CN108456897A - For the silicon source of electrolytic preparation aluminium-containing alloy, preparation method and the method for preparing aluminium-containing alloy using it - Google Patents
For the silicon source of electrolytic preparation aluminium-containing alloy, preparation method and the method for preparing aluminium-containing alloy using it Download PDFInfo
- Publication number
- CN108456897A CN108456897A CN201710087088.9A CN201710087088A CN108456897A CN 108456897 A CN108456897 A CN 108456897A CN 201710087088 A CN201710087088 A CN 201710087088A CN 108456897 A CN108456897 A CN 108456897A
- Authority
- CN
- China
- Prior art keywords
- aluminium
- halide
- containing alloy
- source
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
Abstract
The present invention provides a kind of silicon source for electrolytic preparation aluminium-containing alloy, source of aluminium includes the double salt formed by aluminum halide and alkali halide.It solves aluminum halide and is easy water suction at normal temperatures, distillation is easy under high temperature, the problem of being difficult to control the amount of being actually added into of silicon source, solves the harm that the distillation of aluminum halide silicon source brings environment simultaneously, it solves the problems, such as that the water suction of aluminum halide silicon source generates aluminum hydroxide precipitation, extends deslagging period and the service life of electrolytic cell of electrolytic cell.It uses it for preparing aluminium-containing alloy, the content into the aluminium element in electrolyte can be controlled, and then realize the controllable of aluminium-containing alloy element ratio, it realizes the stability of element ratio in different batches aluminium-containing alloy, omits second melting when aluminium-containing alloy material preparation workpiece；In addition the distillation that aluminium element can be reduced using silicon source provided by the present invention, reduces environmental hazard.
Description
Technical field
The invention belongs to metallurgical and Material Fields, and in particular to a kind of silicon source for electrolytic preparation aluminium-containing alloy, use
It prepares the method for aluminium-containing alloy.
Background technology
Magnesium alloy, lithium-aluminium alloy, aluminizing, manganese aluminium, sial, tin aluminium, scandium aluminium, yttrium aluminium, zirconium aluminium, rare earth aluminium alloy etc. contain aluminium
Alloy has distinctive excellent properties, be widely used in preparing new material or as new material application in space flight, aviation, military project,
The fields such as vehicular traffic, electronics, 3C.In recent years, product miniaturization, intelligent, lightweight development are getting faster, new material demand
It is more and more urgent.For example, magnesium alloy has the spies such as light-weight, specific strength is high, electromagnetism interference, damping property are good, are easily recycled
Point is known as " the epoch metal material of 21 century ".Lithium-aluminium alloy, which manufactures secondary molten salt lithium battery, has high power density, high energy
Metric density and long circulation life.
Conventional alloys are prepared using smelting process (also referred to as to the method for mixing), it is to be placed in alloy in smelting furnace with metal, in gas
Make material melting with holding high temperature enough time under flux protection and spread mixing, and then subject alloy is prepared.This method
It has the following disadvantages：1. alloy production process is cumbersome：Metal needs needed for alloying will be obtained by respective metallurgical process, then
Subject alloy could be obtained by secondary or even multiple melting；2. product lack of homogeneity：Due to participating in the different metal of alloying
Density variation is big, and (such as magnesium metal density is 1.74g/cm3, the density of rare earth metal neodymium is 7.00g/cm3), even if in high-temperature liquid-phase
Shi Caiyong mechanical agitations also are difficult to the magnesium alloy that guarantee alloying element can be mixed well, therefore be obtained, and there are certain ingredient is inclined
Analysis；3. stability is poor：Cause different batches alloy property difference larger because burning the reasons such as mistake during alloy melting；4. environment is endangered
Evil is big：Some metals such as magnesium cannot form the oxidation film isolation metal of densification and reacting for oxygen at high temperature, so fusion process
Good safeguard measure must be used, and now still in the SF largely used6Protective gas huge prestige can be caused to environment
The side of body；5. scaling loss is serious：The oxidization burning loss for heating active metal in fusion process is serious.
In order to solve problem above, fused salt electrolysis process prepares alloy and obtains extensive concern in recent years, and this method is in halogenation
In object (such as chloride or fluoride) molten salt system, adds direct current in cathode deposit alloy or alloying element, finally obtain alloy.
The fused salt electrolysis process, which prepares alloy, following two methods：
One kind is electrolysis diffusion method.This method uses the metal or alloy of solid-state or liquid as cathode, other alloys
Element deposits on it, and diffusion-alloying, obtains the alloy of required component.When this method electrolysis magnesium alloy, need to adopt
Use liquid aluminium or liquid aluminium alloy as cathode electrolytic deposition active metal magnesium, then by diffusion-alloying, and aluminium or aluminium close
Au cathode must be prepared by other metallurgical process.
Another kind is electrolytic codeposition of nickel method.This method is to occur to be co-deposited and close in cathode by a variety of alloying element ions
Aurification.Electrolytic codeposition of nickel method has the following advantages：1. flow is short：It is whole to produce without each alloyed metal (AM) is prepared separately
Flow is short；2. alloy uniformity is good：Various alloying elements are that atomic level mixes under electrolysis conditions, and obtained alloying component is equal
Even property is good；3. alloy stability is good：Automation control may be implemented in electrolytic process, and electrolytic parameter can accurately control, artificial dry
Disturb that factor is small, therefore the stability of product is good.
Fused salt electrolysis codeposition solves the problems, such as that smelting process exists well, greatly reduces cost, environmental protection and energy saving simultaneously
Obtain the alloy of high-quality.
The research of the electrolytic preparation of aluminium-containing alloy receives extensive concern, and it mostly uses anhydrous aluminum halide as silicon source.With
When anhydrous aluminum halide uses electrolytic preparation aluminium-containing alloy as silicon source, the method that molten salt electrolyte is added in anhydrous aluminum halide has two
Kind：One is be directly added with anhydrous halogenation aluminium powder；Another kind be by after anhydrous aluminum halide tabletting to be added at graininess.
For being carried out with anhydrous halogenation aluminium powder or with being added in electrolyte system with graininess after aluminum halide tabletting
The method of electrolysis aluminium-containing alloy processed, there are the following problems：
(1) anhydrous aluminum halide, especially anhydrous Aluminum chloride easily distil, highly volatile so that Wu Fagen under electrolysis temperature
The addition of silicon source is determined according to the aluminium content of aluminium-containing alloy, it is difficult to control the content of aluminium element in aluminium-containing alloy；Further, since
It is difficult to control the amount for the aluminium element for actually entering aluminium-containing alloy, although causing the silicon source that every batch of is added identical, every batch of is closed containing aluminium
The aluminium content of gold is unstable；
(2) anhydrous aluminum halide, especially anhydrous Aluminum chloride easily absorb water, formed with the crystallization water aluminum halide, by itself plus
After entering into electrolyte, it is easy to generate alumina deposit in bottom of electrolytic tank, it is difficult to remove, the oxygen for needing power-off clearly to sink to the bottom
Change aluminium, influences bath life.
This field needs to develop a kind of silicon source for electrolytic preparation aluminium-containing alloy, can be in electrolytic preparation aluminium-containing alloy
It solves aluminium element in aluminium-containing alloy caused by distillation, water suction in the process to be unable to control containing aluminium, and aluminium member in every batch of aluminium-containing alloy
Element is unstable, and the problem that caused bath life is short.
Invention content
One of the objects of the present invention is to provide a kind of silicon source for electrolytic preparation aluminium-containing alloy, source of aluminium include by
The double salt that aluminum halide and alkali halide are formed.
