, is easy to sublimate and extremely volatile at the electrolysis temperature, so that the adding amount of an aluminum source cannot be determined according to the aluminum content of the aluminum-containing alloy, and the content of the aluminum element in the aluminum-containing alloy is difficult to control; in addition, since it is difficult to control the amount of aluminum actually entering the aluminum-containing alloy, the aluminum content of each aluminum-containing alloy is unstable although the aluminum source added to each batch is the same;

(2) the anhydrous aluminum halide, especially the anhydrous aluminum chloride, is very easy to absorb water to form aluminum halide with crystal water, and after the aluminum halide is added into an electrolyte, aluminum oxide is easily generated and deposited at the bottom of an electrolytic cell, is difficult to remove, and needs to be powered off to clearly remove the aluminum oxide at the bottom, so that the service life of the electrolytic cell is influenced.

The aluminum source for preparing the aluminum-containing alloy through electrolysis is required to be developed in the field, and the problems that aluminum contained in the aluminum-containing alloy cannot be controlled due to sublimation and water absorption, the aluminum contained in the aluminum-containing alloy is unstable in each batch of aluminum-containing alloy, and the service life of an electrolytic cell is short can be solved in the process of preparing the aluminum-containing alloy through electrolysis.

Disclosure of Invention

It is an object of the present invention to provide an aluminum source for the electrolytic preparation of aluminum-containing alloys comprising a double salt formed from an aluminum halide and an alkali metal halide.

The invention takes the double salt formed by the aluminum halide and the alkali metal halide as the aluminum source for preparing the aluminum-containing alloy by electrolysis, has stable components, is not inflammable, is not easy to explode and hydrolyze, has compact structure, large density and higher melting point, and brings the following advantages: firstly, in the air at normal temperature, the components and properties are stable, the material is not flammable or explosive, is not easy to generate violent chemical reaction, has low corrosivity and high safety; the aluminum source has compact structure, small specific surface area and difficult water absorption, can reduce the requirements on the storage condition and the transportation condition of the aluminum source, and can be stored for a longer time in the environment with the same water content compared with the aluminum source of aluminum halide; the density is large, the volume is small, the space for storage and transportation is small, and the storage, transportation and use are convenient; the water absorption is low, the water absorption is not easy, hydrolysis does not occur in the temperature rise process, the utilization rate of aluminum element in the aluminum source is improved, aluminum oxide introduced by aluminum halide hydrolysis is greatly reduced in the electrolysis process, and the reduction of the service life of the electrolytic cell caused by the generation of aluminum oxide precipitate by the hydrolysis of the aluminum oxide in the electrolysis process is relieved; the aluminum source provided by the invention is not easy to volatilize in the temperature rising process, the volatilization loss of the aluminum element is reduced, the utilization rate of the aluminum element in the aluminum source is improved, and in addition, the volatilization loss of the aluminum element is small, so the input stability of the aluminum element can be improved by adopting the aluminum source provided by the invention, and the content of the aluminum element in the aluminum-containing alloy is controlled to be stable; the aluminum source provided by the invention has lower saturated vapor pressure, the safety of the use environment is improved, and the corrosion and pollution to the environment caused by the aluminum halide serving as the aluminum source in the prior art are reduced.

Preferably, the molar ratio of aluminum element to alkali metal element in the double salt is 50 or less, exemplary such as 50, 49, 46, 45, 44, 41, 40, 39, 36, 35, 34, 31, 30, 29, 26, 25, 24, 21, 20, 19, 16, 15, 14, 11, 10, 9.0, 8.0, 7.9, 7.5, 7.4, 7.1, 7.0, 6.9, 6.5, 6.4, 6.1, 6.0, 5.9, 5.5, 5.4, 5.1, 5.0, 4.9, 4.5, 4.4, 4.1, 4.0, 3.9, 3.5, 3.4, 3.1, 3.0, 2.9, 2.5, 2.4, 2.1, 2.0, 1.9, 1.5, 1.4, 1.1, 1.0, 1.1, 1.4, 1.0, 0.0, 0.5, 0.0, 0, 0.0, 0.05, preferably 0, 0.0, 0, 0.05, more preferably 0, 0.0, 0, etc.

In the double salt, the molar ratio of the aluminum element to the alkali metal element is less than or equal to 50, when the molar ratio is between 0.2 and 25, the volatility and the water absorption of the obtained aluminum source are lower on the basis of ensuring the content of aluminum, when the molar ratio is between 0.5 and 10, the obtained aluminum source is more stable in the storage and transportation processes, and the components of the aluminum-containing alloy are more stable in the electrolysis process.

Preferably, the alkali metal comprises any 1 or combination of at least 2 of lithium, sodium, potassium, rubidium, cesium and francium.

Preferably, the halogen elements in the aluminum halide and the alkali metal halide are each independently selected from any 1 or a combination of at least 2 of chlorine, bromine and iodine.

Preferably, the aluminum halide comprises a combination of any 1 or at least 2 of aluminum chloride, aluminum bromide, and aluminum iodide;

preferably, the alkali metal halide comprises any 1 or a combination of at least 2 of lithium, sodium, potassium, rubidium, cesium, and francium halides; further preferably contains any 1 or a combination of at least 2 of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, lithium iodide, sodium iodide, potassium iodide, and rubidium iodide; particularly preferably lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide; still more preferably any 1 or a combination of at least 2 of sodium chloride, potassium chloride, sodium bromide, potassium bromide.

Preferably, the aluminum halides and alkali metal halides of the present invention have a water content of 5 wt.% or less, exemplary include 4.9 wt.%, 4.5 wt.%, 4.4 wt.%, 4.1 wt.%, 4.0 wt.%, 3.9 wt.%, 3.0 wt.%, 2.9 wt.%, 2.5 wt.%, 2.4 wt.%, 2.1 wt.%, 2.0 wt.%, 1.9 wt.%, 1.5 wt.%, 1.1 wt.%, 1.0 wt.%, 0.9 wt.%, 0.8 wt.%, 0.6 wt.%, 0.5 wt.%, 0.4 wt.%, 0.3 wt.%, 0.2 wt.%, 0.1 wt.%, 0.05 wt.%, 0.01 wt.%, preferably a water content of 2.5 wt.%, preferably a water content of 1.0 wt.%, preferably a water content of 0.5 wt.%, preferably a water content of 0.1 wt.% or less.

A second object of the present invention is to provide a method for the electrolytic preparation of an aluminium source containing an aluminium alloy according to the first object, said method comprising the steps of:

mixing an aluminum halide and an alkali metal halide to obtain a mixture, heating the mixture at least until a double salt is formed, and cooling to obtain an aluminum source.

In the present invention, "heating to form a double salt" means heating to any temperature at which a double salt can be formed, and "forming a double salt" includes forming a double salt from part or all of a single salt in the mixture.

Preferably, the method for preparing the aluminum source containing the aluminum alloy through electrolysis comprises the following steps:

mixing an aluminum halide and an alkali metal halide to obtain a mixture, heating the mixture at least until a liquid phase appears, and cooling to obtain an aluminum source; and (3) preserving the heat for 0-5 h after at least the temperature is raised to the liquid phase, such as 1min, 5min, 9min, 11min, 15min, 19min, 21min, 25min, 29min, 31min, 35min, 39min, 1.1h, 1.6h, 1.9h, 2.1h, 2.6h, 2.9h, 3.1h, 3.6h, 3.9h, 4.1h, 4.6h, 4.9h and the like, preferably preserving the heat for 10 min-2 h.

The expression "at least warming to the onset of a liquid phase" as used herein means heating the mixture to the onset of a liquid phase (temperature denoted T)₁) Then continuing heating and keeping the temperature at T₁Or continuing to heat to a temperature above T₁。

And at least raising the temperature until a liquid phase appears, and then preserving the temperature for a period of time, so that the content of the liquid phase can be further improved, the content of the double salt in the aluminum source can be increased, the hydrolysis and volatilization loss of the aluminum source in the electrolytic process can be reduced, and the actual adding amount of the aluminum source in the preparation process of the aluminum-containing alloy can be more easily controlled.

Those skilled in the art can obtain a massive solid after heating to form a double salt and cooling, and optionally granulating, such as ball milling, grinding and the like, so as to facilitate transportation, storage and transportation. The transportation and storage are preferably in a block form, the transportation and feeding can be granulated according to the size of a feeding hole, the size is not particularly limited, and the preferable particle size is less than or equal to 0.1m, and further preferably between 0.001 and 0.1 m.

Further preferably, the method for preparing the aluminum source containing the aluminum alloy through electrolysis comprises the following steps:

mixing aluminum halide and alkali metal halide to obtain a mixture, heating the mixture until the mixture completely becomes a liquid phase, and cooling to obtain an aluminum source; the temperature at which the mixture is heated to completely change into a liquid phase is preferably 0 to 50 ℃ higher than the temperature at which the mixture is heated to start to appear as a liquid phase, for example, 1 ℃, 5 ℃, 9 ℃, 11 ℃, 15 ℃, 19 ℃, 21 ℃, 25 ℃, 29 ℃, 31 ℃, 35 ℃, 39 ℃, 41 ℃, 45 ℃, 49 ℃ and the like, and more preferably 0 to 20 ℃.

Preferably, the maximum temperature of the temperature rise is 50 ℃ or higher, and exemplary ones include 51 ℃, 54 ℃, 55 ℃, 56 ℃, 59 ℃, 60 ℃, 61 ℃, 64 ℃, 65 ℃, 66 ℃, 69 ℃, 70 ℃, 71 ℃, 74 ℃, 75 ℃, 76 ℃, 79 ℃, 80 ℃, 81 ℃, 84 ℃, 85 ℃, 86 ℃, 89 ℃, 80 ℃, 91 ℃, 94 ℃, 95 ℃, 96 ℃, 99 ℃, 100 ℃, 101 ℃, 104 ℃, 105 ℃, 106 ℃, 109 ℃, 110 ℃, 111 ℃, 114 ℃, 115 ℃, 116 ℃, 119 ℃, 120 ℃, 121 ℃, 124 ℃, 125 ℃, 126 ℃, 129 ℃, 130 ℃, 131 ℃, 134 ℃, 135 ℃, 136 ℃, 139 ℃, 140 ℃, 151 ℃, 154 ℃, 155 ℃, 156 ℃, 159 ℃, 160 ℃, 161 ℃, 164 ℃, 165 ℃, 166 ℃, 169 ℃, 170 ℃, 171 ℃, 175 ℃, 176 ℃, 179 ℃, 180 ℃, 181 ℃, 184 ℃, 185 ℃, 186 ℃, 189 ℃, 190 ℃, 191 ℃, 194 ℃, 195 ℃, 196 ℃, 199 ℃, 200 ℃, 210 ℃, 220 ℃, 240 ℃, 250 ℃, 260 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 340 ℃, 350 ℃, 360 ℃, 390 ℃, 400 ℃, 450 ℃, 480 ℃, 530 ℃, 550 ℃, 660 ℃, 790 ℃ and the like, preferably 60 ℃ or more, more preferably 65 ℃ or more, further preferably between 70 ℃ and 400 ℃, and particularly preferably between 70 ℃ and 350 ℃.

Preferably, the minimum cooling temperature is 200 ℃ or less, and exemplary ones are 199 ℃, 195 ℃, 194 ℃, 191 ℃, 190 ℃, 189 ℃, 185 ℃, 184 ℃, 181 ℃, 180 ℃, 179 ℃, 175 ℃, 174 ℃, 171 ℃, 170 ℃, 169 ℃, 165 ℃, 164 ℃, 161 ℃, 160 ℃, 159 ℃, 155 ℃, 154 ℃, 151 ℃, 150 ℃, 149 ℃, 145 ℃, 144 ℃, 141 ℃, 140 ℃, 139 ℃, 135 ℃, 134 ℃, 131 ℃, 130 ℃, 129 ℃, 125 ℃, 124 ℃, 121 ℃, 120 ℃, 119 ℃, 115 ℃, 114 ℃, 111 ℃, 110 ℃, 109 ℃, 105 ℃, 104 ℃, 101 ℃, 100 ℃, 99 ℃, 95 ℃, 94 ℃, 91 ℃, 90 ℃, 89 ℃, 85 ℃, 84 ℃, 81 ℃, 80 ℃, 79 ℃, 75 ℃, 74 ℃, 71 ℃, 70 ℃, 69 ℃, 65 ℃, 64 ℃, 61 ℃, 60 ℃, 59 ℃, 55 ℃, 54 ℃, 51 ℃, 50 ℃, 49 ℃, 45 ℃, 44 ℃. (see, 41 ℃, 40 ℃, 39 ℃, 35 ℃, 34 ℃, 31 ℃, 30 ℃, 29 ℃, 25 ℃, 24 ℃, 21 ℃, 0 ℃, preferably below 160 ℃, more preferably below 100 ℃, more preferably below 50 ℃.