The double salt that the present invention forms aluminum halide and alkali halide, as the aluminium for electrolytic preparation aluminium-containing alloy
Source, stable components, nonflammable, non-explosive, facile hydrolysis, compact structure, density is not big, fusing point is higher, brings following advantage：①
In normal temperature air, ingredient and property it is stable, it is nonflammable, non-explosive, be not susceptible to acutely chemically react, corrosivity it is low, safety
Property it is high；2. compact structure, specific surface area be not small, hygroscopic, the requirement to silicon source storage condition and traffic condition can be reduced,
In the environment of identical water content, the silicon source compared to aluminum halide can store the longer time；3. density is big, small, storage and
Transport space used is small, convenient for storage, transport and uses；4. water imbibition is low, not hygroscopic, in temperature-rise period, water does not occur
Solution, improves the utilization rate of aluminium element in silicon source, and is greatly reduced because of the oxygen that aluminum halide hydrolysis introduces in electrolytic process
Change aluminium, alleviates the shortening of bath life caused by aluminium oxide hydrolyzes generation precipitation of alumina in electrolytic process；5. this hair
It is not volatile in the silicon source temperature-rise period of bright offer, the volatilization loss of aluminium element is reduced, the profit of aluminium element in silicon source is improved
With rate, further, since the volatilization loss of aluminium element is small, the input that aluminium element can also be improved using silicon source of the present invention is steady
It is qualitative, control the stable content of aluminium element in aluminium-containing alloy；6. silicon source provided by the invention has lower saturated vapour pressure, carry
The high safety of use environment, reduces aluminum halide in the prior art and corrodes and pollute caused by environment as silicon source.
Preferably, in the double salt, molar ratio≤50 of aluminium element and alkali metal element, it is illustrative 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、0.9、0.8、0.7、
0.6,0.5,0.4,0.3,0.2,0.1,0.05 etc., preferably≤25, more preferably≤10, further preferably≤8, particularly preferably≤6.
In double salt of the present invention, aluminium element and alkali metal element molar ratio≤50, between molar ratio is in 0.2~25
When, gained silicon source volatility and water imbibition on the basis of ensureing aluminium content is lower, when molar ratio is between 0.5~10,
Gained silicon source is more stable in storage and transportational process, and the ingredient of aluminium-containing alloy is more stable in electrolytic process.
Preferably, the alkali metal includes arbitrary a kind or at least two kinds of of the combination in lithium, sodium, potassium, rubidium, caesium and francium.
Preferably, the halogen element in the aluminum halide and alkali halide is respectively independently selected from chlorine element, bromine member
Arbitrary a kind or at least two kinds of of combination in element and iodine.
Preferably, the aluminum halide includes arbitrary a kind or at least two kinds of of the combination in aluminium chloride, aluminium bromide and silver iodide；
Preferably, the alkali halide includes lithium halide, sodium halide, potassium halide, rubidium halide, caesium halide and halogenation francium
In arbitrary a kind or at least two kinds of of combination；Further preferably comprising lithium chloride, sodium chloride, potassium chloride, rubidium chloride, lithium bromide,
Arbitrary a kind or at least two kinds of of combination in sodium bromide, potassium bromide, rubidium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide；It is special
Lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide are not preferably included；Still more preferably it is sodium chloride, chlorination
Arbitrary a kind or at least two kinds of of combination in potassium, sodium bromide, potassium bromide.
Preferably, water content≤5wt% of aluminum halide and alkali halide of the present invention includes illustratively
4.9wt%, 4.5wt%, 4.4wt%, 4.1wt%, 4.0wt%, 3.9wt%, 3.0wt%, 2.9wt%, 2.5wt%,
2.4wt%, 2.1wt%, 2.0wt%, 1.9wt%, 1.5wt%, 1.1wt%, 1.0wt%, 0.9wt%, 0.8wt%,
0.6wt%, 0.5wt%, 0.4wt%, 0.3wt%, 0.2wt%, 0.1wt%, 0.05wt%, 0.01wt%, preferably water content
≤ 2.5wt%, preferably water content≤1.0wt%, preferably water content≤0.5wt%, preferably water content≤0.1wt%.
The two of the object of the invention are to provide a kind of silicon source for electrolytic preparation aluminium-containing alloy as described in the first purpose
Preparation method, described method includes following steps：
Mixing aluminum halide and alkali halide obtain mixture, and the mixture is at least warming up to form double salt, cold
But after, silicon source is obtained.
" being warming up to form double salt " of the present invention means to be warming up to any temperature that can form double salt, so-called " to be formed
Double salt " includes part or all of mono-salt formation double salt in the mixture.
Preferably, the preparation method of the silicon source for electrolytic preparation aluminium-containing alloy includes the following steps：
Mixing aluminum halide and alkali halide obtain mixture, and the mixture is at least warming up to and liquid phase occurs, cold
But after, silicon source is obtained；It is described be at least warming up to there is liquid phase after keep the temperature 0~5h, 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 etc. preferably keep the temperature 10min~2h.
" be at least warming up to and liquid phase occur " of the present invention means to heat the mixture, and to starting liquid phase occur, (temperature is remembered
For T1), continue heating and thermal insulation later in T1, or continuing heating makes temperature be higher than T1。
It is described be at least warming up to there is liquid phase after keep the temperature a period of time, can further increase liquid content, increase silicon source
The content of middle double salt reduces hydrolysis and volatilization loss of the silicon source in electrolytic process is added, makes aluminium in aluminium-containing alloy preparation process
The amount of being actually added into source is easier to control.
Those skilled in the art are being warming up to form double salt, and blocks of solid is obtained after cooling, can selectivity progress
Granulation, such as ball milling, grinding mode, with convenience in transport, storage and conveying.Transport and store preferred bulk form, conveying charging
It can be not specifically limited according to feed inlet size particles, size, preferred size≤0.1m, further preferred 0.001~
Between 0.1m.
It is further preferred that the preparation method of the silicon source for electrolytic preparation aluminium-containing alloy includes the following steps：
Mixing aluminum halide and alkali halide obtain mixture, and the mixture is warming up to the mixture to be become completely
At liquid phase silicon source is obtained after cooling；It is described be warming up to the mixture and become the temperature of liquid phase completely be relatively warming up to and start to occur
The temperature of liquid phase is preferably 0~50 DEG C high, for example, 1 DEG C, 5 DEG C, 9 DEG C, 11 DEG C, 15 DEG C, 19 DEG C, 21 DEG C, 25 DEG C, 29 DEG C, 31 DEG C, 35
DEG C, 39 DEG C, 41 DEG C, 45 DEG C, 49 DEG C etc., further preferred 0~20 DEG C.
Preferably, the maximum temperature of the heating is at 50 DEG C or more, it is illustrative include 51 DEG C, 54 DEG C, 55 DEG C, 56 DEG C,
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℃、174℃、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 DEG C, 400 DEG C, 450 DEG C, 480 DEG C, 530 DEG C, 550 DEG C, 660 DEG C, 790 DEG C etc., preferably 60 DEG C or more, more preferable 65 DEG C with
On, it is further preferred between 70~400 DEG C, it is particularly preferred between 70~350 DEG C.
Preferably, the cooling minimum temperature at 200 DEG C hereinafter, it is illustrative as 199 DEG C, 195 DEG C, 194 DEG C, 191 DEG C,
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℃、41℃、40℃、39℃、35℃、34℃、31℃、30℃、29
DEG C, 25 DEG C, 24 DEG C, 21 DEG C, 0 DEG C etc., preferably 160 DEG C hereinafter, more preferable 100 DEG C hereinafter, further preferred 50 DEG C or less.
Preferably, in terms of aluminium element and alkali metal element, the mixing molar ratio of the aluminum halide and alkali halide≤
50, it is illustrative 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、
1.1,1.0,0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2,0.1,0.05 etc., preferably≤25, more preferably≤10, further
It is preferred that≤8, particularly preferably≤6.
The three of the object of the invention are to provide a kind of method of electrolytic preparation aluminium-containing alloy, aluminium in aluminium-containing alloy in the method
The source of element includes the silicon source described in the first purpose.
Using silicon source provided by the invention, the volatilization and hydrolysis of silicon source can be reduced, improves the conversion of aluminium element in silicon source
Rate improves the stability of aluminium element content in aluminium-containing alloy, reduces in aluminium-containing alloy preparation process since silicon source is volatilized to environment
Caused by pollute, solve aluminum halide silicon source and absorb water to form aluminium oxide and hydrolyze to form precipitation of alumina in high-temperature electrolysis matter and cause
The problem of cell life shortens, extends the service life of electrolytic cell；Become in the electrolyte using silicon source provided by the invention
It is less than the sublimation point or fusing point of aluminum halide at the temperature of liquid phase, homogenising time can be shortened, can joins rapidly after entering liquid phase
With electrolysis, the technical process required time for producing identical aluminium-containing alloy material is shortened.