Preferably, the molar ratio of the aluminum halide to the alkali metal halide in the mixture is 50 or less, exemplary such as 50, 49, 46, 45, 44, 41, 40, 39, 36, 35, 34, 31, 30, 29, 26, 25, 24, 21, 20, 19, 16, 15, 14, 11, 10, 9.0, 8.0, 7.9, 7.5, 7.4, 7.1, 7.0, 6.9, 6.5, 6.4, 6.1, 6.0, 5.9, 5.5, 5.4, 5.1, 5.0, 4.9, 4.5, 4.4, 4.1, 4.0, 3.9, 3.5, 3.4, 3.1, 3.0, 2.9, 2.5, 2.4, 2.1, 2.0, 1.9, 1.5, 1.0, 0, 0.05, 0, 0.0, 0, 0.05, preferably 0, 0.0, 0, 0.05, and more preferably 0.

The third purpose of the invention is to provide a method for preparing an aluminum-containing alloy by electrolysis, wherein the source of aluminum element in the aluminum-containing alloy comprises an aluminum source described in one purpose.

The aluminum source provided by the invention can reduce volatilization and hydrolysis of the aluminum source, improve the conversion rate of the aluminum element in the aluminum source, improve the stability of the content of the aluminum element in the aluminum-containing alloy, reduce the pollution to the environment caused by volatilization of the aluminum source in the preparation process of the aluminum-containing alloy, solve the problem that the service life of an electrolytic cell is shortened because aluminum halide aluminum source absorbs water to form alumina, and the alumina precipitates are formed by hydrolysis in high-temperature electrolyte, and prolong the service life of the electrolytic cell; the temperature of the aluminum source which is changed into the liquid phase in the electrolyte is lower than the sublimation point or the melting point of the aluminum halide, so that the homogenization time can be shortened, the aluminum source can rapidly participate in electrolysis after entering the liquid phase, and the time required by the process for producing the same aluminum-containing alloy material is shortened.

The present invention is not particularly limited to the method for electrolytically producing an aluminum-containing alloy, and the aluminum source provided by the present invention can be used as any method for electrolytically producing an aluminum-containing alloy, for example, the aluminum source is added to a liquid electrolyte of an electrolyte and other alloy sources, or the aluminum source and other alloy sources are added to a liquid electrolyte, or the aluminum source is continuously added to an electrolyte in the form of particles under a conveyor belt, or the aluminum source is intermittently added to an electrolyte in the form of particles in batches, and the like.

In an alternative technical scheme, the method for preparing the aluminum-containing alloy through electrolysis comprises the following steps:

electrolyzing the aluminum source and the alloy element source in the electrolyte to obtain liquid aluminum-containing alloy, and cooling the liquid aluminum-containing alloy to obtain aluminum-containing alloy solid.

In the technical scheme, the aluminum source is added at one time, so that the volatilization amount of the aluminum source is small, the conversion rate of the aluminum element in the aluminum source is high, stable and controllable, the influence of the volatilization of the aluminum source on the instability of the content of the aluminum element in the aluminum-containing alloy is reduced, the production of the aluminum-containing alloy with stable aluminum content can be ensured under the same aluminum source and electrolysis conditions, and the pollution to the environment is reduced.

In the prior art, aluminum halide is used as an aluminum source, the volatilization amount of the aluminum halide is not controlled, the water absorption amount is not controlled, and the hydrolysate aluminum oxide after water absorption can not participate in electrolysis, so that the problems that the content of aluminum in aluminum-containing alloy is not controlled, the aluminum waste is serious, the service life of an electrolytic cell is influenced by the aluminum oxide, and the like are caused. In view of the problems of the prior art, the aluminum source provided by the invention can be effectively used.

Preferably, the method for electrolytically producing an aluminum-containing alloy is carried out under an inert gas.

The electrolysis is carried out under the inert gas, so that the anode gas generated by the electrolysis can be discharged in time, the concentration of the anode gas in the electrolyte is reduced, and the secondary reaction of the generated alloy and the anode gas is reduced; in addition, the protection of the inert gas can also prevent water vapor from entering the electrolytic cell, so that the hydroscopic electrolyte is prevented from being hydrolyzed at high temperature; the protective gas can also prevent the entry of oxidizing gas, avoid the oxidation of aluminum alloy containing aluminum during electrolysis, not only improve the metal yield, but also prevent the deterioration of an electrolytic system caused by metal oxide obtained by hydrolysis and oxidation, and prolong the service life of the electrolytic cell.

The inert gas illustratively includes one or more of an inert gas comprising any 1 or a combination of at least 2 of argon, helium, and nitrogen.

Preferably, the aluminum source and the non-aluminum alloy element source are continuously added, or the aluminum source and the non-aluminum alloy element source are added at one time, or the aluminum source and the non-aluminum alloy element source are added in multiple batches.

The continuous addition means that the aluminum source or the non-aluminum metal element source (metal element source except aluminum in the target aluminum-containing alloy) provided by the invention is continuously added into the electrolyte for electrolysis through a conveying device (such as a conveyor belt and the like), and the adding rate can be adjusted to control the content of the metal element in the electrolyte, so that the controllability of the proportion of the metal element in the aluminum-containing alloy is realized. It will also be appreciated by those skilled in the art that the alkali metal halide is introduced when the aluminum source is continuously added, but the amount of the alkali metal halide introduced can be controlled to selectively remove the electrolyte to stabilize the contents of the electrolyte, aluminum and metal elements during electrolysis in order to stabilize the contents of the elements in the aluminum-containing alloy.

The term "adding at one time" in the invention means that the aluminum source and the non-aluminum metal element source provided by the invention are added into the electrolyte at one time for electrolysis. In this way, in the case of excessive aluminum element initially, the proportion of the elements in the aluminum-containing alloy is stable, but as the aluminum source is consumed, the content of the aluminum element in the aluminum-containing alloy is reduced, but one skilled in the art can choose to stop the electrolysis before the aluminum element is not excessive, and ensure that the aluminum element is excessive all the time, so as to ensure that the content of the elements in the aluminum-containing alloy is stable.

The term "multi-batch addition" as used herein means that the aluminum source and the non-aluminum metal element source provided by the present invention are added to the electrolyte in batches in any manner available to those skilled in the art, and similar to the manner of "one-shot addition", in order to obtain a stable proportion of aluminum-containing alloy, the aluminum source needs to be added before the aluminum-containing alloy is not in excess, so as to ensure that the content of aluminum element in the electrolyte is in excess.

The addition time points of the aluminum source and the non-aluminum alloy element source are not limited in the invention.

Preferably, the aluminum source and the non-aluminum alloy element source are respectively and independently selected to be added at the same time of electrifying electrolysis or added when power is cut off.