The present invention is not specifically limited the method for the electrolytic preparation aluminium-containing alloy, and silicon source provided by the invention can be used
Make the method for any type electrolytic preparation aluminium-containing alloy, such as silicon source is added to the liquid electrolyte of electrolyte and other alloy sources
In matter, either silicon source and other alloy sources are added into liquid electrolyte or by silicon source in a manner of particle in conveyer belt
Under be continuously added into electrolyte, or be added portionwise silicon source is intermittent in the form of granular to electrolyte
In, etc..
In an optional technical solution, the method for the electrolytic preparation aluminium-containing alloy is：
In the electrolyte containing silicon source and alloying element source described in the first purpose, the electrolysis that is powered obtains liquid and contains
Aluminium alloy obtains aluminium-containing alloy solid after later cooling down the liquid aluminium-containing alloy.
In the technical solution, source of aluminium is added at one time, during silicon source provided by the invention is added, silicon source
Volatile quantity is few, the high conversion rate of aluminium element in silicon source, and stably and controllable, reduces because silicon source volatilization is to aluminium member in aluminium-containing alloy
The unstable influence of cellulose content can ensure in the case where identical silicon source and electrolytic condition is added, and produce containing for aluminium content stabilization
Aluminium alloy, and reduce the pollution to environment.
And for the prior art using aluminum halide as silicon source, since its (aluminum halide) volatile quantity is uncontrolled, water absorption is not
It is controlled, and hydrolysate aluminium oxide can not participate in being electrolysed after absorbing water, and cause aluminium element content in aluminium-containing alloy uncontrollable, aluminium element
The problems such as waste is serious, and aluminium oxide influences bath life.For these problems of the prior art, using aluminium of the present invention
Source can effectively solve.
Preferably, the method for the electrolytic preparation aluminium-containing alloy carries out under an inert gas.
It is electrolysed under an inert gas, the anodic gas that electrolysis generates can be made to be discharged in time, reduce electrolyte middle-jiao yang, function of the spleen and stomach
Pole gas concentration reduces the alloy of generation and the secondary response of anodic gas；In addition, the protection of inert gas can also prevent water
Steam enters electrolytic cell, it is therefore prevented that the hydrolysis under water imbibition electrolyte high-temperature；Protective gas can also prevent oxidizing gas
Into, avoid the oxidation for being electrolysed out aluminium-containing alloy, not only improve metal yield, but also prevent hydrolysis and oxidation gained metal
The deterioration of electrolysis system caused by oxide improves electrolytic cell service life.
The inert gas includes illustratively one or more of inert gas, the inert gas include argon gas,
Arbitrary a kind or at least two kinds of of combination in helium and nitrogen.
Preferably, source of aluminium and non-aluminum alloying element source are each independently selected continual addition, Huo Zheyi
Source of aluminium and non-aluminum alloying element source or multiple batches of addition source of aluminium and non-aluminum alloying element source is added in secondary property.
" continual addition " of the present invention means will be provided by the invention by transmission equipment (such as conveyer belt)
Silicon source or non-aluminum metal element source (the metallic element source in target aluminium-containing alloy in addition to aluminium) are continuously added into electrolyte
It is electrolysed, the rate being added can be adjusted, and to control the content of metallic element in electrolyte, realize in aluminium-containing alloy
The controllability of metallic element ratio.Art technology arbitrarily should also be as being illustrated, and when continual addition silicon source, can introduce alkali
Metal halide, but the introduction volume of the alkali halide can control, in order to make the constituent content in aluminium-containing alloy more
Stablize, can selectivity taking-up electrolyte, stablize electrolytic process in electrolyte, aluminium element and metallic element content.
" being added at one time " of the present invention is it is meant that silicon source provided by the invention and non-aluminum metal element source are disposably added
Enter and is electrolysed into electrolyte.This mode is excessive in initial aluminium element, and element ratio is stablized in aluminium-containing alloy,
But with the consumption of silicon source, the reduction of aluminium element content in aluminium-containing alloy can be caused, but those skilled in the art can select
Stop electrolysis before the non-excess of aluminium element, the steady of constituent content in aluminium-containing alloy can both have been ensured by ensureing that aluminium element is excessive always
It is fixed.
" multiple batches of addition " of the present invention is it is meant that by silicon source provided by the invention and non-aluminum metal element source with any
The mode that field technology personnel can obtain is added portionwise into electrolyte, similar with the mode of " being added at one time ", in order to obtain
The aluminium-containing alloy that ratio must be stablized needs that silicon source is added before the non-excess of aluminium-containing alloy, and aluminium element contains in guarantee electrolyte
Amount is excessive.
The present invention does not limit the addition time point of source of aluminium and non-aluminum alloying element source.
Preferably, source of aluminium and non-aluminum alloying element source are each independently selected is added while being powered and being electrolysed,
Or it is added when power is off.
Preferably, the temperature of the electrolysis that is powered is 350~1000 DEG C, it is illustrative as 350 DEG C, 356 DEG C, 359 DEG C,
365℃、370℃、380℃、391℃、399℃、409℃、421℃、430℃、440℃、450℃、460℃、471℃、480
℃、499℃、505℃、521℃、530℃、540℃、550℃、560℃、571℃、580℃、599℃、609℃、621℃、
630℃、640℃、650℃、660℃、671℃、680℃、699℃、709℃、721℃、730℃、740℃、750℃、760
℃、771℃、780℃、799℃、809℃、821℃、830℃、840℃、850℃、860℃、871℃、880℃、899℃、
909 DEG C, 921 DEG C, 930 DEG C, 940 DEG C, 950 DEG C, 960 DEG C, 971 DEG C, 980 DEG C, 999 DEG C, 1000 DEG C etc., preferably 430~900
DEG C, further preferred 450~800 DEG C.
Preferably, the cathode voltage for electrolysis will be less than the precipitation electricity of all metallic elements in the aluminium-containing alloy
Position, preferably it is low go out 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 0.2~2V.
Illustratively, the voltage of the electrolysis can be：Anode voltage is 0V, the precipitation electricity of metallic element in aluminium-containing alloy
The minimum 5V in position, then cathode voltage need to be arranged in -5V hereinafter, such as -6V, -7V, -8V etc..
As optional example, the voltage of electrolysis of the present invention is 1~10V, it is illustrative as 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、8.0V、8.1V、8.4V、8.5V、8.6V、8.9V、9.0V、
9.1V, 9.4V, 9.5V, 9.6V, 9.9V, 10.0V etc., preferably 1.1~9V, further preferred 1.2~9V, particularly preferred 3~7V.
The voltage of the electrolysis can be understood as the voltage absolute value of the difference between cathode and anode.
Preferably, the anode of the electrolysis is graphite electrode.
Preferably, the cathode of the electrolysis includes by arbitrary a kind or at least two kinds of formation in carbon and metallic element
Simple substance or alloy；The existence form of the cathode of the electrolysis includes liquid or solid-state.
It is further preferred that the cathode includes arbitrary a kind or at least two kinds of of the combination in steel, molybdenum, tungsten, titanium and graphite.
Preferably, the electrolyte for being powered electrolysis includes arbitrary 1 in alkali halide and alkaline-earth halide
Kind or at least two kinds of combinations.
Preferably, the alkaline-earth halide includes halogenation beryllium, magnesium halide, calcium halide, halogenation strontium, barium halide and halogenation
Arbitrary a kind or at least two kinds of of combination in radium；Further preferably comprising beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, chlorination
In barium, beryllium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, beryllium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide
Arbitrary a kind or at least two kinds of of combination；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 it is arbitrary in magnesium chloride, calcium chloride, strontium chloride, barium chloride
1 kind or at least two kinds of of combination.
Preferably, the non-aluminum alloying element includes in Main Group Metal Elements, transition metal element and nonmetalloid
Arbitrary a kind or at least two kinds of of combination；It is preferred that 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 in arbitrary a kind or at least two kinds of of combination；Further preferred 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,
Arbitrary a kind or at least two kinds of in tantalum, tungsten, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, uranium, thorium, ytterbium and lutetium
Combination；Particularly preferred lithium, beryllium, boron, magnesium, silicon, titanium, vanadium, manganese, iron, zinc, yttrium, zirconium, lanthanum, cerium, praseodymium, samarium, europium, gadolinium, erbium, ytterbium and
Arbitrary a kind or at least two kinds of of combination in silicon；
Preferably, non-aluminum alloying element source includes arbitrary a kind or at least two kinds of in non-aluminum alloying element compound
Combination, the oxide of further preferred non-aluminum alloying element and/or the chloride of non-aluminum alloying element.
The four of the object of the invention are to provide a kind of aluminium-containing alloy, and the aluminium-containing alloy is by the electrolytic preparation described in the third purpose
The method of aluminium-containing alloy is prepared.
The aluminium-containing alloy that the method is prepared through the invention, constituent content is stably and controllable, secondary without carrying out
Melting, can direct forging molding, obtain aluminium-containing alloy part.
The fifth object of the present invention is to provide a kind of preparation method of aluminium-containing alloy product, and the method is：
In the electrolyte containing silicon source and alloying element source described in the first purpose, the electrolysis that is powered obtains liquid and contains
The liquid aluminium-containing alloy is cooled down, obtains aluminium-containing alloy product by aluminium alloy in a mold later；
Preferably, in the preparation method of the aluminium-containing alloy product, the condition of processing step is identical as the third purpose, specifically
It is as follows：
In one optionally technical solution, the method for the electrolytic preparation aluminium-containing alloy product is：
In the electrolyte containing silicon source and alloying element source described in the first purpose, the electrolysis that is powered obtains liquid and contains
The liquid aluminium-containing alloy is cooled down, obtains aluminium-containing alloy product by aluminium alloy in a mold later.
Aluminium-containing alloy product of the present invention directly can obtain liquid aluminium by being electrolysed silicon source and non-aluminum alloying element source
Alloy, in a mold cooling can be obtained aluminium-containing alloy product, without carrying out secondary smelting, save the energy, protect environment,
And reduce the scaling loss of aluminium-containing alloy during secondary smelting, it is most important that under the premise of omitting secondary smelting, Neng Goushi
The stabilization of existing constituent content of the aluminium containing alloy product.
The stabilization of the constituent content of the aluminium-containing alloy product includes following meaning：
1. in the technique for being continuously added to silicon source and non-aluminum metal element source, aluminium-containing alloy material that each period obtains
The element ratio all same of material, aluminium-containing alloy product or workpiece；
2. in the technique for being added at one time silicon source and non-aluminum alloying element source, an element source is often added, electrolysis finishes
It needs to power off, silicon source and the non-aluminum alloying element source of next batch is added in property again, and each batch provided by the invention obtains
The element ratio all same of the aluminium-containing alloy material, aluminium-containing alloy product or the workpiece that arrive；
3. in the technique in multiple batches of addition silicon source and non-aluminum alloying element source, continues the aluminium-containing alloy material of output, contains
The element ratio all same of Al-alloy products or workpiece.
Preferably, the method for the electrolytic preparation aluminium-containing alloy carries out under an inert gas.
The inert gas includes illustratively arbitrary a kind or at least two kinds of of the combination in argon gas, helium and nitrogen.
Preferably, source of aluminium and non-aluminum alloying element source are each independently selected continual addition, Huo Zheyi
Source of aluminium and non-aluminum alloying element source or multiple batches of addition source of aluminium and non-aluminum alloying element source is added in secondary property.
" continual addition " of the present invention means will be provided by the invention by transmission equipment (such as conveyer belt)
Silicon source or non-aluminum metal element source (the metallic element source in target aluminium-containing alloy in addition to aluminium) are continuously added into electrolyte
It is electrolysed, the rate being added can be adjusted, and to control the content of metallic element in electrolyte, realize in aluminium-containing alloy
The controllability of metallic element ratio.Art technology arbitrarily should also be as being illustrated, and when continual addition silicon source, can introduce alkali
Metal halide, but the introduction volume of the alkali halide can control, in order to make the constituent content in aluminium-containing alloy more
Stablize, can selectivity taking-up electrolyte, stablize electrolytic process in electrolyte, aluminium element and metallic element content.
" being added at one time " of the present invention is it is meant that silicon source provided by the invention and non-aluminum metal element source are disposably added
Enter and is electrolysed into electrolyte.This mode is excessive in initial aluminium element, and element ratio is stablized in aluminium-containing alloy,
But with the consumption of silicon source, the reduction of aluminium element content in aluminium-containing alloy can be caused, but those skilled in the art can select
Stop electrolysis before the non-excess of aluminium element, the steady of constituent content in aluminium-containing alloy can both have been ensured by ensureing that aluminium element is excessive always
It is fixed.
" multiple batches of addition " of the present invention is it is meant that by silicon source provided by the invention and non-aluminum metal element source with any
The mode that field technology personnel can obtain is added portionwise into electrolyte, similar with the mode of " being added at one time ", in order to obtain
The aluminium-containing alloy that ratio must be stablized needs that silicon source is added before the non-excess of aluminium-containing alloy, and aluminium element contains in guarantee electrolyte
Amount is excessive.
The present invention does not limit the addition time point of source of aluminium and non-aluminum alloying element source.
Preferably, source of aluminium and non-aluminum alloying element source are each independently selected is added while being powered and being electrolysed,
Or it is added when power is off.
Preferably, the temperature of the electrolysis that is powered is 350~1000 DEG C, it is illustrative as 350 DEG C, 356 DEG C, 359 DEG C,
365℃、370℃、380℃、391℃、399℃、409℃、421℃、430℃、440℃、450℃、460℃、471℃、480
℃、499℃、505℃、521℃、530℃、540℃、550℃、560℃、571℃、580℃、599℃、609℃、621℃、
630℃、640℃、650℃、660℃、671℃、680℃、699℃、709℃、721℃、730℃、740℃、750℃、760
℃、771℃、780℃、799℃、809℃、821℃、830℃、840℃、850℃、860℃、871℃、880℃、899℃、
909 DEG C, 921 DEG C, 930 DEG C, 940 DEG C, 950 DEG C, 960 DEG C, 971 DEG C, 980 DEG C, 999 DEG C, 1000 DEG C etc., preferably 430~900
DEG C, further preferred 450~800 DEG C.
Preferably, the cathode voltage for electrolysis will be less than the precipitation electricity of all metallic elements in the aluminium-containing alloy
Position, preferably it is low go out 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 0.2~2V.
Illustratively, the voltage of the electrolysis can be：Anode voltage is 0V, the precipitation electricity of metallic element in aluminium-containing alloy
The minimum 5V in position, then cathode voltage need to be arranged in -5V hereinafter, such as -6V, -7V, -8V etc..
As optional example, the voltage of electrolysis of the present invention is 1~10V, it is illustrative as 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、8.0V、8.1V、8.4V、8.5V、8.6V、8.9V、9.0V、
9.1V, 9.4V, 9.5V, 9.6V, 9.9V, 10.0V etc., preferably 1.1~9V, further preferred 1.2~9V, particularly preferred 3~7V.
The voltage of the electrolysis can be understood as the voltage absolute value of the difference between cathode and anode.
Preferably, the anode of the electrolysis is graphite electrode.
Preferably, the cathode of the electrolysis includes by arbitrary a kind or at least two kinds of formation in carbon and metallic element
Simple substance or alloy；The existence form of the cathode of the electrolysis includes liquid or solid-state.
It is further preferred that the cathode includes arbitrary a kind or at least two kinds of of the combination in steel, molybdenum, tungsten, titanium and graphite.
Preferably, the electrolyte for being powered electrolysis includes arbitrary 1 in alkali halide and alkaline-earth halide
Kind or at least two kinds of combinations.