Preferably, the temperature of the electrolysis is 350-1000 deg.C, such as 350 deg.C, 356 deg.C, 359 deg.C, 365 deg.C, 370 deg.C, 380 deg.C, 391 deg.C, 399 deg.C, 409 deg.C, 421 deg.C, 430 deg.C, 440 deg.C, 450 deg.C, 460 deg.C, 471 deg.C, 480 deg.C, 499 deg.C, 505 deg.C, 521 deg.C, 530 deg.C, 540 deg.C, 550 deg.C, 571 deg.C, 580 deg.C, 599 deg.C, 609 deg.C, 621 deg.C, 630 deg.C, 640 deg.C, 650 deg.C, 660 deg.C, 671 deg.C, 699 deg.C, 709 deg.C, 721 deg.C, 730 deg.C, 740 deg.C, 750 deg.C, 760 deg.C, 771.

Preferably, the cathodic voltage for electrolysis is lower than the precipitation potential of all metal elements in the aluminum-containing alloy, preferably lower by at least 0.2V, such as 0.3V, 0.4V, 0.5V, 0.6V, 0.8V, 0.9V, 1.3V, 1.5V, 1.8V, 2.3V, 2.5V, 2.8V, 3.3V, 3.5V, 3.8V, etc., preferably 0.2 to 2V.

Illustratively, the voltage of the electrolysis may be: when the anodic voltage is 0V and the minimum precipitation potential of the metal element in the aluminum-containing alloy is 5V, the cathodic voltage needs to be set to-5V or less, for example, -6V, -7V, -8V, etc.

As an alternative example, the voltage of the electrolysis of the present invention is 1 to 10V, and exemplified by 1.3V, 1.4V, 1.5V, 1.6V, 1.9V, 2.0V, 2.1V, 2.4V, 2.5V, 2.6V, 2.9V, 3.0V, 3.1V, 3.4V, 3.5V, 3.6V, 3.9V, 4.0V, 4.1V, 4.4V, 4.5V, 4.6V, 4.9V, 5.0V, 5.1V, 5.4V, 5.5V, 5.6V, 5.9V, 6.0V, 6.1V, 6.4V, 6.5V, 6.6V, 6.9V, 7.0V, 7.1V, 7.4V, 7.5V, 7.6V, 7.9V, 7.0V, 7.1V, 8.9V, 9.9V, 9V, 9.0V, 9V, 9.9V, 9V, 8.9V, 9V, 8.6V, 9V, 8.6V, 8.1V, 9V, 8.6V, 9V, 6V.

The voltage of the electrolysis can be understood as the absolute value of the voltage difference between the cathode and the anode.

Preferably, the anode of the electrolysis is a graphite electrode.

Preferably, the cathode of the electrolysis comprises a simple substance or an alloy formed by any 1 or at least 2 of carbon element and metal element; the electrolytic cathode may be present in a liquid or solid state.

Further preferably, the cathode comprises any 1 or combination of at least 2 of steel, molybdenum, tungsten, titanium and graphite.

Preferably, the electrolyte for electrowinning comprises any 1 or a combination of at least 2 of alkali metal halides and alkaline earth metal halides.

Preferably, the alkaline earth metal halide comprises any 1 or combination of at least 2 of beryllium halide, magnesium halide, calcium halide, strontium halide, barium halide, and radium halide; further preferably contains any 1 or a combination of at least 2 of beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, beryllium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, beryllium iodide, magnesium iodide, calcium iodide, strontium iodide, and barium iodide; particularly preferably include beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, beryllium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide; still more preferably any 1 or a combination of at least 2 of magnesium chloride, calcium chloride, strontium chloride, barium chloride.

Preferably, the non-aluminum alloy element includes any 1 or a combination of at least 2 of main group metal elements, transition metal elements, and nonmetal elements; preferably any 1 or a combination of at least 2 of lithium, beryllium, magnesium, calcium, strontium, boron, gallium, indium, carbon, silicon, germanium, tin, lead, nitrogen, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, uranium, thorium, and the like; further preferably any 1 or a combination of at least 2 of lithium, beryllium, magnesium, calcium, strontium, boron, gallium, indium, silicon, germanium, tin, lead, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, hafnium, tantalum, tungsten, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, uranium, thorium, ytterbium and lutetium; particularly preferably any 1 or a combination of at least 2 of lithium, beryllium, boron, magnesium, silicon, titanium, vanadium, manganese, iron, zinc, yttrium, zirconium, lanthanum, cerium, praseodymium, samarium, europium, gadolinium, erbium, ytterbium and silicon;

preferably, the non-aluminum alloy element source includes a combination of any 1 or at least 2 of the non-aluminum alloy element compounds, further preferably an oxide of the non-aluminum alloy element and/or a chloride of the non-aluminum alloy element.

The fourth purpose of the invention is to provide an aluminum-containing alloy which is prepared by the method for preparing the aluminum-containing alloy by electrolysis in the third purpose.

The aluminum-containing alloy prepared by the method has stable and controllable element content, does not need to be smelted for the second time, and can be directly forged and formed to obtain an aluminum-containing alloy part.

The fifth purpose of the invention is to provide a preparation method of an aluminum alloy-containing product, which comprises the following steps:

electrolyzing the aluminum source in an electrolyte containing one of the purposes and an alloying element source by electrifying to obtain a liquid aluminum-containing alloy, and then cooling the liquid aluminum-containing alloy in a mold to obtain an aluminum alloy-containing product;

preferably, in the preparation method of the aluminum alloy-containing product, the conditions of the process steps are the same as the third objective, and the specific conditions are as follows:

in an alternative embodiment, the method for electrolytically producing an aluminum alloy-containing article comprises:

electrolyzing the aluminum source and the alloy element source in an electrolyte to obtain a liquid aluminum-containing alloy, and cooling the liquid aluminum-containing alloy in a mold to obtain an aluminum alloy-containing product.

The aluminum alloy-containing product can be directly prepared into liquid aluminum alloy through an electrolytic aluminum source and a non-aluminum alloy element source, and the aluminum alloy-containing product can be prepared through cooling in a die without secondary smelting, so that the energy is saved, the environment is protected, the burning loss of the aluminum alloy-containing product in the secondary smelting process is reduced, and most importantly, the element content of the aluminum alloy-containing product can be stabilized on the premise of omitting the secondary smelting.

The stabilization of the elemental content of the aluminum alloy-containing article includes the following meanings:

in the process of continuously adding aluminum sources and non-aluminum metal element sources, the element proportion of aluminum-containing alloy materials, aluminum-containing alloy products or workpieces obtained in each time period is the same;

in the process of adding the aluminum source and the non-aluminum alloy element source at one time, each time the element source is added, the power needs to be cut off after the electrolysis is finished, and the aluminum source and the non-aluminum alloy element source of the next batch are added at one time, wherein the element proportion of the aluminum-containing alloy material, the aluminum-containing alloy product or the workpiece obtained from each batch is the same;

thirdly, in the process of adding aluminum sources and non-aluminum alloy element sources in multiple batches, the continuously produced aluminum-containing alloy materials, aluminum-containing alloy products or workpieces have the same element proportion.

The inert gas illustratively includes any 1 or a combination of at least 2 of argon, helium, and nitrogen.

Preferably, the anode of the electrolysis is a graphite electrode.

Compared with the prior art, the invention has the following beneficial effects:

(1) the aluminum source for preparing the aluminum-containing alloy by electrolysis provided by the invention has the advantages that the aluminum halide and the alkali metal halide are double-salted, the problems that the aluminum halide is easy to absorb water at normal temperature and sublimate at high temperature, and the actual adding amount of the aluminum source is difficult to control are solved, the harm to the environment caused by sublimation of the aluminum source of the aluminum halide is solved, the problem that the aluminum source of the aluminum halide absorbs water to generate aluminum hydroxide precipitate is solved, the slag discharge period of an electrolytic cell is prolonged, and the service life of the electrolytic cell is prolonged;

(2) the preparation method of the aluminum source provided by the invention is simple, the operation condition is loose, the double salt can be formed in a wider temperature range, and the aluminum source can be further granulated, so that the use of the aluminum source is convenient;

(3) the preparation method of the aluminum-containing alloy provided by the invention adopts the aluminum source provided by the invention, the content of the aluminum element entering the electrolyte can be controlled, the controllability of the element proportion of the aluminum-containing alloy is further realized, the stability of the element proportion of aluminum-containing alloys in different batches is realized, and the secondary melting of aluminum-containing alloy materials during workpiece preparation is omitted; in addition, the aluminum source provided by the invention can reduce the sublimation of aluminum element and reduce the environmental hazard;

(4) the aluminum alloy of the aluminum-containing alloy product provided by the invention has stable element proportion, does not need to carry out secondary melting on the aluminum-containing alloy material, omits the process, saves the energy and reduces the burning loss of the secondary melting.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Preparation example 1

An aluminum source for the electrolytic production of aluminum-containing alloys, prepared by the process of:

mixing anhydrous AlCl with water content of 0.5%₃12.1mol and 0.5mol of NaCl with the water content of 1.5 percent to obtain an aluminum-containing mixture, heating the aluminum-containing mixture to 105 ℃, preserving the temperature for 30min, and cooling to room temperature to obtain a No. 1 aluminum source. The molar ratio of the aluminum element to the sodium element in the No. 1 aluminum source is 24.0.

Preparation example 2

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the preparation example 1 in that the aluminum-containing mixture is heated to 108.7 ℃, liquid begins to appear, heat preservation is not carried out, and then the aluminum source is cooled to room temperature to obtain a # 2 aluminum source. The molar ratio of the aluminum element to the sodium element in the 2# aluminum source is 24.0.

Preparation example 3

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the preparation example 1 in that the aluminum-containing mixture is heated to 108.7 ℃, kept for 2min and then cooled to room temperature to obtain a 3# aluminum source. The molar ratio of the aluminum element to the sodium element in the 3# aluminum source is 24.0.

Preparation example 4

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the preparation example 1 in that the aluminum-containing mixture is heated to 108.7 ℃, kept for 30min and then cooled to room temperature to obtain a # 4 aluminum source. The molar ratio of the aluminum element to the sodium element in the No. 4 aluminum source is 24.0.

Preparation example 5

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the preparation example 1 in that the aluminum-containing mixture is heated to 108.7 ℃, kept for 60min and then cooled to room temperature to obtain a 5# aluminum source. The molar ratio of the aluminum element to the sodium element in the 5# aluminum source is 24.0.

Preparation example 6

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the preparation example 1 in that the aluminum-containing mixture is heated to 108.7 ℃, kept for 120min and then cooled to room temperature to obtain a 6# aluminum source. The molar ratio of the aluminum element to the sodium element in the 6# aluminum source is 24.0.

Preparation example 7

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the preparation example 1 in that the aluminum-containing mixture is heated to 108.7 ℃, kept for 180min and then cooled to room temperature to obtain a 7# aluminum source. The molar ratio of the aluminum element to the sodium element in the 7# aluminum source is 24.0.

Preparation example 8

An aluminum source for electrolytically preparing an aluminum-containing alloy is different from the preparation example 1 in that the aluminum-containing mixture is heated to 109 ℃ and then cooled to room temperature to obtain an 8# aluminum source. The molar ratio of the aluminum element to the sodium element in the 8# aluminum source is 24.0.

Preparation example 9

An aluminum source for electrolytically preparing an aluminum-containing alloy is different from the preparation example 1 in that the aluminum-containing mixture is heated to 150 ℃ and then cooled to room temperature to obtain a 9# aluminum source. The molar ratio of the aluminum element to the sodium element in the 9# aluminum source is 24.0.

Preparation example 10

An aluminum source for electrolytically preparing an aluminum-containing alloy is different from the preparation example 1 in that the aluminum-containing mixture is heated to 190 ℃ and then cooled to room temperature to obtain a 9# aluminum source. The molar ratio of the aluminum element to the sodium element in the 9# aluminum source is 24.0.

Preparation example 11

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the aluminum source prepared in the preparation example 6 in that AlCl is contained in the aluminum-containing mixture₃The content of (2) is 0.3mol, and the content of NaCl is 0.7mol, thus obtaining a10 # aluminum source. The molar ratio of the aluminum element to the sodium element in the 10# aluminum source is 0.43.

Preparation example 12

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the aluminum source prepared in the preparation example 6 in that AlCl is contained in the aluminum-containing mixture₃The content of (3) was 0.4mol, and the content of NaCl was 0.6mol, to obtain an aluminum source # 11. The molar ratio of the aluminum element to the sodium element in the 11# aluminum source is 0.66.

Preparation example 13

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the aluminum source prepared in the preparation example 6 in that AlCl is contained in the aluminum-containing mixture₃The content of (2) is 5mol, and the content of NaCl is 0.1mol, thus obtaining a12 # aluminum source. The molar ratio of the aluminum element to the sodium element in the 12# aluminum source is 50.

Preparation example 14

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the aluminum source prepared in the preparation example 6 in that AlCl is contained in the aluminum-containing mixture₃The content of (1) and the content of NaCl is 0.1mol, and a12 # aluminum source is obtained. The molar ratio of the aluminum element to the sodium element in the 12# aluminum source is 10.

Preparation example 15

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the aluminum source prepared in the preparation example 6 in that AlCl is contained in the aluminum-containing mixture₃The content of (3) is 0.8mol, and the content of NaCl is 0.1mol, thus obtaining a12 # aluminum source. The molar ratio of the aluminum element to the sodium element in the 12# aluminum source is 8.