Preferably, the non-aluminum alloying element includes in Main Group Metal Elements, transition metal element and nonmetalloid
Arbitrary a kind or at least two kinds of of combination；It is preferred that 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 in arbitrary a kind or at least two kinds of of combination；Further preferred 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,
Arbitrary a kind or at least two kinds of in tantalum, tungsten, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, uranium, thorium, ytterbium and lutetium
Combination；Particularly preferred lithium, beryllium, boron, magnesium, silicon, titanium, vanadium, manganese, iron, zinc, yttrium, zirconium, lanthanum, cerium, praseodymium, samarium, europium, gadolinium, erbium, ytterbium and
Arbitrary a kind or at least two kinds of of combination in silicon；
Preferably, non-aluminum alloying element source includes arbitrary a kind or at least two kinds of in non-aluminum alloying element compound
Combination, the oxide of further preferred non-aluminum alloying element and/or the chloride of non-aluminum alloying element.
Compared with prior art, the invention has the advantages that：
(1) provided by the present invention for the silicon source of electrolytic preparation aluminium-containing alloy, aluminum halide and alkali halide are answered
Salinization solves aluminum halide and is easy water suction at normal temperatures, is easy distillation under high temperature, it is difficult to control asking for the amount of being actually added into of silicon source
Topic, while solving the harm that the distillation of aluminum halide silicon source brings environment, it solves the water suction of aluminum halide silicon source and generates aluminium hydroxide
The problem of precipitation, extends deslagging period and the service life of electrolytic cell of electrolytic cell；
(2) preparation method of silicon source provided by the invention is simple, loose operation condition, can be within the scope of wider temperature
Double salt is formed, can further be granulated, facilitate the use of silicon source；
(3) preparation method of aluminium-containing alloy provided by the invention uses silicon source provided by the invention, can control into electricity
The content of the aluminium element in matter is solved, and then realizes the controllable of aluminium-containing alloy element ratio, realizes member in different batches aluminium-containing alloy
The stability of plain ratio omits second melting when aluminium-containing alloy material preparation workpiece；In addition aluminium provided by the present invention is used
Source can reduce the distillation of aluminium element, reduce environmental hazard；
(4) element ratio is stablized in aluminium-containing alloy product aluminium alloy provided by the invention, need not be by aluminium-containing alloy material
Second melting is carried out, technique is omitted, saves the energy, reduces the scaling loss of second melting.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Those skilled in the art understand the present invention it will be clearly understood that the embodiment is only to aid in, and are not construed as to this hair
Bright concrete restriction.
Preparation example 1
A kind of silicon source for electrolytic preparation aluminium-containing alloy is prepared via a method which：
Mix the anhydrous AlCl that water content is 0.5%3The NaCl 0.5mol that 12.1mol and water content are 1.5% are obtained
Containing aluminium mixture, gained is warming up to 105 DEG C containing aluminium mixture, 30min is kept the temperature, is cooled to room temperature, obtains 1# silicon sources.1# silicon sources
The molar ratio of middle aluminium element and sodium element is 24.0.
Preparation example 2
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature starts liquid occur to 108.7 DEG C, without heat preservation, is cooled to room temperature immediately, obtains 2# silicon sources.Aluminium element in 2# silicon sources
Molar ratio with sodium element is 24.0.
Preparation example 3
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature keeps the temperature 2min, is cooled to room temperature later, obtains 3# silicon sources to 108.7 DEG C.The molar ratio of aluminium element and sodium element in 3# silicon sources
It is 24.0.
Preparation example 4
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature keeps the temperature 30min, is cooled to room temperature later, obtains 4# silicon sources to 108.7 DEG C.Mole of aluminium element and sodium element in 4# silicon sources
Than being 24.0.
Preparation example 5
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature keeps the temperature 60min, is cooled to room temperature later, obtains 5# silicon sources to 108.7 DEG C.Mole of aluminium element and sodium element in 5# silicon sources
Than being 24.0.
Preparation example 6
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature keeps the temperature 120min, is cooled to room temperature later, obtains 6# silicon sources to 108.7 DEG C.Mole of aluminium element and sodium element in 6# silicon sources
Than being 24.0.
Preparation example 7
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature keeps the temperature 180min, is cooled to room temperature later, obtains 7# silicon sources to 108.7 DEG C.Mole of aluminium element and sodium element in 7# silicon sources
Than being 24.0.
Preparation example 8
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature is cooled to room temperature later to 109 DEG C, obtains 8# silicon sources.The molar ratio of aluminium element and sodium element is 24.0 in 8# silicon sources.
Preparation example 9
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature is cooled to room temperature later to 150 DEG C, obtains 9# silicon sources.The molar ratio of aluminium element and sodium element is 24.0 in 9# silicon sources.
Preparation example 10
A kind of silicon source for electrolytic preparation aluminium-containing alloy, difference lies in will the liter containing aluminium mixture with preparation example 1
Temperature is cooled to room temperature later to 190 DEG C, obtains 9# silicon sources.The molar ratio of aluminium element and sodium element is 24.0 in 9# silicon sources.
Preparation example 11
A kind of silicon source for electrolytic preparation aluminium-containing alloy, with preparation example 6 difference lies in, it is described containing in aluminium mixture,
AlCl3Content be 0.3mol, the content of NaCl is 0.7mol, obtains 10# silicon sources.Aluminium element and sodium element in 10# silicon sources
Molar ratio is 0.43.
Preparation example 12
A kind of silicon source for electrolytic preparation aluminium-containing alloy, with preparation example 6 difference lies in, it is described containing in aluminium mixture,
AlCl3Content be 0.4mol, the content of NaCl is 0.6mol, obtains 11# silicon sources.Aluminium element and sodium element in 11# silicon sources
Molar ratio is 0.66.
Preparation example 13
A kind of silicon source for electrolytic preparation aluminium-containing alloy, with preparation example 6 difference lies in, it is described containing in aluminium mixture,
AlCl3Content be 5mol, the content of NaCl is 0.1mol, obtains 12# silicon sources.Aluminium element and sodium element rubs in 12# silicon sources
You are than being 50.
Preparation example 14
A kind of silicon source for electrolytic preparation aluminium-containing alloy, with preparation example 6 difference lies in, it is described containing in aluminium mixture,
AlCl3Content be 1mol, the content of NaCl is 0.1mol, obtains 12# silicon sources.Aluminium element and sodium element rubs in 12# silicon sources
You are than being 10.
Preparation example 15
A kind of silicon source for electrolytic preparation aluminium-containing alloy, with preparation example 6 difference lies in, it is described containing in aluminium mixture,
AlCl3Content be 0.8mol, the content of NaCl is 0.1mol, obtains 12# silicon sources.Aluminium element and sodium element in 12# silicon sources
Molar ratio is 8.
Preparation example 16
A kind of silicon source for electrolytic preparation aluminium-containing alloy, with preparation example 6 difference lies in, it is described containing in aluminium mixture,
AlCl3Content be 0.6mol, the content of NaCl is 0.1mol, obtains 12# silicon sources.Aluminium element and sodium element in 12# silicon sources
Molar ratio is 6.
Preparation example 17
A kind of silicon source for electrolytic preparation aluminium-containing alloy is prepared via a method which：
Mix the anhydrous AlCl that water content is 1.5%3The KCl 0.29mol that 3.0mol and water content are 2.5% are mixed
Object is closed, gained mixture is warming up to 170 DEG C, is cooled to room temperature, 13# silicon sources are obtained.Aluminium element and potassium element in 13# silicon sources
Molar ratio is 10.
Preparation example 18
A kind of silicon source for electrolytic preparation aluminium-containing alloy is prepared via a method which：
Mix the anhydrous AlCl that water content is 0.6%3The RbCl 0.19mol that 4.0mol and water content are 4.8% are obtained
Gained mixture is warming up to 110 DEG C, is cooled to 20 DEG C, obtains 14# silicon sources by mixture.Aluminium element and rubidium element in 14# silicon sources
Molar ratio be 21.
Preparation example 19
A kind of silicon source for electrolytic preparation aluminium-containing alloy is prepared via a method which：
Mix the anhydrous AlCl that water content is 3.1%3The CsCl 0.15mol that 4.0mol and water content are 2.5% are obtained
Gained mixture is warming up to 120 DEG C, is cooled to 21 DEG C, obtains 15# silicon sources by mixture.Aluminium element and cesium element in 15# silicon sources
Molar ratio be 26.
Preparation example 20
A kind of silicon source for electrolytic preparation aluminium-containing alloy is prepared via a method which：
Mix the anhydrous AlBr that water content is 0.2%3The KBr 0.2mol that 1.0mol and water content are 1.5% are mixed
Object is closed, gained mixture is warming up to 99 DEG C, is cooled to 60 DEG C, obtains 16# silicon sources.Aluminium element and potassium element in 16# silicon sources
Molar ratio is 4.9.
Preparation example 21
A kind of silicon source for electrolytic preparation aluminium-containing alloy is prepared via a method which：
Mix the anhydrous AlI that water content is 0.5%3The NaI 0.5mol that 1.0mol and water content are 0.5% are mixed
Gained mixture is warming up to 290 DEG C, is cooled to 60 DEG C, obtains 17# silicon sources by object.Aluminium element and sodium element rubs in 17# silicon sources
You are than being 1.9.
The alkali metal chloride of the be used as electrolyte of the following example and the water content of alkaline earth metal chloride are below
0.1%, it is below 0.1% as the water content in the compound in non-aluminum alloying element source.
Embodiment A1~embodiment A21
A kind of aluminium-containing alloy, is prepared via a method which：
(1) by 47.0g BaCl2, 94.0g KCl and 109.0gNaCl mixing, be warming up to 680 DEG C, obtain electrolyte solution
Phase；
(2) silicon source of corresponding 1#~21# is added into the electrolyte liquid phase of step (1), makes aluminium member in the silicon source of addition
The theoretical amount of element is that (it be embodiment A2,3# silicon source is that embodiment A3,4# silicon source is that 1# silicon sources are embodiment A1,2# silicon source to 2.0g
It is embodiment A6,7# silicon source be embodiment A7,8# silicon source is embodiment A8 that embodiment A4,5# silicon source, which is embodiment A5,6# silicon source,
It is embodiment A10,11# silicon source be embodiment A11,12# silicon source is embodiment A12,13# that 9# silicon sources, which are embodiment A9,10# silicon source,
It is embodiment A14,15# silicon source be embodiment A15,16# silicon source is embodiment A16,17# that silicon source, which is embodiment A13,14# silicon source,
Silicon source is embodiment 17, and 18# silicon sources are embodiment 18, and 19# silicon sources are embodiment 19, and 20# silicon sources are embodiment 20,21# silicon sources
For embodiment 21)；The theoretical amount of aluminium element is the aluminium element in the aluminium chloride being added during preparing silicon source in source of aluminium
Amount；
(3) anhydrous MgCl is added262.5g is as magnesium source；
(4) it under argon gas atmosphere protection, uses graphite rod for anode, uses rod iron for cathode, in the galvanostatic conditions of 4A
Under (at this time can guarantee anode and cathode voltage difference 6V or more) electrolysis 3h, power-off generates liquid phase in cathode and contains almag；
(5) liquid phase is cooled to room temperature containing almag, obtains solid-state and contains almag.
Comparative example A
Silicon source is replaced with into anhydrous Aluminum chloride with differing only in for embodiment A groups, addition is equally to make the aluminium of addition
The theoretical amount of element is 2g.
The theoretical amount of the aluminium element is the amount of the aluminium element in the aluminium chloride being added during preparing silicon source.
The test result of Aluminum in Alloy content is shown in Table 1：
Table 1
As it can be seen from table 1 addition aluminium element theoretical amount (2g) under the same conditions, the aluminium-containing alloy being prepared
The content of middle aluminium element has differences, and especially compared with comparative example, the content of aluminium element, which has, to be significantly improved, therefore can be seen
Go out, the utilization rate of silicon source can be effectively improved using silicon source of the present invention.
Embodiment B1~embodiment B16
1#~16# silicon sources are placed at room temperature, stores under 20% humidity 1 hour, is repeated later using the silicon source after storage
Carry out that following steps obtain 10 batches for 10 times contains almag：
It in step (4) described in one of embodiment A1~A21, is electrolysed after 3h under the constant current of 4A, adjustment electrolysis
Matter component is allowed to revert to state before electrolysis, and be added again with the same amount of silicon source of B groups experiment, be electrolysed, cathode again
Secondary generation liquid phase contains almag；The liquid phase is cooled to room temperature containing almag, solid-state is obtained and contains aluminium lithium alloy, record is every
Batch containing the aluminium content in aluminium lithium alloy, and calculate the standard deviation of aluminium content and the utilization rate of aluminium element, test result is shown in
Table 2：
Wherein, it is 10, X that N, which is the number repeated,iFor every batch of Aluminum in Alloy content,For 10 batch Aluminum in Alloy contents
Average value；
Comparative example B1
Anhydrous Aluminum chloride is placed at room temperature, is stored 1 hour under 20% humidity, uses the silicon source after storage as aluminium later
The quality such as silicon source after storage are replaced the silicon source in comparative example A by source, the step of repeating B group embodiments.
Comparative example B2
The step of repeating B group embodiments as silicon source using anhydrous Aluminum chloride.
Table 2
From table 2 it can be seen that silicon source stable storage provided by the invention, will not be influenced by humidity and temperature, and nothing
Under room temperature storage, can cause to be prepared aluminium element content in aluminium-containing alloy reduces water aluminium chloride, and carrying cost is caused to rise；
And the selection of silicon source preparation temperature provided by the invention, time is more advantageous to and obtains containing for stable aluminium-containing alloy aluminium element
Amount.
X1 described in embodiment C1~embodiment C16 is the matter for being used to prepare the aluminum halide component for being added to silicon source in electrolytic cell
It measures, that is, aluminium element is scaled the quality of aluminum halide in the silicon source being added, and X2 is to be used to prepare the alkali for being added to silicon source in electrolytic cell
The quality of metal halide component.
Embodiment C1~embodiment C16
A kind of aluminium-containing alloy, is prepared via a method which：
(1) 300.0g KCl and 200.0g NaCl are mixed, 700 DEG C is warming up to, obtains electrolyte；
(2) it uses graphite cake for anode, uses tungsten plate for cathode (S=7.5cm2), add 6A constant-current electrolysis to make two electrodes
Between potential difference brought in 6V or more；
(3) 1#~12# silicon sources are crushed to graininess, and (regulation prepares aluminium by obtained graininess 1#~12# silicon sources
The quality of the aluminum halide component in source is X1, and the quality of alkali halide component is X2) continued not for the speed of 1.27g/h with X1
In disconnected addition electrolyte, while by anhydrous MgCl2With KCl respectively with 9.19g/h andSpeed it is continual
It is added in electrolyte, while withSpeed exports electrolyte, to ensure KCl and NaCl components in electrolyte
Stable content；(it be embodiment C2,3# silicon source be embodiment C3,4# silicon source is embodiment that 1# silicon sources, which are embodiment C1,2# silicon source,
It is embodiment C6,7# silicon source be embodiment C7,8# silicon source is embodiment C8,9# silicon source that C4,5# silicon source, which are embodiment C5,6# silicon source,
For embodiment C9, it be embodiment C11,12# silicon source is embodiment C12 that 10# silicon sources, which are embodiment C10,11# silicon source)；
(4) it can be constantly be generated liquid phase magnesium alloy in the cathode of electrolytic cell, the liquid phase magnesium alloy is taken out, it is cooling
To room temperature, obtains solid-state and contain almag.
Comparative example C
The aluminium elements amounts such as silicon source in C group embodiments are replaced with into anhydrous Aluminum chloride.
After producing 5h, 10h, 15h, 20h, 25h, 30h, takes what is be prepared to be detected containing almag, test it
In aluminium element content, and calculate the standard deviation of the utilization rate and aluminium element content of aluminium element, calculation is as follows, test knot
Fruit is shown in Table 2：
Wherein, N1 is that take the number of alloy sample be 6, XjFor aluminium content in each alloy sample,Contain for aluminium in 6 alloy samples
The average value of amount.
Table 3
From table 3 it can be seen that silicon source provided by the invention be due to that can be stabilized and will not absorb water at normal temperatures, it can
Realize the continuous production of aluminium-containing alloy, and for anhydrous Aluminum chloride, due to absorbing water under its room temperature seriously, as ensured sustained development produces
Continuous progress, the aerial aluminium chloride of exposure causes partial oxidation aluminium to be converted into aluminium oxide, Wu Fa electricity because water absorption increases
Solution is at aluminium-containing alloy.