Preparation example 16

An aluminum source for preparing aluminum-containing alloy through electrolysis is different from the aluminum source prepared in the preparation example 6 in that AlCl is contained in the aluminum-containing mixture₃The content of (2) is 0.6mol, and the content of NaCl is 0.1mol, thus obtaining a12 # aluminum source. The molar ratio of the aluminum element to the sodium element in the 12# aluminum source is 6.

Preparation example 17

mixing anhydrous AlCl with water content of 1.5%₃3.0mol and KCl with the water content of 2.5% 0.29mol to obtain a mixture, heating the obtained mixture to 170 ℃, and cooling to room temperature to obtain a13 # aluminum source. The molar ratio of the aluminum element to the potassium element in the No. 13 aluminum source is 10.

Preparation example 18

mixing anhydrous AlCl with water content of 0.6%₃4.0mol and RbCl 0.19mol with the water content of 4.8 percent to obtain a mixture, heating the obtained mixture to 110 ℃, and cooling to 20 ℃ to obtain a14 # aluminum source. The molar ratio of the aluminum element to the rubidium element in the No. 14 aluminum source is 21.

Preparation example 19

mixing anhydrous AlCl with water content of 3.1%₃4.0mol and 0.15mol of CsCl with the water content of 2.5 percent to obtain a mixture, heating the obtained mixture to 120 ℃, and cooling the mixture to 21 ℃ to obtain a15 # aluminum source. The molar ratio of the aluminum element to the cesium element in the No. 15 aluminum source is 26.

Preparation example 20

mixing anhydrous AlBr with water content of 0.2%₃1.0mol and 0.2mol of KBr with the water content of 1.5 percent to obtain a mixture, heating the obtained mixture to 99 ℃, and cooling to 60 ℃ to obtain a16 # aluminum source. The molar ratio of the aluminum element to the potassium element in the 16# aluminum source is 4.9.

Preparation example 21

mixing anhydrous AlI with water content of 0.5%₃1.0mol and 0.5mol of NaI with the water content of 0.5 percent to obtain a mixture, heating the obtained mixture to 290 ℃, and cooling to 60 ℃ to obtain a 17# aluminum source. The molar ratio of the aluminum element to the sodium element in the 17# aluminum source is 1.9.

The water content of the alkali metal chloride and the alkaline earth metal chloride used as the electrolytes in the following examples was less than 0.1%, and the water content of the compounds as the sources of the non-aluminum alloy elements was less than 0.1%.

Example A1 to example A21

An aluminum-containing alloy is prepared by the following method:

(1) 47.0g of BaCl₂94.0g of KCl and 109.0g of NaCl, and heating to 680 ℃ to obtain an electrolyte liquid phase;

(2) adding corresponding aluminum sources of 1# to 21# into an electrolyte liquid phase in the step (1), wherein the theoretical amount of aluminum element in the added aluminum sources is 2.0g (the 1# aluminum source is example A1, the 2# aluminum source is example A2, the 3# aluminum source is example A3, the 4# aluminum source is example A4, the 5# aluminum source is example A5, the 6# aluminum source is example A6, the 7# aluminum source is example A7, the 8# aluminum source is example A8, the 9# aluminum source is example A9, the 10# aluminum source is example A10, the 11# aluminum source is example A11, the 12# aluminum source is example A12, the 13# aluminum source is example A13, the 14# aluminum source is example A14, the 15# aluminum source is example A15, the 16# aluminum source is example A16, the 17# is example 17, the 18# aluminum source is example 18, the aluminum source # 19, the # 20 is example # 20); the theoretical amount of the aluminum element in the aluminum source is the amount of the aluminum element in aluminum chloride added in the process of preparing the aluminum source;

(3) adding anhydrous MgCl₂62.5g as magnesium source;

(4) under the protection of argon atmosphere, a graphite rod is used as an anode, a steel rod is used as a cathode, electrolysis is carried out for 3 hours under the constant current condition of 4A (the voltage difference between the cathode and the anode can be ensured to be more than 6V), power is cut off, and liquid-phase aluminum-magnesium-containing alloy is generated at the cathode;

(5) and cooling the liquid-phase aluminum-magnesium-containing alloy to room temperature to obtain a solid aluminum-magnesium-containing alloy.

Comparative example A

The only difference from the group of examples A is that the aluminium source was replaced by anhydrous aluminium chloride, again in such an amount that the theoretical amount of aluminium element added was 2 g.

The theoretical amount of the aluminum element is the amount of the aluminum element in the aluminum chloride added in the process of preparing the aluminum source.

The results of the aluminum content in the alloy are shown in table 1:

TABLE 1

As can be seen from table 1, under the condition that the theoretical amount (2g) of the added aluminum element is the same, the content of the aluminum element in the prepared aluminum-containing alloy is different, and particularly, compared with the comparative example, the content of the aluminum element is obviously increased, so that the utilization rate of the aluminum source can be effectively increased by using the aluminum source of the present invention.

Example B1 to example B16

Storing the 1# to 16# aluminum source for 1 hour at room temperature under 20% humidity, and then repeating the following steps for 10 times by using the stored aluminum source to obtain 10 batches of aluminum-magnesium-containing alloy:

in the step (4) of one of examples A1 to A21, after 3 hours of electrolysis at a constant current of 4A, the electrolyte composition was adjusted to return to the state before electrolysis, and the same amount of aluminum source as that in the B group experiment was added again to perform electrolysis, thereby regenerating a liquid-phase aluminum-magnesium-containing alloy at the cathode; cooling the liquid-phase aluminum-magnesium-containing alloy to room temperature to obtain a solid aluminum-lithium-containing alloy, recording the aluminum content in each batch of aluminum-lithium-containing alloy, and calculating the standard deviation of the aluminum content and the utilization rate of aluminum elements, wherein the test results are shown in table 2:

wherein N is 10 times of repetition, X_iThe amount of aluminum in each batch of alloy is,

is the average value of the aluminum content in 10 batches of alloy;

comparative example B1

The procedure of group B example was repeated using the stored aluminum source as the aluminum source after storing anhydrous aluminum chloride at room temperature under 20% humidity for 1 hour, and the stored aluminum source was substituted by the aluminum source in comparative example a in equal mass.

Comparative example B2

The procedure of group B examples was repeated using anhydrous aluminum chloride as the aluminum source.

TABLE 2

As can be seen from Table 2, the aluminum source provided by the invention is stable in storage and cannot be influenced by humidity and temperature, and the anhydrous aluminum chloride can cause the content of aluminum in the prepared aluminum-containing alloy to be reduced and the storage cost to be increased when being stored at normal temperature; the selection of the preparation temperature and time of the aluminum source provided by the invention is more beneficial to obtaining stable content of aluminum element in the aluminum-containing alloy.

Examples C1 to C16X 1 is the mass of the aluminum halide component used to prepare the aluminum source added to the electrolytic cell, i.e. the aluminum element in the added aluminum source is converted to the mass of the aluminum halide, and X2 is the mass of the alkali metal halide component used to prepare the aluminum source added to the electrolytic cell.

Example C1 to example C16

An aluminum-containing alloy is prepared by the following method:

(1) mixing 300.0g of KCl and 200.0g of NaCl, and heating to 700 ℃ to obtain an electrolyte;

(2) graphite plate is used as anode, tungsten plate is used as cathode (S is 7.5cm ═²) Adding 6A constant current for electrolysis to maintain the potential difference between the two electrodes above 6V;

(3) crushing 1# to 12# aluminum sources into particles, continuously adding the obtained 1# to 12# aluminum sources (the mass of an aluminum halide component for preparing the aluminum sources is specified to be X1, and the mass of an alkali metal halide component is specified to be X2) into an electrolyte at the speed of X1 being 1.27g/h, and simultaneously adding anhydrous MgCl₂And KCl at 9.19g/h and

is continuously added to the electrolyte at the same time as

Outputting electrolyte at a speed to ensure the content of KCl and NaCl components in the electrolyte to be stable; (example # 1 aluminum source is example C1, example # 2 aluminum source is example C2, example # 3 aluminum source is example C3, example # 4 aluminum source is example C4, example # 5 aluminum source is example C5, example # 6 aluminum source is example C6, example # 7 aluminum source is example C7, example # 8 aluminum source is example C8, example # 9 aluminum source is example C9, example # 10 aluminum source is example C10, example # 11 aluminum source is example C11, and example # 12 aluminum source is example C12);

(4) and continuously generating liquid-phase magnesium-aluminum alloy at the cathode of the electrolytic cell, taking out the liquid-phase magnesium-aluminum alloy, and cooling to room temperature to obtain the solid aluminum-magnesium-containing alloy.

Comparative example C

The amount of aluminum element such as aluminum source in group C examples was replaced with anhydrous aluminum chloride.

After 5h, 10h, 15h, 20h, 25h and 30h of production, the prepared aluminum-magnesium-containing alloy is detected, the content of aluminum element in the alloy is tested, the utilization rate of the aluminum element and the standard deviation of the content of the aluminum element are calculated in the following way, and the test results are shown in table 2:

wherein, the number of times of taking the alloy sample is 6 for N1, and X is_jFor the aluminum content in each sample of the alloy,

the average value of the aluminum content in the 6 times of alloy samples.

TABLE 3

As can be seen from table 3, the aluminum source provided by the present invention can stably exist at room temperature and does not absorb water, so that continuous production of aluminum-containing alloys can be achieved, and as for anhydrous aluminum chloride, due to severe water absorption at room temperature, with continuous production, part of aluminum chloride exposed in the air is converted into aluminum oxide due to increased water absorption, so that the aluminum chloride cannot be electrolyzed into aluminum-containing alloys.

Example 2

An aluminum-containing alloy is prepared by the following method:

(1) 200.0g LiCl and 100.0g KCl were mixed with Er source₂O₃3.0g, heating to 700 ℃ to obtain an electrolyte liquid phase;

(2) adding a No. 15 aluminum source into the electrolyte liquid phase in the step (1) to ensure that the mass X1 of an aluminum chloride component for preparing the aluminum source is 10.0 g;

(3) graphite rod is used as anode, molybdenum rod is used as cathode, under 2A constant current (current density 6.37A/cm)²) Electrolyzing for 2h to ensure that the voltage between the two electrodes is more than 7V, and generating a liquid-phase aluminum-lithium-erbium-containing alloy at the cathode;

(4) and cooling the liquid-phase aluminum-lithium-erbium-containing alloy to room temperature to obtain a solid-state aluminum-lithium-erbium-containing alloy, wherein the aluminum content is 20.01%, and the conversion rate of aluminum element is 30.21%.

Example 3

An aluminum-containing alloy is prepared by the following method:

(1) mix 70.0g KCl, 200.0g NaCl, and anhydrous MgCl, a source of magnesium₂30.0g and anhydrous ZnCl as zinc source₂1.0g, heating to 700 ℃ to obtain an electrolyte liquid phase;

(2) an aluminum source # 16 was added to the electrolyte, wherein the aluminum bromide component from which this source was prepared had a mass X1 of 20.0 g. The graphite rod is used as an anode, the graphite rod is used as a cathode, and the constant current (the current density is 0.67A/cm) at 4A is adopted²) And (5) electrolyzing for 3 hours. The voltage difference between the positive and negative two stages is ensured to be more than 5V during electrolysis, and liquid-phase aluminum-containing magnesium-zinc alloy is generated at the cathode;

(3) cooling the liquid-phase aluminum-containing magnesium-zinc alloy to room temperature to obtain a solid aluminum-containing magnesium-zinc alloy, wherein the aluminum content is 12.48 percent, and the conversion rate of aluminum element is 34.02 percent

Example 4

An aluminum-containing alloy is prepared by the following method:

(1) 100.0g LiCl and 100.0g KCl were mixed with erbium source Y₂O₃2.0g, heating to 650 ℃ to obtain an electrolyte liquid phase;

(2) adding a 17# aluminum source to the electrolyte liquid phase of the step (1) so that the mass X1 of the aluminum iodide component in which the aluminum source is prepared is 25.0 g;

(3) graphite rod is used as anode, tungsten rod is used as cathode, and under the constant current of 2A (S is 0.322 cm)²) Electrolyzing for 2h to ensure that the voltage between the two electrodes is more than 7V, and generating a liquid-phase aluminum-lithium-yttrium-containing alloy at the cathode;

(4) and cooling the liquid-phase aluminum-lithium-erbium-containing alloy to room temperature to obtain a solid-state aluminum-lithium-erbium-containing alloy, wherein the aluminum content is 25.71%, and the conversion rate of aluminum element is 40.13%.

The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims

1. A method for electrolytically preparing an aluminium-containing alloy, wherein the aluminium source in the aluminium-containing alloy in the method comprises a double salt formed from an aluminium halide and an alkali metal halide;

the method comprises the following steps: electrifying and electrolyzing in an electrolyte containing the aluminum source and a non-aluminum alloy element source to obtain a liquid aluminum-containing alloy, and then cooling the liquid aluminum-containing alloy to obtain an aluminum-containing alloy solid;

the temperature of the electrification electrolysis is 350-1000 ℃;

the non-aluminum alloy elements include any 1 or a combination of at least 2 of lithium, magnesium, or erbium.

2. The method of claim 1 wherein the aluminum source has a molar ratio of aluminum element to alkali metal element of 50 or less.

3. The method of claim 2 wherein the aluminum source has a molar ratio of aluminum element to alkali metal element of 25 or less.

4. The method of claim 3 wherein the aluminum source has a molar ratio of aluminum element to alkali metal element of 10 or less.

5. The method of claim 4 wherein the aluminum source has a molar ratio of aluminum element to alkali metal element of 8 or less.

6. The method of claim 5 wherein the aluminum source has a molar ratio of aluminum element to alkali metal element of 6 or less.

7. The method of claim 1, wherein the alkali metal comprises any 1 or a combination of at least 2 of lithium, sodium, potassium, rubidium, cesium, and francium.

8. The method of claim 1, wherein the halogen elements of the aluminum halide and the alkali metal halide are each independently selected from any 1 or a combination of at least 2 of chlorine, bromine, and iodine.

9. The method of claim 1, wherein the aluminum halide is an anhydrous aluminum halide.

10. The method of claim 9, wherein the aluminum halide is any 1 or a combination of at least 2 of aluminum chloride, aluminum bromide, and aluminum iodide.

11. The method of claim 1, wherein the alkali metal halide comprises any 1 or a combination of at least 2 of lithium halide, sodium halide, potassium halide, rubidium halide, cesium halide, and francium halide.

12. The method of claim 11, wherein the alkali metal halide comprises any 1 or a combination of at least 2 of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, lithium iodide, sodium iodide, potassium iodide, and rubidium iodide.

13. The method of claim 12, wherein the alkali metal halide comprises any 1 or a combination of at least 2 of lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide.

14. The method of claim 13, wherein the alkali metal halide is any 1 or a combination of at least 2 of sodium chloride, potassium chloride, sodium bromide, and potassium bromide.

15. The method of claim 1, wherein the aluminum halide and the alkali metal halide each have a water content of 5 wt.% or less.

16. The method of claim 15, wherein the aluminum halide and the alkali metal halide each have a water content of 2.5 wt.% or less.

17. The method of claim 16, wherein the aluminum halide and the alkali metal halide each have a water content of 1.0 wt.% or less.

18. The method of claim 17, wherein the aluminum halide and the alkali metal halide each have a water content of 0.5 wt.% or less.

19. The method of claim 18, wherein the aluminum halide and the alkali metal halide each have a water content of 0.1 wt.% or less.

20. The method of claim 1, wherein the method of preparing the aluminum source comprises the steps of:

21. The method of claim 20 wherein the aluminum source is prepared by a method comprising the steps of:

mixing an aluminum halide and an alkali metal halide to obtain a mixture, heating the mixture at least until a liquid phase appears, and cooling to obtain an aluminum source; and at least heating until a liquid phase appears, and then preserving the heat for 0-5 h.

22. The method of claim 21 wherein the aluminum source is prepared by heating to at least the liquid phase and holding for a period of time ranging from 10min to 2 hours.

23. The method of claim 21 wherein the aluminum source is prepared by a process comprising the steps of:

mixing aluminum halide and alkali metal halide to obtain a mixture, heating the mixture until the mixture completely becomes a liquid phase, and cooling to obtain an aluminum source; the temperature of raising the temperature until the mixture completely becomes the liquid phase is 0-50 ℃ higher than the temperature of raising the temperature until the liquid phase begins to appear.

24. The method of claim 23, wherein the temperature of the warming to complete the change of the mixture to the liquid phase is 0 to 20 ℃ higher than the temperature of the warming to initiate the appearance of the liquid phase.

25. The method of claim 20, wherein the maximum temperature of the temperature increase in the method for producing the aluminum source is 50 ℃ or higher.

26. The method of claim 25, wherein the maximum temperature of the aluminum source is 60 ℃ or higher in the method for producing the aluminum source.

27. The method of claim 26, wherein the maximum temperature of the aluminum source is 65 ℃ or higher in the method for producing the aluminum source.

28. The method of claim 27, wherein the maximum temperature of the aluminum source is 70 to 400 ℃ in the method for preparing the aluminum source.

29. The method of claim 28, wherein the aluminum source is prepared by raising the temperature at a maximum temperature of 70 to 350 ℃.

30. The method of claim 20 wherein the minimum cooling temperature in the method of making the aluminum source is less than 200 ℃.

31. The method of claim 30 wherein the minimum cooling temperature in the method of making the aluminum source is less than 160 ℃.

32. The method of claim 31 wherein the minimum cooling temperature in the method of making the aluminum source is less than 100 ℃.

33. The method of claim 32 wherein the minimum cooling temperature in the method of making the aluminum source is less than 50 ℃.

34. The method of claim 1, wherein the process for electrolytically producing the aluminum-containing alloy is carried out under an inert gas.

35. The method of claim 1 wherein the aluminum source and the non-aluminum alloying element source are each independently selected to be added continuously, or added at once, or added in multiple batches.

36. The method of claim 35 wherein the aluminum source and the non-aluminum alloy element source are each independently selected to be added simultaneously with electrolysis on electrical power, or when power is removed.

37. The method of claim 1, wherein the temperature of the electrowinning is 430-900 ℃.

38. The method of claim 37, wherein the temperature of the electrowinning is 450-800 ℃.

39. The process of claim 1, wherein the cathodic voltage for electrolysis is less than the precipitation potential of all metallic elements in said aluminum-containing alloy.

40. The process of claim 39, wherein the cathodic voltage for electrolysis is at least 0.2V below the precipitation potential of all metallic elements in said aluminum-containing alloy.

41. The process of claim 40, wherein the cathodic voltage for electrolysis is 0.2 to 2V below the precipitation potential of all metal elements in said aluminum-containing alloy.

42. The method of claim 1, wherein the anode of the electrolysis is a graphite electrode.

43. The method of claim 1, wherein the cathode of the electrolysis comprises a simple substance or an alloy formed of any 1 or at least 2 of carbon element and metal element; the electrolytic cathode may be present in a liquid or solid state.

44. The method of claim 43, wherein the cathode comprises any 1 or a combination of at least 2 of steel, molybdenum, tungsten, titanium, and graphite.

45. A preparation method of an aluminum-containing alloy casting is characterized by comprising the following steps:

electrolyzing an aluminum source as defined in any of claims 1 to 44 in an electrolyte comprising a source of an alloying element in combination with a source of the alloying element by application of electricity to obtain a liquid aluminum-containing alloy, and thereafter cooling the liquid aluminum-containing alloy in a mold to obtain a cast aluminum-containing alloy;

in the preparation method of the aluminum-containing alloy casting, the process step conditions are the same as any one of claims 1 to 44.