Embodiment 2
A kind of aluminium-containing alloy, is prepared via a method which：
(1) 200.0g LiCl and 100.0g KCl and erbium source Er are mixed2O33.0g is warming up to 700 DEG C, obtains electrolyte
Liquid phase；
(2) 15# silicon sources are added into the electrolyte liquid phase of step (1), make the aluminium chloride group sub-prime for wherein preparing this silicon source
Amount X1 is 10.0g；
(3) it uses graphite rod for anode, uses molybdenum bar for cathode, (the current density 6.37A/cm under 2A constant currents2) electricity
2h is solved, ensures that in 7V or more, the liquid phase erbium alloy of lithium containing aluminium is generated in cathode for two voltage across poles；
(4) liquid phase lithium containing the aluminium erbium alloy is cooled to room temperature, obtains the solid-state erbium alloy of lithium containing aluminium, wherein aluminium content
It is 20.01%, the conversion ratio of aluminium element is 30.21%.
Embodiment 3
A kind of aluminium-containing alloy, is prepared via a method which：
(1) 70.0gKCl, 200.0gNaCl and the anhydrous MgCl in magnesium source are mixed2The 30.0g and anhydrous ZnCl in zinc source21.0g
700 DEG C are warming up to, electrolyte liquid phase is obtained；
(2) 16# silicon sources are added into electrolyte, wherein the aluminium bromide constituent mass X1 for preparing this silicon source is 20.0g.Using
Graphite rod is anode, uses graphite rod for cathode, in constant current (the current density 0.67A/cm of 4A2) under be electrolysed 3h.Ensure electricity
Negative and positive two-stage voltage difference generates liquid phase kirsite containing magnalium in 5V or more in cathode when solution；
(3) the liquid phase kirsite containing magnalium is cooled to room temperature, obtains solid-state kirsite containing magnalium, wherein aluminium content
It is 12.48%, the conversion ratio of aluminium element is 34.02%
Embodiment 4
A kind of aluminium-containing alloy, is prepared via a method which：
(1) 100.0g LiCl and 100.0g KCl and erbium source Y are mixed2O32.0g is warming up to 650 DEG C, obtains electrolyte
Liquid phase；
(2) 17# silicon sources are added into the electrolyte liquid phase of step (1), make the silver iodide group sub-prime for wherein preparing this silicon source
Amount X1 is 25.0g；
(3) it uses graphite rod for anode, uses tungsten bar for cathode, (the S=0.322cm under the constant current of 2A2) electrolysis 2h,
Ensure that in 7V or more, the liquid phase yittrium alloy of lithium containing aluminium is generated in cathode for two voltage across poles；
(4) liquid phase lithium containing the aluminium erbium alloy is cooled to room temperature, obtains the solid-state erbium alloy of lithium containing aluminium, wherein aluminium content
It is 25.71%, the conversion ratio of aluminium element is 40.13%.
Applicant states that the present invention illustrates the process of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of silicon source for electrolytic preparation aluminium-containing alloy, which is characterized in that source of aluminium includes by aluminum halide and alkali metal
The double salt that halide is formed.
2. silicon source as described in claim 1, which is characterized in that in source of aluminium, the molar ratio of aluminium element and alkali metal element
≤ 50, preferably≤25, more preferably≤10, further preferably≤8, particularly preferably≤6；
Preferably, the alkali metal includes arbitrary a kind or at least two kinds of of the combination in lithium, sodium, potassium, rubidium, caesium and francium；
Preferably, the halogen element in the aluminum halide and alkali halide be respectively independently selected from chlorine element, bromo element and
Arbitrary a kind or at least two kinds of of combination in iodine；
Preferably, the aluminum halide is anhydrous aluminum halide, preferably include arbitrary a kind in aluminium chloride, aluminium bromide and silver iodide or
At least two kinds of combinations；
Preferably, the alkali halide includes in lithium halide, sodium halide, potassium halide, rubidium halide, caesium halide and halogenation francium
Arbitrary a kind or at least two kinds of of combination；Further preferably comprising lithium chloride, sodium chloride, potassium chloride, rubidium chloride, lithium bromide, bromination
Arbitrary a kind or at least two kinds of of combination in sodium, potassium bromide, rubidium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide；It is especially excellent
Choosing includes lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide；Still more preferably be sodium chloride, potassium chloride,
Arbitrary a kind or at least two kinds of of combination in sodium bromide, potassium bromide；
Preferably, the water content of the aluminum halide and alkali halide≤5wt%, preferably water content≤2.5wt%, it is excellent
Select water content≤1.0wt%, preferably water content≤0.5wt%, preferably water content≤0.1wt%.
3. a kind of preparation method of the silicon source as claimed in claim 1 or 2 for electrolytic preparation aluminium-containing alloy, feature exist
In described method includes following steps：
Mixing aluminum halide and alkali halide obtain mixture, and the mixture is at least warming up to form double salt, after cooling,
Obtain silicon source；
Preferably, described method includes following steps：
Mixing aluminum halide and alkali halide obtain mixture, and the mixture is at least warming up to and liquid phase occurs, after cooling,
Obtain silicon source；It is described be at least warming up to there is liquid phase after keep the temperature 0~5h, preferably keep the temperature 10min~2h；
Preferably, described method includes following steps：
Mixing aluminum halide and alkali halide obtain mixture, and the mixture is warming up to the mixture becomes liquid completely
Phase obtains silicon source after cooling；It is described be warming up to the mixture and become the temperature of liquid phase completely be relatively warming up to and start liquid phase occur
Temperature preferably it is 0~50 DEG C high, further preferred 0~20 DEG C.
4. preparation method as claimed in claim 3, which is characterized in that the maximum temperature of the heating is at 50 DEG C or more, preferably
60 DEG C or more, more preferable 65 DEG C or more, further preferred 70~400 DEG C, particularly preferred 70~350 DEG C；
Preferably, the cooling minimum temperature at 200 DEG C hereinafter, it is preferred that 160 DEG C hereinafter, more preferable 100 DEG C hereinafter, further it is excellent
Select 50 DEG C or less；
Preferably, in terms of aluminium element and alkali metal element, mixing molar ratio≤50 of the aluminum halide and alkali halide are excellent
Choosing≤25, more preferably≤10, further preferably≤8, particularly preferably≤6.
5. a kind of method of electrolytic preparation aluminium-containing alloy, which is characterized in that in the method in aluminium-containing alloy aluminium element source
Including silicon source as claimed in claim 1 or 2；
Preferably, the method is：
In the electrolyte containing silicon source as claimed in claim 1 or 2 and non-aluminum alloying element source, the electrolysis that is powered obtains liquid
State aluminium-containing alloy obtains aluminium-containing alloy solid after later cooling down the liquid aluminium-containing alloy；
Preferably, the method for the electrolytic preparation aluminium-containing alloy carries out under an inert gas.
6. method as claimed in claim 5, which is characterized in that source of aluminium and non-aluminum alloying element source are selected each independently
Continual addition is selected, source of aluminium and non-aluminum alloying element source or the multiple batches of addition aluminium are either added at one time
Source and non-aluminum alloying element source；
Preferably, source of aluminium and non-aluminum alloying element source are each independently selected is added while being powered and being electrolysed, or
It is added when power is off.
7. such as method described in claim 5 or 6, which is characterized in that the temperature of the electrolysis that is powered is 350~1000 DEG C, excellent
Select 430~900 DEG C, further preferred 450~800 DEG C；
Preferably, the cathode voltage for electrolysis will be less than the deposition potential of all metallic elements in the aluminium-containing alloy,
It is preferred that it is low go out at least 0.2V, preferably 0.2~2V；
Preferably, the anode of the electrolysis is graphite electrode；
Preferably, the cathode of the electrolysis includes the simple substance by arbitrary a kind in carbon and metallic element or at least two kinds of formation
Or alloy；The existence form of the cathode of the electrolysis includes liquid or solid-state；
It is further preferred that the cathode includes arbitrary a kind or at least two kinds of of the combination in steel, molybdenum, tungsten, titanium and graphite；
Preferably, the electrolyte for being powered electrolysis include arbitrary a kind in alkali halide and alkaline-earth halide or
At least two kinds of combinations；
Preferably, the alkaline-earth halide includes in halogenation beryllium, magnesium halide, calcium halide, halogenation strontium, barium halide and halogenation radium
Arbitrary a kind or at least two kinds of of combination；Further preferably comprising beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, bromine
Change arbitrary 1 in beryllium, magnesium bromide, calcium bromide, strontium bromide, barium bromide, beryllium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide
Kind or at least two kinds of combinations；Particularly preferably include beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, beryllium bromide, bromination
Magnesium, calcium bromide, strontium bromide, barium bromide；Still more preferably it is arbitrary a kind in magnesium chloride, calcium chloride, strontium chloride, barium chloride
Or at least two kinds of combination.
8. the method as described in one of claim 5~7, which is characterized in that the non-aluminum alloying element includes main group metal member
Arbitrary a kind or at least two kinds of of combination in element, transition metal element and nonmetalloid；It is preferred that 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 in arbitrary a kind or at least 2
The combination of kind；Further preferred 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,
Arbitrary a kind or at least two kinds of of combination in uranium, thorium, ytterbium and lutetium；Particularly preferred lithium, beryllium, boron, magnesium, silicon, titanium, vanadium, manganese, iron, zinc,
Arbitrary a kind or at least two kinds of of combination in yttrium, zirconium, lanthanum, cerium, praseodymium, samarium, europium, gadolinium, erbium, ytterbium and silicon；
Preferably, non-aluminum alloying element source includes arbitrary a kind or at least two kinds of of the group in non-aluminum alloying element compound
It closes；The oxide of further preferred non-aluminum alloying element and/or the halide of non-aluminum alloying element.
9. a kind of aluminium-containing alloy, which is characterized in that the aluminium-containing alloy is contained by the electrolytic preparation described in one of claim 5~8
The method of aluminium alloy is prepared.
10. a kind of preparation method of aluminium-containing alloy casting, which is characterized in that the method is：
In the electrolyte containing silicon source as claimed in claim 1 or 2 and alloying element source, the electrolysis that is powered obtains liquid and contains
The liquid aluminium-containing alloy is cooled down, obtains aluminium-containing alloy casting by aluminium alloy in a mold later；
Preferably, in the preparation method of the aluminium-containing alloy product, the condition of processing step is identical as claim 5~8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710087088.9A CN108456897B (en) | 2017-02-17 | 2017-02-17 | Aluminum source for preparing aluminum-containing alloy through electrolysis, preparation method and method for preparing aluminum-containing alloy through aluminum source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710087088.9A CN108456897B (en) | 2017-02-17 | 2017-02-17 | Aluminum source for preparing aluminum-containing alloy through electrolysis, preparation method and method for preparing aluminum-containing alloy through aluminum source |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108456897A true CN108456897A (en) | 2018-08-28 |
| CN108456897B CN108456897B (en) | 2020-11-20 |
Family
ID=63228809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710087088.9A Active CN108456897B (en) | 2017-02-17 | 2017-02-17 | Aluminum source for preparing aluminum-containing alloy through electrolysis, preparation method and method for preparing aluminum-containing alloy through aluminum source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108456897B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798140A (en) * | 1973-02-01 | 1974-03-19 | Us Interior | Process for producing aluminum and silicon from aluminum silicon alloys |
| US4846943A (en) * | 1986-06-06 | 1989-07-11 | Lilliwyte Societe Anonyme | Manufacture of an alkali metal aluminum halide compound and alkali metal |
| CN102061490A (en) * | 2010-12-24 | 2011-05-18 | 淄博德丰化工有限公司 | Method for performing continuous codeposition on Al-Mn alloy plating layer in molten salt system |
| CN102154661A (en) * | 2011-03-22 | 2011-08-17 | 中国科学院过程工程研究所 | Method for preparing aluminum ingot by low-temperature electrolysis of metal monocrystal surface electrodes |
| CN104694974A (en) * | 2015-02-13 | 2015-06-10 | 中国科学院高能物理研究所 | Electrolysis preparation method of uranium-aluminum alloy and fused salt thereof |
| WO2015179973A1 (en) * | 2014-05-26 | 2015-12-03 | Procede Ethanol Vert Technologie | Process for pure aluminum production from aluminum-bearing materials |
-
2017
- 2017-02-17 CN CN201710087088.9A patent/CN108456897B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798140A (en) * | 1973-02-01 | 1974-03-19 | Us Interior | Process for producing aluminum and silicon from aluminum silicon alloys |
| US4846943A (en) * | 1986-06-06 | 1989-07-11 | Lilliwyte Societe Anonyme | Manufacture of an alkali metal aluminum halide compound and alkali metal |
| CN102061490A (en) * | 2010-12-24 | 2011-05-18 | 淄博德丰化工有限公司 | Method for performing continuous codeposition on Al-Mn alloy plating layer in molten salt system |
| CN102154661A (en) * | 2011-03-22 | 2011-08-17 | 中国科学院过程工程研究所 | Method for preparing aluminum ingot by low-temperature electrolysis of metal monocrystal surface electrodes |
| WO2015179973A1 (en) * | 2014-05-26 | 2015-12-03 | Procede Ethanol Vert Technologie | Process for pure aluminum production from aluminum-bearing materials |
| CN104694974A (en) * | 2015-02-13 | 2015-06-10 | 中国科学院高能物理研究所 | Electrolysis preparation method of uranium-aluminum alloy and fused salt thereof |
Non-Patent Citations (1)
| Title |
|---|
| 厉衡隆 等: "《铝冶炼生产技术手册（下册）》", 31 July 2011, 冶金工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108456897B (en) | 2020-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100562608C (en) | A kind of preparation method of high rare-earth content magnesium master alloy | |
| CN101724769B (en) | Rare earth aluminum alloy, and method and device for preparing same | |
| CN1936085B (en) | Method for preparing aluminium and aluminium alloy by low temperature molten-salt electrolysis | |
| CN107130264B (en) | A kind of method of nearly room temperature electrolytic preparation aluminium-based rare-earth alloy | |
| CN108138343B (en) | Metal refining method using electrolytic reduction and electrolytic refining process | |
| JP3927238B2 (en) | Production method of rare earth metals | |
| CN109055994A (en) | A kind of method of titanium-containing blast furnace slag serialization electrolytic preparation high purity titanium | |
| CN103572318A (en) | Deoxidized anode, fluoride fused salt electrolysis deoxidizing device and electrolytic method | |
| CN103498060B (en) | Method for preparing metal vanadium | |
| CN105648465A (en) | Method for preparing tungsten carbide through molten salt electrolysis | |
| CN107557817A (en) | The method of electrolytic preparation aluminium-scandium alloy | |
| CN112921360B (en) | Method for preparing rare earth metal by molten salt electrolysis | |
| EP3327178B1 (en) | Spent fuel dry post-treatment method for directly obtaining zirconium alloy fuel | |
| CN108456897A (en) | For the silicon source of electrolytic preparation aluminium-containing alloy, preparation method and the method for preparing aluminium-containing alloy using it | |
| CN113279022B (en) | Reducing molten salt medium and preparation method thereof | |
| CN107034487B (en) | A kind of rare earth molten-salt electrolysis matter and electrolysis method for production | |
| CN107502923A (en) | The preparation method of aluminium-scandium alloy | |
| CN112725841A (en) | Rare earth alloy material and preparation method thereof | |
| CN101994133B (en) | Molten salt system for dry post-treatment of oxide spent fuel | |
| Piper et al. | Electrolytic production of uranium metal from uranium oxides | |
| CN216304003U (en) | Device for preparing metal by thermally reducing metal oxide with alkali metal | |
| CN112921362B (en) | Method for preparing rare earth alloy by molten salt electrolysis | |
| CN102628131B (en) | Aluminum lutecium ytterbium alloy and method for preparing same through molten salt electrolysis | |
| RU2450373C2 (en) | Method of nuclear fuel synthesis for power fast neutron reactors with reactor core from molten salt | |
| CN114016083A (en) | Method for regenerating alkali metal reducing agent in process of preparing metal by thermally reducing metal oxide with alkali metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |