CN104213153A - Method for electrolytic preparation of magnesium alloy by using hydrated magnesium chloride as raw material - Google Patents

Abstract

The invention provides a method for electrolytic preparation of a magnesium alloy by using hydrated magnesium chloride as a raw material. The method comprises the steps: (a) evenly mixing hydrated magnesium chloride, compounds of other metal elements in the magnesium alloy, ammonium chloride, potassium chloride and an additive to prepare a mixture, wherein the compounds of the other metal elements in the magnesium alloy are selected from one of the group consisting of the following components: chlorides of the other metal elements in the magnesium alloy, oxides of the other metal elements in the magnesium alloy, and chlorides and oxides of the other metal elements in the magnesium alloy; (b) heating the mixture prepared in the step (a) to a molten state, to prepare an electrolyte melt; and (c) electrolyzing the electrolyte melt prepared in the step (b) to obtain the magnesium alloy. The method is simple in process, capable of continuous production, high in degree of automation, easy to operate and control, and good in environmental protection property, at the same time, omits production processes of metal magnesium and alloy-used metals, overall shortens the manufacturing process of the magnesium alloy, and reduces emissions and energy consumption.

Description

Utilize hydrated magnesium chloride for the method for raw material electrolytic preparation magnesium alloy

Technical field

The invention belongs to reasonable offer field, particularly, relate to a kind of preparation method of magnesium alloy, particularly relate to a kind of hydrated magnesium chloride that utilizes for the method for raw material electrolytic preparation magnesium alloy.

Background technology

Magnesium alloy because its density is little, specific tenacity and specific rigidity is high, damping property is good, easy recovery etc. is excellent performance, make it have a wide range of applications in the industry such as automobile industry, aerospace, 21 century " time substituting metal " will be become.

At present, magnesium alloy preparation method has following several:

(1) to the method for mixing.It is added after pre-treatment in smelting furnace at MAGNESIUM METAL and various metallic element, carries out melting and make its alloying under the protections such as flux, and then obtained magnesium alloy.The method technique is simple, is current industrial conventional method, but, because the fusing point of MAGNESIUM METAL is compared with low (649 DEG C), the little (1.6g/cm of density ³), if the fusing point of alloy metal is high, density is large and in aluminium alloy solubleness little, it is serious to adopt the magnesium alloy segregation prepared in this way, and alloying effect is poor; Moreover for the alloy metal that chemically reactive is strong, it is serious to adopt alloy metal loss when preparing magnesium alloy in this way.Reference 1 (Ai Yanling; " microstructure and crystallographic analysis containing Ca, Si magnesium alloy " [Ph.D. Dissertation]; Guangzhou: South China Science & Engineering University; 2004:20-41) with MAGNESIUM METAL and calcium metal for raw material; first magnesium ingot is melted in alloy smelting furnace under the condition of gas shield; add calcium metal when temperature being risen to 650 DEG C fully to stir; then temperature is risen to 720 DEG C and leave standstill obtained magnesium alloy; its interalloy is by stir or thermodiffusion reaches and mixes more difficult after heating and melting, and alloy exists segregation phenomena.Reference 2 (CN102220505), on the basis of the method for mixing, carries out supersound process, reduces component segregation and the oxide inclusion of magnesium lanthanum alloy in the process of heating.

(2) cathode alloy method.It is using MAGNESIUM METAL or magnesium alloy as negative electrode, in molten salt electrolyte, under DC electric field effect, metal ion is to cathodic migration, diffusion, and electrochemical reduction is carried out on negative electrode, the metal that negative electrode is separated out and negative electrode carry out alloying, obtained required magnesium alloy.Such as, reference 3 (Ren Chunxu, Zhang Kangning, " magnesium catholyte-vacuum distillation method prepares neodymium metal ", China rare earth journal, 1986,4 (4): 73-76) using liquid metal magnesium as negative electrode, with NdCl ₃-KCl-NaCl is ionogen (wherein NdCl ₃content be 20%), cathode current density is 1.5A/cm ², at 820 DEG C ± 20 DEG C, carry out electrolysis, in the mg-nd alloy obtained, neodymium content can reach about 30%, and current efficiency is 65%-70%.Reference 4 (Li Ping, Sun Jinye etc., " sinking negative electrode fused salt electrolysis process produces yttrium-rich RE-magnesium alloy ", China rare earth journal, 1987,5 (2): 55-59) negative electrode is made, RE (Y) Cl with the magnesium alloy containing yttrium-rich RE being 10wt% ₃-NaCl-KCl is ionogen (content of rare earth is 15-20%), and cathode current density is 1-1.5A/cm ²condition under, obtain the yttrium-rich RE magnesium alloy of 20-30% at 750 DEG C by electrolysis.Reference 5 (CN1908238A) is adopted in this way, with Lithium chloride (anhydrous) and Repone K for ionogen fused salt prepared by raw material, with magnesium rod for negative electrode, carry out electrolysis at 450 ~ 480 DEG C, metallic lithium is deposited on negative electrode magnesium surface and internally diffusion obtains magnesium lithium alloy.The advantage of the method is that alloying constituent segregation is little, burning loss of alloy is little; Weak point is that negative electrode needs to change in time, not easily carries out continuous prodution, is difficult to industrialization; In addition, MAGNESIUM METAL or magnesium alloy negative electrode are prepared separately, increase technical process like this, add cost.

(3) fused salt electrolysis codeposition method.It is the ionogen fused salt being contained Magnesium Chloride Anhydrous and alloy metal ion by electrolysis, and common deposition realizes alloying, and then obtained magnesium alloy.The advantage of the method is that the segregation of (a) alloying constituent is little, burning loss of alloy is little; B () is suitable for the magnesium alloy that MAGNESIUM METAL and alloy melting point metal difference are large, density difference is large and prepares; (c) continuous prodution.The key link of the method is the preparation of the high-quality ionogen fused salt containing Magnesium Chloride Anhydrous and alloy metal ion, current employing Magnesium Chloride Anhydrous and some anhydrous metal inorganic salt prepare ionogen fused salt, but Magnesium Chloride Anhydrous and some anhydrous metal inorganic salt complicated process of preparation, production cost is high, makes the method prepare the commercialization difficulty of magnesium alloy.

Reference 6 (Ren Yonghong, " rare earth Progress & New Products " [M]. China rare earth association compiles, 2000:216-220) adopt CeCl ₃crystallization material and anhydrous MgCl ₂for raw material, with CeCl ₃-MgCl ₂-KCl is ionogen (CeCl ₃/ MgCl ₂/ KCl=(25-35/ (3-5)/(60-70), mass ratio), cathode current density is 900-920 DEG C, and prepared the magnesium cerium alloy containing cerium 40-60%, current efficiency reaches 75%.Reference 7 (Xu Guangxian, " rare earth " (middle volume) [M]. Beijing: metallurgical industry press, 2002,189-190), with YCl ₃-MgCl ₂-KCl is ionogen, at 900 DEG C, carry out electrolysis, obtains containing the magnesium yittrium alloy that yttrium amount is about 60%, and current efficiency is 70%.Above method adopts anhydrous rare-earth chlorination and Magnesium Chloride Anhydrous as raw material, and the dehydration of anhydrous rare-earth chlorination and Magnesium Chloride Anhydrous is complicated, considerably increases cost.The method utilizing chloride hydrate raw material to prepare magnesium-rare earth is described in detail: first the mixture of Repone K, Magnesium Chloride Anhydrous and anhydrous chlorides of rase earth elements is carried out electrolysis and open stove in reference 8 (CN102220607A), then the compound containing hydrated magnesium chloride and moisture rare earth chloride is added, electrolysis is carried out, obtained magnesium-rare earth at 820-1100 DEG C.But, at high temperature add hydrated magnesium chloride and hydrated lanthanum chloride, serious (the reference 9: Han Jilong of both hydrolysis, Sun Qingguo etc., " vacuum dehydration method prepares the research of anhydrous cerium chloride ", inorganic chemicals industry, 2009,10:25-26), thus seriously reduce the current efficiency of electrolytic process; In addition, the method electrolysis temperature is too high, increases operation difficulty, adds the cost of electrolysis.

Reference 10 and 11 (Cao P, Zhang ML etc., prepared (Electrochemical Preparation of Mg-Li-Zn-Mn Alloys by Codeposition) by the electrochemistry of the Mg-Li-Zn-Mn alloy of codeposition, metallurgy and material journal B (Metallurgical and Materials Transactions B), 2011,42 (4): 914-920; Ye K, Zhang ML etc., about by electrochemical co-deposition from LiCl-KCl-MgCl ₂-MnCl ₂fused salt prepares research (the Study on the preparation of Mg-Li-Mn alloys by electrochemical codeposition from LiCl-KCl-MgCl of Mg-Li-Mn alloy ₂-MnCl ₂molten salt), Applied Electrochemistry magazine (Journal of applied electrochemistry), 2010,40 (7): 1387-1393) the anhydrous raw material such as Magnesium Chloride Anhydrous and Manganese chloride anhydrous is utilized by electrolytic codeposition of nickel legal system for Mg-Li-Zn-Mn alloy and Mg-Li-Mn alloy.The use of Magnesium Chloride Anhydrous and Manganese chloride anhydrous has increased considerably cost.

The preparation of magnesium lithium calcium alloy is described in detail: take inert metal as negative electrode in reference 12 (CN101148773), take graphite as anode, the mixture of Repone K, lithium chloride and Calcium Fluoride (Fluorspan) to be joined in electrolyzer after hot melt as ionogen, magnesium oxide powder is added and melting again according to 2% of ionogen total mass, be 450-640 DEG C at electrolysis temperature, cathodic current intensity is not less than 5A/cm ³, bath voltage is carry out electrolysis under 4.5-6.5V condition, and electrolytic process argon gas is protected, and often in electrolyzer, adds material oxidation magnesium at regular intervals.The method utilizes Calcium Fluoride (Fluorspan) dissolved oxygen magnesium in fused salt, but magnesium oxide meltage is little, magnesian addition is also subject to great restriction (magnesium oxide is the detrimental impurity of electrolysis), consider every physical and chemical performance of fused salt simultaneously, the addition of Calcium Fluoride (Fluorspan) is restricted, disadvantageous effect may be brought to electrolysis, cause current efficiency to reduce.

Reference 13 (Cao Peng, " polynary codeposition Mg-Li-X (X=Sn; La; Zn-Mn) alloy and study mechanism " [Ph.D. Dissertation]. Harbin: Harbin Engineering University, 2012:61-71) utilize Magnesium Chloride Anhydrous, lithium chloride and zinc chloride for raw material, in LiCl-KCl molten salt system, add the magnesium chloride of 9.0wt.%, the zinc chloride of 0.3-0.4wt.%, the Manganous chloride tetrahydrate of 0.2-0.3wt.%, by electrolytic codeposition of nickel legal system for Mg-Li-Zn-Mn alloy.(Yan YD, Zhang ML etc., by electrochemical co-deposition from LiCl-KCl-MgCl for reference 14 ₂-ZnCl ₂melt prepares research (the Study on the preparation of Mg-Li-Zn alloys by electrochemical codeposition from LiCl-KCl-MgCl of Mg-Li-Zn alloy ₂-ZnCl ₂melts), Electrochimica Acta, 2009,54 (12): 3387-3393) Magnesium Chloride Anhydrous and zinc chloride is utilized to be raw material, add (LiCl50wt.% in LiCl-KCl molten salt system, KCl50wt.%), by the standby Mg-Li-Zn alloy of electrolytic codeposition of nickel legal system.Reference 14 (Liu Ruiguo, " Mg-Zr and Mg-Zn-Zr alloy prior and cathodic process research are prepared in fused salt electrolysis " [Ph.D. Dissertation]: Harbin Engineering University, Magnesium Chloride Anhydrous and zinc chloride 2011:15-16) is adopted to be raw material, with MgCl ₂-KCl-K ₂zrF ₆-ZnCl ₂for ionogen (wherein MgCl ₂30wt.%, ZnCl ₂1wt.%), be 6.4Acm in current density ^-2condition under the Mg-Zr-Zn alloy of obtained zinc content 3.55-47.42%.

With RECl ₃-LiCl-KCl-MgCl ₂for ionogen, realize rare earth metal, metallic lithium and MAGNESIUM METAL by regulating voltage and electric current and jointly deposit.Reference 15 (Cao P, Zhang ML etc., the electrochemical behavior of erbium and prepare Mg-Li-Er alloy (Electrochemical behaviour of erbium and preparation of Mg-Li-Er alloys by codeposition) by codeposition, rare earth magazine (Journal of Rare Earths), 2011,29 (8): 763-767) KCl, anhydrous LiCl, anhydrous MgCl is utilized ₂and K ₃erCl ₆for raw material, be prepared into KCl-10wt.%MgCl ₂-4wt.%K ₃erCl ₆melt.After carrying out electrolysis at 600 DEG C, prepare Mg-Li-Er alloy.(Han W, Tian Y etc., by LiCl-KCl-MgCl for reference 16 ₂-SmCl ₃out of phase Mg-Li-Sm alloy (Preparing different phases of Mg-Li-Sm alloys by molten salt electrolysis in LiCl-KCl-MgCl is prepared in fused salt electrolysis in melt ₂-SmCl ₃melts), rare earth magazine (Journal of Rare Earths), 2010,28 (2): 227-231) utilize KCl, anhydrous LiCl, anhydrous MgCl ₂with anhydrous SmCl ₃for raw material, obtain the alloy of Mg-Li-Sm at 670 DEG C by electrolysis.Reference 17 (Zheng Tao, " Mg-Li-RE (Pr, Ho, Er) alloy study mechanism is prepared in fused salt electrolysis " [Master's thesis], Harbin: Harbin Engineering University 2011:47-51) utilizes KCl, anhydrous LiCl, anhydrous MgCl ₂and K ₃rECl ₆(RE=Pr, Ho, Er) is prepared into KCl-MgCl ₂-LiCl-K ₃rECl ₆melt, obtain the alloy of Mg-Li-RE at 700 DEG C by electrolytic preparation.Above electrolytic process, owing to utilizing Magnesium Chloride Anhydrous, Lithium chloride (anhydrous) and anhydrous rare-earth chlorination, makes the preparation cost of alloy greatly increase.

Fused salt electrolysis codeposition legal system is for magnesium alloy advantages, and it demonstrates has industrialization and business-like feasible prospect.The key issue of restriction the method commercial applications is exactly: preparation is containing the high-quality electrolyte melt of other metal ion in anhydrous chlorides of rase Magnesium and magnesium alloys economically.The preparation of current this electrolyte melt adopts Magnesium Chloride Anhydrous and anhydrous metal inorganic salt to be that raw material carries out, and Magnesium Chloride Anhydrous and some anhydrous metal inorganic salt preparation process complexity, production cost is high, constrains the commercialization that the method prepares magnesium alloy like this.

Summary of the invention

Based on the problems referred to above, present inventor has performed intensive research, provide a kind of hydrated magnesium chloride that utilizes for the method for raw material electrolytic preparation magnesium alloy.The method does not adopt Magnesium Chloride Anhydrous and some anhydrous metal inorganic salt as raw material, but adopt hydrated magnesium chloride and hydrated metal inorganic salt or oxide compound to be raw material (this raw material is easy to get, cost low), to dewater the high-quality electrolyte melt prepared containing other metal ion in anhydrous chlorides of rase magnesium and its alloys by forming double salt-fused salt, then going out magnesium alloy by electrolytic preparation.Can under relatively simple processing condition by described method, electrolytic codeposition of nickel high-quality electrolyte melt containing Magnesium Chloride Anhydrous and alloying metal ions can be prepared in certain preferred circumstances (in the Magnesium Chloride Anhydrous of 100 % by weight, content of MgO is less than 0.1 % by weight), it meets advanced electrolyzer requirement, in electrolytic process, current efficiency is more than 80%, having good uniformity of alloying element.

Particularly, the invention provides a kind of hydrated magnesium chloride that utilizes for the method for raw material electrolytic preparation magnesium alloy, described method comprises the following steps:

A (), by the compound of other metallic element in hydrated magnesium chloride, magnesium alloy, ammonium chloride, Repone K and additive Homogeneous phase mixing to prepare mixture, in wherein said magnesium alloy, the compound of other metallic element is selected from the one in the group be made up of the following: the muriate of other metallic element in described magnesium alloy; The oxide compound of other metallic element in described magnesium alloy; With muriate and the oxide compound of other metallic element in described magnesium alloy;

B the described mixture of preparation in step (a) is heated to molten state, to prepare the electrolyte melt containing other metal ion in Magnesium Chloride Anhydrous and described magnesium alloy by (); With

C () is by the described electrolyte melt electrolysis of preparation in step (b) thus obtained described magnesium alloy.

Compared with prior art, the invention has the advantages that: (1) electrolytic preparation magnesium alloy raw material used is hydrated magnesium chloride and hydrated metal inorganic salt muriate and/or oxide compound, and this raw material is easy to get, cost is low; (2) prepared the electrolytic codeposition of nickel high-quality electrolyte melt (in Magnesium Chloride Anhydrous, content of MgO is less than 0.1 % by weight) containing other metal ion in anhydrous chlorides of rase Magnesium and magnesium alloys, it meets advanced electric tank working requirement; (3) obtained magnesium alloy component segregation is little, burning loss of alloy is little; (4) efficiently solve the problem that fusing point difference is large, density difference is difficult to greatly alloying due to MAGNESIUM METAL and alloy metal, and reduce the production cost of this kind of magnesium alloy; (5) technique is simple, and continuous prodution, level of automation is high, easy operation control, and the feature of environmental protection is good.

In addition, with current industrial usual employing to compared with the method for mixing, method of the present invention eliminates the production process of MAGNESIUM METAL and alloy metal, and entirety shortens the manufacturing processed of magnesium alloy and reduces discharge and energy consumption.

Accompanying drawing explanation

Fig. 1 is the process flow sheet according to the inventive method;

Fig. 2 is the element Surface scan figure of magnesium lithium alloy prepared according to the methods of the invention;

Fig. 3 is the XRD figure of magnesium lithium alloy prepared according to the methods of the invention;

Fig. 4 is the energy spectrum analysis figure of magnesium lanthanum alloy prepared according to the methods of the invention;

Fig. 5 is the element Surface scan figure of magnesium lanthanum alloy prepared according to the methods of the invention;

Fig. 6 is the XRD figure of magnesium lanthanum alloy prepared according to the methods of the invention;

Fig. 7 is the element Surface scan figure of magnesium-zinc alloy prepared according to the methods of the invention;

Fig. 8 is the energy spectrum analysis figure of magnesium-zinc alloy prepared according to the methods of the invention;

Fig. 9 is the XRD figure of magnesium-zinc alloy prepared according to the methods of the invention;

Figure 10 is the element Surface scan figure of magnesium-manganese alloy prepared according to the methods of the invention;

Figure 11 is the energy spectrum analysis figure of magnesium-manganese alloy prepared according to the methods of the invention;

Figure 12 is the XRD figure of magnesium-manganese alloy prepared according to the methods of the invention;

Figure 13 is the element Surface scan figure of magnesium calcium alloy prepared according to the methods of the invention;

Figure 14 is the XRD figure of magnesium calcium alloy prepared according to the methods of the invention;

Figure 15 is the element Surface scan figure of magnesium zinc calcium alloy prepared according to the methods of the invention;

Figure 16 is the XRD figure of magnesium zinc calcium alloy prepared according to the methods of the invention;

Figure 17 is the element Surface scan figure of magnesium lithium lanthanum alloy prepared according to the methods of the invention;

Figure 18 is the energy spectrum analysis figure of magnesium lithium lanthanum alloy prepared according to the methods of the invention; With

Figure 19 is the XRD figure of magnesium lithium lanthanum alloy prepared according to the methods of the invention.

Embodiment

In the present invention, unless otherwise noted, term " hydrated magnesium chloride " refers to the magnesium chloride (MgCl containing crystal water ₂mH ₂o, wherein m represents the number of the crystal water contained in hydrated magnesium chloride described in per molecule, m > 0).Term " in magnesium alloy other metallic element " refers to the metallic element except MAGNESIUM METAL element in magnesium alloy, and the manganese metal element in such as magnesium manganese (Mg-Mn) alloy is " in magnesium alloy other metallic element ".Term " electrolyte melt containing other metal ion in Magnesium Chloride Anhydrous and described magnesium alloy " refers to that prepared according to the methods of the invention other metal ion that to comprise in anhydrous chlorides of rase magnesium and its alloys is as the electrolyte melt of main component, except other metal ion in anhydrous chlorides of rase magnesium and its alloys, this electrolyte melt can also comprise Repone K, calcium chloride, sodium-chlor, bariumchloride, Calcium Fluoride (Fluorspan), Potassium monofluoride, lithium fluoride, magnesium fluoride, Sodium Fluoride etc.Term " waste cell melt " refers to the ionogen that in electrolyte melt, the weight percentage of Magnesium Chloride Anhydrous is less than 1%.Term " correction factor " refers in electrolytic preparation magnesium alloy process of the present invention, in order to the activity value that adjusts other metal ion in the magnesium alloy in electrolyte melt is to meet the composition of target magnesium alloy and the correction factor introduced, or in order to the physicochemical property that adjust electrolyte melt so that the electrolytic process correction factor that well runs and introduce.

In addition, in the present invention, unless otherwise noted, magnesium oxide (MgO) content in the described electrolyte melt containing other metal ion in Magnesium Chloride Anhydrous and described magnesium alloy refers to the magnesian weight percentage for the Magnesium Chloride Anhydrous of 100 % by weight.

Particularly, the invention provides a kind of hydrated magnesium chloride that utilizes for the method for raw material electrolytic preparation magnesium alloy, described method comprises the following steps:

A (), by the compound of other metallic element in hydrated magnesium chloride, magnesium alloy, ammonium chloride, Repone K and additive Homogeneous phase mixing to prepare mixture, in wherein said magnesium alloy, the compound of other metallic element is selected from the one in the group be made up of the following: the muriate of other metallic element in described magnesium alloy; The oxide compound of other metallic element in described magnesium alloy; With muriate and the oxide compound of other metallic element in described magnesium alloy;

B the described mixture of preparation in step (a) is heated to molten state, to prepare the electrolyte melt containing other metal ion in Magnesium Chloride Anhydrous and described magnesium alloy by (); With

C () is by the described electrolyte melt electrolysis of preparation in step (b) thus obtained described magnesium alloy.

According to certain embodiments of the present invention, wherein in step (a), in described magnesium alloy, other metallic element is selected from one or more in following elements: rare earth element, zinc, aluminium, manganese, lithium, calcium, zirconium, silver, strontium, antimony, cadmium, thorium, beryllium, lead and gallium etc.

According to certain embodiments of the present invention, wherein in step (a), in described magnesium alloy, the muriate of other metallic element is selected from one or more in following muriate: rare earth element muriate, zinc chloride, aluminum chloride, Manganous chloride tetrahydrate, lithium chloride, calcium chloride, zirconium chloride, silver chloride, strontium chloride, antimony chloride, Cadmium chloride fine powder, Thorium tetrachloride, beryllium chloride, lead chloride and gallium chloride etc.

According to certain embodiments of the present invention, wherein in step (a), in described magnesium alloy, the oxide compound of other metallic element has to react to ammonium chloride and generates corresponding muriatic chemical property, and is selected from one or more in following oxide compound: rare earth oxide, calcium oxide, manganese oxide and weisspiessglanz etc.

According to certain embodiments of the present invention, wherein in step (a), described additive be selected from the following one or more: CaF ₂, KF, NaF, LiF, MgF ₂, CaCl ₂, BaCl ₂with NaCl etc., the effect of described additive is the physicochemical property regulating electrolyte melt, so that electrolytic process well runs.

According to certain embodiments of the present invention, wherein said hydrated magnesium chloride is expressed from the next: MgCl ₂mH ₂o, wherein m represents the number of the crystal water contained in hydrated magnesium chloride described in per molecule, m > 0.

In step (a) when in described magnesium alloy, other metallic element compound is muriate, in hydrated magnesium chloride, magnesium alloy, the principle of the mixture composition and ratio of the muriate of other metallic element, ammonium chloride, Repone K and additive is: first, according to the muriatic consumption of other metallic element in the weight percentage determination hydrated magnesium chloride consumption of metallic element in magnesium alloy, magnesium alloy, described mixture composition and ratio is 1.00 parts by weight in magnesium chloride (with not containing crystal water) add-on, hydrated magnesium chloride (MgCl ₂mH ₂o) weight part of consumption is (1+0.19m).The weight part of other metallic element muriate consumption in magnesium alloy (in not containing crystal water), in formula: for correction factor, zero dimension, value scope is 0.1 to 145.0; for the weight percentage of other metallic element in magnesium alloy; M _icfor the nucleidic mass of other metallic element in magnesium alloy; for the valency of metallic element in other metallic element muriate in magnesium alloy.According to the weight part of other metallic element muriatic water content determination ammonium chloride consumption in chloride hydrate Magnesium and magnesium alloys be greater than in formula: β is the weight ratio of water and Magnesium Chloride Anhydrous in hydrated magnesium chloride, β _ifor the weight ratio of water and anhydrous chloride in the muriate of other metallic element in magnesium alloy.The weight part of the consumption determination potassium chloride dosage of the anhydrous chloride of other metallic element in the amount of Magnesium Chloride Anhydrous and magnesium alloy is converted into according to hydrated magnesium chloride in formula: Z1 is correction factor, zero dimension, Z1 value scope is 0.05 to 150.00.The weight part of additive amount $W_{\mathrm{ad}}^c,$ $W_{\mathrm{ad}}^c=Z2\×(1.00+\mathrm{\Σ}{W_i}^c+W_{\mathrm{KCl}}^c),$ In formula: Z2 is correction factor, zero dimension, Z2 value scope is 0.005 to 0.500.

In step (a) when in described magnesium alloy, other metallic element compound is oxide compound, in hydrated magnesium chloride, magnesium alloy, the principle of the mixture composition and ratio of the oxide compound of other metallic element, ammonium chloride, Repone K and additive is: first, according to the consumption of other metal oxides in the weight percentage determination hydrated magnesium chloride consumption of metallic element in magnesium alloy, magnesium alloy, described mixture composition and ratio is 1.00 parts by weight in magnesium chloride (with not containing crystal water) add-on, hydrated magnesium chloride (MgCl ₂mH ₂o) weight part of consumption is (1+0.19m).The weight part of other metal oxides consumption in magnesium alloy $W_j^o,$ $W_j^o=0.25\×Z_j^o\×\frac{{\mathrm{\α}}_j^o}{(1-\mathrm{\Σ}{\mathrm{\α}}_j^o)}\×\frac{(M_{\mathrm{jo}}+8n_j^o)}{M_{\mathrm{jo}}},$ In formula: $Z_j^o$ For correction factor, zero dimension, value scope is 0.05 to 100.00; for the weight percentage of other metallic element in magnesium alloy; M _jofor the nucleidic mass of other metallic element in magnesium alloy; for the valency of metallic element in other metal oxides in magnesium alloy.The weight part of ammonium chloride consumption is determined according to the amount of other metal oxides in the water content of hydrated magnesium chloride and magnesium alloy be greater than in formula: β is the weight ratio of water and Magnesium Chloride Anhydrous in hydrated magnesium chloride.The oxygenate conversion being converted into other metallic element in the amount of Magnesium Chloride Anhydrous and magnesium alloy according to hydrated magnesium chloride is the weight part that the amount of anhydrous chloride determines potassium chloride dosage $W_{\mathrm{KCl}}^o=0.78+Z3\×\mathrm{\Σ}(0.25\×Z_j^o\×\frac{{\mathrm{\α}}_j^o\×(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\Σ}{\mathrm{\α}}_j^o)\×M_{\mathrm{jo}}})$ , in formula: Z3 is correction factor, zero dimension, Z3 value scope is 0.05 to 150.00.The weight part of additive amount $W_{\mathrm{ad}}^o=Z4$ $\×(1.00+\mathrm{\Σ}(0.25\×Z_j^o\×\frac{{\mathrm{\α}}_j^o\×(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\Σ}{\mathrm{\α}}_j^o)\×M_{\mathrm{jo}}})+W_{\mathrm{KCl}}^o),$ In formula: Z4 is correction factor, zero dimension, Z4 value scope is 0.005 to 0.500.

In step (a) when other metallic element compound in described magnesium alloy be muriate and oxide compound time, hydrated magnesium chloride, other metallic element muriate and oxide compound in magnesium alloy, ammonium chloride, the principle of the mixture composition and ratio of Repone K and additive is: first, according to the weight percentage determination hydrated magnesium chloride consumption of metallic element in magnesium alloy, the consumption of other metallic element muriate and oxide compound in magnesium alloy, described mixture composition and ratio is 1.00 parts by weight in magnesium chloride (with not containing crystal water) add-on, hydrated magnesium chloride (MgCl ₂mH ₂o) weight part of consumption is (1+0.19m).When in magnesium alloy other metallic element introduce with its muriate for raw material time, the weight part of its muriate consumption $W_i^c$ (in not containing crystal water), ${W_i}^c=0.25\×Z_i^c\×\frac{{\mathrm{\α}}_i^c\×(M_{\mathrm{ic}}+35.5n_i^c)}{(1-\mathrm{\Σ}{\mathrm{\α}}_i^c-\mathrm{\Σ}{\mathrm{\α}}_j^o)\×M_{\mathrm{ic}}},$ In formula: $Z_i^c$ For correction factor, zero dimension, value scope is 0.1 to 145.0; for the weight percentage of other metallic element in magnesium alloy (referring to other metallic element introduced with muriate raw material); for the weight percentage of other metallic element in magnesium alloy (referring to other metallic element introduced with oxide raw material); M _icfor the nucleidic mass (referring to other metallic element introduced with muriate raw material) of other metallic element in magnesium alloy; for the valency of other metallic element in anhydrous chloride in magnesium alloy (referring to other metallic element introduced with muriate raw material).When in magnesium alloy other metallic element introduce with its oxide compound for raw material time, the weight part of its oxide compound consumption $W_j^o=0.25\×Z_j^o\×\frac{{\mathrm{\α}}_j^o}{(1-\mathrm{\Σ}{\mathrm{\α}}_i^c-\mathrm{\Σ}{\mathrm{\α}}_j^o)}\×\frac{(M_{\mathrm{jo}}+8n_j^o)}{M_{\mathrm{jo}}},$ In formula: $Z_j^o$ For correction factor, zero dimension, value scope is 0.05 to 100.00; M _jofor the nucleidic mass (referring to other metallic element introduced with oxide raw material) of other metallic element in magnesium alloy; for the valency (referring to other metallic element introduced with oxide raw material) of metallic element in the oxide compound of other metallic element in magnesium alloy.The weight part of ammonium chloride consumption is determined according to the amount of other metal oxides in the muriatic water content of other metallic element, magnesium alloy in the water content of hydrated magnesium chloride, magnesium alloy be greater than $(0.10\×\mathrm{\β}+$ $0.08\×\mathrm{\Σ}({\mathrm{\β}}_i\·{W_i}^c)+\mathrm{\Σ}\frac{13.37\×Z_j^o\×n_j^o\×{\mathrm{\α}}_j^o}{(1-\mathrm{\Σ}{\mathrm{\α}}_i^c-\mathrm{\Σ}{\mathrm{\α}}_j^o)\×M_{\mathrm{jo}}}),$ In formula, β is the weight ratio of water and Magnesium Chloride Anhydrous in hydrated magnesium chloride; β _ifor the weight ratio of water and anhydrous chloride in the muriate of other metallic element in magnesium alloy (referring to other metallic element introduced with muriate raw material).Be converted into other metal oxides in the amount of the anhydrous chloride of other metallic element in the amount of Magnesium Chloride Anhydrous, magnesium alloy and magnesium alloy according to hydrated magnesium chloride and be converted into the amount of anhydrous chloride, determine the weight part of potassium chloride dosage $W_{\mathrm{KCl}}^{\mathrm{co}}=0.78+Z5\·(\mathrm{\Σ}{W_i}^c+\mathrm{\Σ}(0.25\×Z_j^o\×\frac{{\mathrm{\α}}_j^o(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\Σ}{\mathrm{\α}}_i^c-\mathrm{\Σ}{\mathrm{\α}}_j^o)\×M_{\mathrm{jo}}})),$ In formula, Z5 is correction factor, zero dimension, and Z5 value scope is 0.05 to 150.00.The weight part of additive amount $W_{\mathrm{ad}}^{\mathrm{co}}=Z6\×(1.00+\mathrm{\Σ}{W_i}^c+\mathrm{\Σ}(0.25\×Z_j^o\×\frac{{\mathrm{\α}}_j^o\×(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\Σ}{\mathrm{\α}}_i^c-\mathrm{\Σ}{\mathrm{\α}}_j^o)\×M_{\mathrm{jo}}})+$ $W_{\mathrm{KCl}}^{\mathrm{co}}),$ In formula: Z6 is correction factor, zero dimension, Z6 value scope is 0.005 to 0.500.

According to certain embodiments of the present invention, wherein in step (b), described heat-processed is: first in 200 ~ 550 DEG C (preferably 300 ~ 450 DEG C) insulation, 0.5 ~ 4.5 hour (preferably 1 ~ 3 hour), then in 400 ~ 850 DEG C (preferably 450 ~ 750 DEG C) insulation, 0.2 ~ 4.0 hour (preferably 1 ~ 2.5 hour), with the obtained electrolyte melt containing other metal ion in anhydrous chlorides of rase magnesium and its alloys.

According to certain embodiments of the present invention, wherein in step (c), the condition of described electrolysis is: anode is made up of graphite material, and negative electrode is made up of steel; During electrolysis, temperature is 400 ~ 850 DEG C (preferably 400 ~ 700 DEG C), and electrolysis voltage is 5 ~ 10V, and cathode current density is greater than 3A/cm ².

Negative electrode is made up of steel, and it is solid-state form, can adopt common commercial products, is preferably the steel that carbon content is less than 0.2wt%.Anode is made up of graphite material, and it is solid-state form, can adopt common commercial products; In electrolytic process, anode separates out chlorine.

According to certain embodiments of the present invention, the ammonia nitrogen recovery wherein step (b) discharged turning back in step (a) recycles, and the Ammonia recovery that will discharge utilizes.

According to certain embodiments of the present invention, wherein the waste cell melt melt of discharging in the electrolytic process of step (c) is turned back in step (a) and recycle, and the chlorine of generation is utilized through Recovery Purifying.

For in the present invention adopt raw material (e.g., the muriate of other metallic element and oxide compound, ammonium chloride, Repone K etc. in hydrated magnesium chloride, magnesium alloy) to be not specifically limited, they all can adopt common commercial products.The preferred powder morphology of described raw material, is not particularly limited described powder diameter, only otherwise affect its Homogeneous phase mixing.

In the magnesium alloy adopted in the present invention, the muriate of other metallic element is not limited to the pointed muriate such as rare earth element muriate, zinc chloride, aluminum chloride, Manganous chloride tetrahydrate, lithium chloride, calcium chloride, zirconium chloride, silver chloride, strontium chloride, antimony chloride, Cadmium chloride fine powder, Thorium tetrachloride, beryllium chloride, lead chloride, gallium chloride; In magnesium alloy, the muriate of other metallic element is chloride monohydrate or anhydrous chloride.

In the magnesium alloy adopted in the present invention, the oxide compound of other metallic element has to react to ammonium chloride and generates corresponding muriatic chemical property, is not limited to the oxide compounds such as pointed rare earth oxide, calcium oxide, manganese oxide, weisspiessglanz.

Have employed ammonium chloride and Repone K in the method according to the invention, wherein their effect is as follows:

The effect of ammonium chloride is corresponding muriate by the oxygenate conversion of other metallic element in magnesium alloy, and the hydrogenchloride that ammonium chloride decomposition at a certain temperature produces simultaneously suppresses muriatic hydrolysis to occur, and ensure that the purity of anhydrous chloride.

Repone K, as the main component of molten salt electrolyte, plays following effect: (1) reduces the melt temperature of molten salt electrolyte; (2) to a certain degree molten salt electrolyte electroconductibility can be improved; (3) under suppressing high temperature, molten salt electrolyte is hydrolyzed; (4) Repone K deposition potential is high, and potassium metal is not easily separated out, and does not affect magnesium alloy purity.

For (e.g., the CaF of additive therefor in the present invention ₂, MgF ₂, KF, NaF, LiF, CaCl ₂, BaCl ₂, NaCl) be not specifically limited, they all can adopt common commercial products.The preferred powder morphology of described raw material, is not particularly limited described powder diameter, only otherwise affect its Homogeneous phase mixing.In the present invention, the effect of additive therefor is the physicochemical property regulating electrolyte melt.The physicochemical property of electrolyte melt mainly comprise: the specific conductivity, viscosity, surface tension, melt temperature, density etc. of electrolyte melt.The specific conductivity of electrolyte melt is high, viscosity is low favourable to electrolytic process.Add the specific conductivity that sodium-chlor is conducive to improving electrolyte melt.The adding of fluorochemical be conducive to liquid magnesium alloy in electrolyte melt to collect.For the magnesium alloy of difference composition, regulate the surface tension, melt temperature, density etc. of electrolyte melt according to particular case.

Fig. 1 shows the hydrated magnesium chloride that utilizes according to the present invention for the process flow sheet of the method for raw material electrolytic preparation magnesium alloy.In the above-mentioned methods, a (), by the compound of other metallic element in hydrated magnesium chloride, magnesium alloy, ammonium chloride, Repone K and additive Homogeneous phase mixing by a certain percentage, in wherein said magnesium alloy, the compound of other metallic element is selected from the one in the group be made up of the following: the muriate of other metallic element in described magnesium alloy; The oxide compound of other metallic element in described magnesium alloy; With muriate and the oxide compound of other metallic element in described magnesium alloy; B product that step (a) obtains by (), first 200 ~ 550 DEG C of insulations 0.5 ~ 4.5 hour, is then incubated 0.2 ~ 4.0 hour with the obtained electrolyte melt containing other metal ion in anhydrous chlorides of rase magnesium and its alloys at 400 ~ 850 DEG C; C electrolyte melt obtained for step (b) is 400 ~ 850 DEG C in temperature by (), electrolysis voltage is 5 ~ 10V, and cathode current density is greater than 3A/cm ²condition under carry out electrolysis thus obtained magnesium alloy, electrolytic process discharges waste cell melt melt, produces chlorine simultaneously.The waste cell melt melt of discharging in the electrolytic process of step (c) is turned back in step (a) and recycles, and the chlorine of generation is utilized through Recovery Purifying.

The present inventor be experimental studies have found that by a large amount of, and the mechanism of above-mentioned reaction is as follows: below 300 DEG C, and hydrated magnesium chloride and ammonium chloride react and generates double salt NH ₄clMgCl ₂nH ₂o (0≤n < 6), the structure of double salt reduces the combination of crystal water and magnesium chloride, be conducive to the carrying out dewatered, reduce hydrolysis (the Zhang ZM of dehydration, Lu XC etc., Magnesium Chloride Anhydrous (Preparation of anhydrous magnesium chloride from magnesium chloride hexahydrate) is prepared from Magnesium dichloride hexahydrate, metallurgy and material journal B (Metallurgical and Materials Transactions B), 2013,44 (2): 354-358).Ammonium chloride is all right and hydrolyzed reaction product at a certain temperature, generate Magnesium Chloride Anhydrous (Zhang ZM, Lu XC etc., Magnesium Chloride Anhydrous (Preparation of anhydrous magnesium chloride from magnesia) is prepared from hydrated magnesium chloride, industry & engineering chemistry research (Industrial & Engineering Chemistry Research), 2012,51 (29): 9713-9718).Meanwhile, contriver studies discovery by experiment, when temperature rises to about 300-500 DEG C, forms double salt KMgCl ₃, this double salt is at high temperature more stable, not easily reacts with the oxygen in air and water vapour, inhibits the generation of Magnesium Chloride Anhydrous hydrolysis reaction, ensure that the purity of product.The hydrogen chloride gas decomposing generation under ammonium chloride high temperature can suppress the hydrolysis reaction of other metallic element chloride monohydrate in magnesium alloy effectively, and ammonium chloride can react with hydrolysate at a certain temperature, generate corresponding anhydrous chloride, ensure that the purity of product.Rare earth oxide and ammonium chloride react when temperature is greater than 140 DEG C and generate double salt nNH ₄clRECl ₃(in eight-legged essay, Li Guanfeng, Zhao Yonghe, Zhu Guocai, " ammonium chloride chloride oxidation lanthanum cerium oxide mixture and kinetics thereof ", Xinyang Normal College's journal (natural science edition), 2005,18 (2): 155-158), temperature rises to about 400 DEG C and forms double salt K ₃rECl ₆this double salt is at high temperature more stable, not easily react with the oxygen in air and water vapour, inhibit the generation (Zheng Tao of anhydrous rare-earth chlorination hydrolysis reaction, Mg-Li-RE (Pr is prepared in fused salt electrolysis, Ho, Er) alloy study mechanism [master thesis]. Harbin: Harbin Engineering University, 2011:14-15).Other metal oxide (as calcium oxide, weisspiessglanz, manganese oxide etc.) also can react with ammonium chloride at 300-400 DEG C, generate corresponding anhydrous metal muriate (Shao Yuchang. the reaction of ammonium chloride and application. soda industry, 2008,4:3-12).Contriver studies discovery, and between 200-500 DEG C, chloride mix material sintering shrinkage slow down the effusion speed of ammonium chloride, makes ammonium chloride chemical reaction effect can fully occur.The ammonium chloride of discharging in step (b) is turned back to recycle in step (a), thus reduces production cost, improve productivity.By regulating activity value and the polarization value of magnesium ion and alloying ion in electrolyte melt, making the deposition potential of magnesium ion and alloying ion close or equal, to realize the common deposition of MAGNESIUM METAL and other metal, forming magnesium alloy.

For preparing for magnesium alloy, present method versatility is very strong.Due to magnesium alloy materials progressively widespread use, development potentiality is very large, and the magnesium alloy limitednumber developed at present, the exploitation of novel high-performance magnesium alloy materials exists very large space, and present method is that development of new high-performance magnesium-alloy provides preparation method.

Testing method

Measure containing the electrolyte melt of other metal ion in Magnesium Chloride Anhydrous and described magnesium alloy according to following method.

Titration measuring sample aqueous solution throw out is to determine the magnesian content in the electrolyte melt containing other metal ion in anhydrous chlorides of rase Magnesium and magnesium alloys: soluble in water containing the electrolyte melt sample of other metal ion in anhydrous chlorides of rase Magnesium and magnesium alloys by what obtain, repeatedly filters at least three times with the quantitative paper (Hangzhou Special Paper Industry Co., Ltd.) of four Φ 90mm till filtrate is clarified especially to the aqueous solution.Filter paper deionized water is rinsed repeatedly wash away the magnesium ion adhered to above, putting into beaker by washing the rear filter paper containing magnesium oxide particle, adding sulfuric acid (analytical pure, the purity 95.98% of 1: 100 of excessive preparation; Producer: Beijing North fine chemicals limited liability company), beaker heated and boiled also leaves standstill by electric furnace and within five minutes, makes to react completely.Solution in beaker is carried out EDTA titration to determine the content of magnesium ion, thus obtain magnesian content in electrolyte melt.

According to following method, gained magnesium alloy is characterized.

1. alloy material phase analysis: utilize X-ray diffractometer (model: X ' Pert PRO MPD; Producer: Philips) adopt X-ray diffraction (XRD) to determine the thing phase composite of product.

2. element uniformity analysis: (1) element microcell analysis of Uniformity: utilize mineral disaggregation analyser (model: FEI MLA250; Producer: FEI electron chemistry company of the U.S.) the Quanta250 environmental scanning electronic microscope that carries carries out Surface scan (can not carry out Surface scan to elemental lithium) to the magnesium in sample and other alloying element; (2) element macro-uniformity is analyzed: three different positionss gained alloy sample being about respectively the ecto-entad of 5mm from interval utilize inductively coupled plasma atomic emission spectrometer (model: Optima5300DV; Producer: PerkinElmer company of the U.S.) measure the content of alloying element.

3. energy spectrum analysis: utilize mineral disaggregation analyser (model: FEI MLA250; Producer: FEI electron chemistry company of the U.S.) the EDAX GENESIS energy spectrometer that carries carries out energy spectrum analysis to sample.

4. the calculating of current efficiency: in electrolytic process current efficiency calculate according to the following formula (formula source see document: Wei H, Chen Q etc., by the brand-new standby (New preparation of Mg-Li-Al alloys by electrolysis) of the Mg-Li-Al alloy of electrolysis, Acta Metall.Sin. (Engl.Lett.), 2010,23 (2): 129-136):

$\mathrm{\&eta;}=\frac{F\&times;\mathrm{\&Sigma;}\frac{m\&times;w_i}{M_i}\&times;n_i}{\mathrm{It}}\&times;100\%$

Wherein, the quality of the alloy of m-electrolysis gained, g;

W _ithe mass percentage of-each component metals, %, utilizes icp ms to measure;

M _ithe nucleidic mass of-each component metals;

N _i-each component metals number of electrons in electrode reaction equation;

F-Faraday's number, 26.801Ahmol-l;

I-Faradaic current intensity, A;

T-electrolysis time, h.

Embodiment

For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:

Raw material involved in the present invention is commercially available product, comprising:

Magnesium chloride hexahydrate: Xilong Chemical Co., Ltd, purity >=98.0%;

Seventy flavors pearl pill: Tianjin great Mao chemical reagent factory, purity >=98.0%;

One water lithium chloride: Xilong Chemical Co., Ltd, purity >=97.0%;

Tetrahydrate manganese chloride: Xilong Chemical Co., Ltd, purity >=99.0%;

Zinc chloride: Xilong Chemical Co., Ltd, purity >=98.0%;

Calcium chloride: Xilong Chemical Co., Ltd, purity >=96.0%;

Lanthanum trioxide: Chemical Reagent Co., Ltd., Sinopharm Group, purity >=99.99%;

Calcium oxide: Tianjin chemical reagent company limited of Jin Hui the Pacific-Asian, purity >=99.8%;

Manganese oxide: Guangzhou ten thousand from Chemical Co., Ltd., purity >=99.0%;

Ammonium chloride: Xilong Chemical Co., Ltd, purity >=99.5%;

Repone K: Xilong Chemical Co., Ltd, purity >=99.5%;

Calcium Fluoride (Fluorspan): Chemical Reagent Co., Ltd., Sinopharm Group, purity >=98.5%;

Hydrated magnesium chloride (self-control): heated by above-mentioned magnesium chloride hexahydrate, judge final product according to reduced gravity situations;

Hydrated lanthanum chloride (self-control): heated by above-mentioned seventy flavors pearl pill, judge final product according to reduced gravity situations;

Chloride hydrate lithium (self-control): heated by an above-mentioned water lithium chloride, judge final product according to reduced gravity situations;

Chloride hydrate manganese (self-control): heated by above-mentioned tetrahydrate manganese chloride, judge final product according to reduced gravity situations.

Embodiment 1

Add in 200mL crucible after 13.25g magnesium chloride hexahydrate, 80.04g mono-water lithium chloride, 56.19g Repone K, 3.18g Calcium Fluoride (Fluorspan) and 17.21g ammonium chloride are mixed.At 300 DEG C, 1 hour is incubated by after crucible cover upper cover, then at 500 DEG C, be incubated 1 hour, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and Lithium chloride (anhydrous): KCl (45.10wt.%)-NaCl (2.26wt.%)-MgCl ₂(4.98wt.%)-LiCl (45.10wt.%)-CaF ₂(3.18wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the plumbago crucible of 200mL is electrolyzer, and electrolysis temperature is 440 DEG C, pole span is 4cm, and cathode current density is 5.1A/cm ², bath voltage is 7.9-8.6V, and electrolysis time is 3.5h.

According to above-mentioned measuring method, electrolyte melt and magnesium lithium alloy are characterized.Its result is as follows:

Be 0.09 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Lithium chloride (anhydrous).The lithium content of sample ecto-entad three positions is respectively 48.65%, 47.98%, 48.05%, and visible sample is uniform macroscopically elemental lithium distributes.The Surface scan of alloy is shown in accompanying drawing 2, and as seen from the figure, element is evenly distributed in the alloy.The current efficiency of electrolytic process is 81.0%.The XRD figure spectrum of alloy is shown in accompanying drawing 3, and as seen from the figure, the thing phase composite of alloy is Li and Li ₃mg ₁₇.

Embodiment 2

By 22.48g hydrated magnesium chloride (MgCl21.9H ₂o), 26.30g chloride hydrate lithium (LiCl0.5H ₂o), add in 200mL crucible after the mixing of 43.40g Repone K, 2.17g sodium-chlor, 4.02g Calcium Fluoride (Fluorspan) and 28.45g ammonium chloride.At 300 DEG C, 1.5 hours are incubated by after crucible cover upper cover, then at 450 DEG C, be incubated 1 hour, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and Lithium chloride (anhydrous): KCl (39.61wt.%)-NaCl (1.98wt.%)-MgCl ₂(15.13wt.%)-LiCl (39.61wt.%)-CaF ₂(3.67wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the plumbago crucible of 200mL is electrolyzer, and electrolysis temperature is 450 DEG C, pole span is 4cm, and cathode current density is 6.6A/cm ², bath voltage is 9.4-9.8V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium lithium alloy obtained are characterized.Its result is as follows:

Be 0.11 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Lithium chloride (anhydrous).The lithium content of sample ecto-entad three positions is respectively 5.23%, 5.65%, 5.62%, and visible sample is uniform macroscopically elemental lithium distributes.The current efficiency of electrolytic process is 83.6%.The thing phase composite of the XRD figure spectrum display alloy of alloy is Li and Li ₃mg ₁₇.

Embodiment 3

Add in 200mL crucible after 70.77g magnesium chloride hexahydrate, 100.00g Repone K, 11.40g seventy flavors pearl pill, 4.88g Calcium Fluoride (Fluorspan) and 55.95g ammonium chloride are mixed.At 400 DEG C, be incubated 2 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 2 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and anhydrous lanthanum chloride: KCl (68.65wt.%)-MgCl ₂(23.14wt.%)-LaCl ₃(5.17wt.%)-CaF ₂(3.35wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the plumbago crucible of 200mL is electrolyzer, and electrolysis temperature is 680 DEG C, pole span is 4cm, and cathode current density is 5.8A/cm ², bath voltage is 7.2-7.6V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium lanthanum alloy obtained are characterized.Its result is as follows:

Be 0.18 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and anhydrous lanthanum chloride.The lanthanum content of sample ecto-entad three positions is respectively 4.89%, 4.68%, 4.95%, and visible sample is uniform macroscopically lanthanum element distributes.Accompanying drawing 4 is shown in the energy spectrum analysis of alloy, and wherein, the energy spectrum analysis Fig. 1 and 2 being arranged in bottom corresponds respectively to the EDAX results of the 1 and 2 places detection marked at upper figure.Visible alloy be by magnesium and lanthanum two kinds elementary composition.The element Surface scan figure of alloy is shown in accompanying drawing 5, and as seen from the figure, element is even in microdistribution.The current efficiency of electrolytic process is 97.8%.The XRD figure spectrum of alloy is shown in accompanying drawing 6, and as seen from the figure, the thing phase composite of alloy is Mg and La ₂mg ₁₇.

Embodiment 4

By 46.92g hydrated magnesium chloride (MgCl ₂2.2H ₂o), add in 200mL crucible after the mixing of 100.00g Repone K, 5.00g lanthanum trioxide, 4.88g Calcium Fluoride (Fluorspan) and 38.35g ammonium chloride.At 400 DEG C, be incubated 2 hours by after crucible cover upper cover, then at 750 DEG C, be incubated 1.5 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and anhydrous lanthanum chloride: (68.65wt.%)-MgCl ₂(23.14wt.%)-LaCl ₃(5.17wt.%)-CaF ₂(3.35wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the plumbago crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 5.8A/cm ², bath voltage is 7.7-7.9V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium lanthanum alloy obtained are characterized.Its result is as follows:

Be 0.17 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and anhydrous lanthanum chloride.The lanthanum content of sample ecto-entad three positions is respectively 7.36%, 7.57%, 7.63%, and visible sample is uniform macroscopically lanthanum element distributes.The current efficiency of electrolytic process is 95.2%.The thing phase composite of the XRD figure spectrum display alloy of alloy is Mg and La ₂mg ₁₇.

Embodiment 5

By 52.57g hydrated magnesium chloride (MgCl ₂3.1H ₂o), 100.00g Repone K, 9.96g hydrated lanthanum chloride (LaCl ₃4.6H ₂o), add in 200mL crucible after 4.88g Calcium Fluoride (Fluorspan) and the mixing of 35.61g ammonium chloride.At 400 DEG C, be incubated 2.5 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 2 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and anhydrous lanthanum chloride: (68.65wt.%)-MgCl ₂(23.14wt.%)-LaCl ₃(5.17wt.%)-CaF ₂(3.35wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the plumbago crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 7.1A/cm ², bath voltage is 7.9-8.3V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium lanthanum alloy obtained are characterized.Its result is as follows:

Be 0.22 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and anhydrous lanthanum chloride.The lanthanum content of sample ecto-entad three positions is respectively 8.76%, 8.95%, 8.68%, and visible sample is uniform macroscopically lanthanum element distributes.The current efficiency of electrolytic process is 92.3%.The thing phase composite of the XRD figure spectrum display alloy of alloy is Mg and La ₂mg ₁₇.

Embodiment 6

Add in 200mL crucible after 70.77g magnesium chloride hexahydrate, 8.28g zinc chloride, 82.78g Repone K and 27.98g ammonium chloride are mixed.At 450 DEG C, be incubated 2 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 2.5 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and zinc chloride: KCl (66.66wt.%)-MgCl ₂(26.67wt.%)-ZnCl ₂(6.67wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 3.85A/cm ², bath voltage is 4.7-5.0V, and electrolysis time is 4h.

According to above-mentioned measuring method, electrolytic process and the magnesium-zinc alloy obtained are characterized.Its result is as follows:

Be 0.05 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Zinc Chloride Anhydrous.The Zn content of sample ecto-entad three positions is respectively 25.46%, 24.86%, 25.51%, and visible sample is uniform macroscopically zinc element distributes.The element Surface scan figure of alloy is shown in accompanying drawing 7, and as seen from the figure, magnesium and zinc are evenly distributed in the alloy.Accompanying drawing 8 is shown in the energy spectrum analysis of alloy, wherein, is arranged in the EDAX results that energy spectrum analysis Fig. 1 of bottom, 2 and 3 corresponds respectively to 1, the 2 and 3 places detection marked at upper figure.Magnesium-zinc alloy is comparatively active, easily reacts with oxygen or water, O and the Cl element detected in power spectrum be grind and polishing process in mix.The current efficiency of electrolytic process is 97.99%.Accompanying drawing 9 is the XRD figure spectrum of alloy, and as seen from the figure, the thing phase composite of alloy is Mg, MgZn ₂and Mg ₇zn ₃.

Embodiment 7

By 50.06g hydrated magnesium chloride (MgCl ₂2.7H ₂o), add in 200mL crucible after the mixing of 8.28g zinc chloride, 82.78g Repone K and 27.98g ammonium chloride.At 450 DEG C, be incubated 2.5 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 1.5 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and zinc chloride: KCl (66.66wt.%)-MgCl ₂(26.67wt.%)-ZnCl ₂(6.67wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 6.41A/cm ², bath voltage is 6.1-6.5V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium-zinc alloy obtained are characterized.Its result is as follows:

Be 0.05 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Zinc Chloride Anhydrous.The Zn content of sample ecto-entad three positions is respectively 25.53%, 25.68%, 27.62%, and visible sample is uniform macroscopically zinc element distributes.The current efficiency of electrolytic process is 97.25%.The thing phase composite of the XRD figure spectrum display alloy of alloy is Mg, MgZn ₂and Mg ₇zn ₃.

Embodiment 8

Add in 200mL crucible after 70.77g magnesium chloride hexahydrate, 82.78g Repone K, 7.80g tetrahydrate manganese chloride and 27.98g ammonium chloride are mixed.At 350 DEG C, be incubated 3 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 1.5 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and Manganese chloride anhydrous: KCl (82.78wt.%)-MgCl ₂(33.12wt.%)-MnCl ₂(4.96wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 5.5A/cm ², bath voltage is 5.8-6.5V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium-manganese alloy obtained are characterized.Its result is as follows:

Be 0.03 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Manganese chloride anhydrous.The Fe content of sample ecto-entad three positions is respectively 31.25%, 32.16%, 32.01%, and visible sample is uniform macroscopically manganese element distributes.The element Surface scan figure of alloy is shown in accompanying drawing 10, and as seen from the figure, magnesium and manganese are evenly distributed in the alloy.Accompanying drawing 11 is shown in the energy spectrum analysis of alloy, and wherein, the energy spectrum analysis Fig. 1 and 2 being arranged in bottom corresponds respectively to the EDAX results of the 1 and 2 places detection marked at upper figure.Alloy is made up of MAGNESIUM METAL and manganese metal.The current efficiency of electrolytic process is 98.32%.Accompanying drawing 12 is the XRD figure spectrum of alloy, and as seen from the figure, the thing of alloy is made up of MAGNESIUM METAL and manganese metal.

Embodiment 9

By 60.10g hydrated magnesium chloride (MgCl ₂4.3H ₂o), 82.78g Repone K, 6.03g chloride hydrate manganese (MnCl ₂1.6H ₂o) and after the mixing of 27.98g ammonium chloride add in 200mL crucible.At 400 DEG C, be incubated 2.5 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 2 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and Manganese chloride anhydrous: KCl (82.78wt.%)-MgCl ₂(33.12wt.%)-MnCl ₂(4.96wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 5.7A/cm ², bath voltage is 7.1-8.0V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium-manganese alloy obtained are characterized.Its result is as follows:

Be 0.02 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Manganese chloride anhydrous.The Fe content of sample ecto-entad three positions is respectively 27.69%, 27.96%, 27.75%, and visible sample is uniform macroscopically manganese element distributes.The current efficiency of electrolytic process is 87.68%.The thing of the XRD figure spectrum display alloy of alloy is made up of MAGNESIUM METAL and manganese metal.

Embodiment 10

Add in 200mL crucible after 70.77g magnesium chloride hexahydrate, 82.78g Repone K, 16.56g calcium chloride and 27.98g ammonium chloride are mixed.At 400 DEG C, be incubated 3 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 2.5 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and Calcium Chloride Powder Anhydrous: KCl (62.5wt.%)-MgCl ₂(25.0wt.%)-CaCl ₂(12.5wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 2mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 5.6A/cm ², bath voltage is 7.0-8.2V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium calcium alloy obtained are characterized.Its result is as follows:

Be 0.08 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Calcium Chloride Powder Anhydrous.The calcium contents of sample ecto-entad three positions is respectively 0.72%, 0.75%, 0.69%, and visible sample is uniform macroscopically calcium constituent distributes.The element Surface scan figure of alloy is shown in accompanying drawing 13, and as seen from the figure, magnesium and calcium are evenly distributed in the alloy.The current efficiency of electrolytic process is 83.9%.Accompanying drawing 14 is the XRD figure spectrum of alloy, and as seen from the figure, the thing of alloy is made up of MAGNESIUM METAL.Because the content of calcium is less than 5%, therefore XRD can't detect the characteristic spectrum of calcium simple substance or calcium cpd.

Embodiment 11

By 40.81g hydrated magnesium chloride (MgCl ₂1.2H ₂o), add in 200mL crucible after the mixing of 82.78g Repone K, 5.97g calcium oxide and 27.98g ammonium chloride.At 450 DEG C, be incubated 2 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 2 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous and Calcium Chloride Powder Anhydrous: KCl (62.5wt.%)-MgCl ₂(25.0wt.%)-CaCl ₂(12.5wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 2mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 6.5A/cm ², bath voltage is 7.0-8.3V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium calcium alloy obtained are characterized.Its result is as follows:

Be 0.07 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous and Calcium Chloride Powder Anhydrous.The calcium contents of sample ecto-entad three positions is respectively 0.96%, 0.99%, 0.92%, and visible sample is uniform macroscopically calcium constituent distributes.The current efficiency of electrolytic process is 87.6%.The thing of the XRD figure spectrum display alloy of alloy is made up of MAGNESIUM METAL.Because the content of calcium is less than 5%, therefore XRD can't detect the characteristic spectrum of calcium simple substance or calcium cpd.

Embodiment 12

Add in 200mL crucible after 70.77g magnesium chloride hexahydrate, 82.78g Repone K, 8.28g zinc chloride, 16.56g calcium chloride and 27.98g ammonium chloride are mixed.At 450 DEG C, be incubated 1.5 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 2.5 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous, zinc chloride and Calcium Chloride Powder Anhydrous: KCl (58.82wt.%)-MgCl ₂(23.50wt.%)-ZnCl ₂(5.88wt.%)-CaCl ₂(11.77wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 5.2A/cm ², bath voltage is 5.5-5.7V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium zinc calcium alloy obtained are characterized.Its result is as follows:

Be 0.10 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous, Calcium Chloride Powder Anhydrous and Zinc Chloride Anhydrous.The Zn content of sample ecto-entad three positions is respectively 38.92%, 38.68%, 38.68%, and the content of calcium constituent is respectively 0.76%, 0.68%, 0.77%, and visible sample is uniform macroscopically zinc element and calcium constituent distribute.The element Surface scan figure of alloy is shown in accompanying drawing 15, and as seen from the figure, magnesium, zinc, calcium are evenly distributed in the alloy.The current efficiency of electrolytic process is 80.9%.Accompanying drawing 16 is the XRD figure spectrum of alloy, and as seen from the figure, the thing of alloy is by Mg ₇zn ₃and MgZn ₂composition.Because the content of calcium is lower than 5%, therefore in XRD figure spectrum, do not observe the thing phase about Ca.

Embodiment 13

By 40.81g hydrated magnesium chloride (MgCl ₂1.2H ₂o), add in 200mL crucible after the mixing of 82.78g Repone K, 8.28g zinc chloride, 5.97g calcium oxide and 27.98g ammonium chloride.At 400 DEG C, be incubated 2 hours by after crucible cover upper cover, then at 700 DEG C, be incubated 1.5 hours, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous, zinc chloride and Calcium Chloride Powder Anhydrous: KCl (58.82wt.%)-MgCl ₂(23.50wt.%)-ZnCl ₂(5.88wt.%)-CaCl ₂(11.77wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the corundum crucible of 200mL is electrolyzer, and electrolysis temperature is 700 DEG C, pole span is 4cm, and cathode current density is 6.8A/cm ², bath voltage is 7.3-7.5V, and electrolysis time is 4h.

According to above-mentioned measuring method, electrolytic process and the magnesium zinc calcium alloy obtained are characterized.Its result is as follows:

Be 0.09 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous, Calcium Chloride Powder Anhydrous and Zinc Chloride Anhydrous.The Zn content of sample ecto-entad three positions is respectively 18.26%, 18.19%, 18.38%, and the content of calcium constituent is respectively 1.79%, 1.86%, 1.82%, and visible sample is uniform macroscopically zinc element and calcium constituent distribute.The current efficiency of electrolytic process is 86.5%.The thing of the XRD figure spectrum display alloy of alloy is by Mg ₇zn ₃and MgZn ₂composition.Because the content of calcium is lower than 5%, therefore in XRD figure spectrum, do not observe the thing phase about Ca.

Embodiment 14

Add in 200mL crucible after 35.53g magnesium chloride hexahydrate, 73.15g Repone K, 73.15g mono-water lithium chloride, 1.625g lanthanum trioxide, 0.33g Calcium Fluoride (Fluorspan), 1.46g sodium-chlor and 27.98g ammonium chloride are mixed.At 400 DEG C, be incubated 2 hours by after crucible cover upper cover, then at 600 DEG C, be incubated 1 hour, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous, Lithium chloride (anhydrous) and anhydrous lanthanum chloride: KCl (50.76wt.%)-MgCl ₂(11.54wt.%)-LiCl (35.61wt.%)-NaCl (1.01wt.%)-LaCl ₃(0.85wt.%)-CaF ₂(0.33wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the plumbago crucible of 200mL is electrolyzer, and electrolysis temperature is 550 DEG C, pole span is 4cm, and cathode current density is 5.0A/cm ², bath voltage is 4.9-6.3V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium lithium lanthanum alloy obtained are characterized.Its result is as follows:

Be 0.11 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous, Lithium chloride (anhydrous) and anhydrous lanthanum chloride.The lithium content difference 6.52%, 6.46%, 6.43% of sample ecto-entad three positions, the content of lanthanum element is respectively 26.95%, 26.87%, 26.68%, and visible sample is uniform macroscopically elemental lithium and lanthanum element distribute.The element Surface scan figure of alloy is shown in accompanying drawing 17, and as seen from the figure, magnesium, lithium, lanthanum are evenly distributed in the alloy.The current efficiency of electrolytic process is 83.9%.Accompanying drawing 18 is shown in the energy spectrum analysis of alloy, and wherein, the energy spectrum analysis Fig. 1 and 2 being arranged in bottom corresponds respectively to the EDAX results of the 1 and 2 places detection marked at upper figure.Because energy spectrum analysis can not test elemental lithium, therefore magnesium elements and lanthanum element can only be detected; The XRD figure spectrum of alloy is shown in accompanying drawing 19, and the thing of alloy is Mg, Li mutually _0.92mg _4.08, LaMg ₂.

Embodiment 15

By 27.65g hydrated magnesium chloride (MgCl ₂3.5H ₂o), 73.15g Repone K, 64.44g chloride hydrate lithium (LiCl0.6H ₂o), 1.62g hydrated lanthanum chloride (LaCl ₃4.1H ₂o), add in 200mL crucible after the mixing of 0.33g Calcium Fluoride (Fluorspan), 1.46g sodium-chlor and 28.10g ammonium chloride.At 450 DEG C, be incubated 2.5 hours by after crucible cover upper cover, then at 600 DEG C, be incubated 1 hour, (bath component is the melt obtaining containing Magnesium Chloride Anhydrous, Lithium chloride (anhydrous) and anhydrous lanthanum chloride: KCl (50.76wt.%)-MgCl ₂(11.54wt.%)-LiCl (35.61wt.%)-NaCl (1.01wt.%)-LaCl ₃(0.85wt.%)-CaF ₂(0.33wt.%)).Melt is very pure, does not observe impurity.Then, described melt is carried out electrolysis in a cell, wherein electrolytic condition is: this melt is ionogen, the spectroscopically pure graphite rod of Φ 6mm is anode, the steel wire of Φ 1mm is negative electrode, and volume is the plumbago crucible of 200mL is electrolyzer, and electrolysis temperature is 600 DEG C, pole span is 4cm, and cathode current density is 7.5A/cm ², bath voltage is 7.8-8.5V, and electrolysis time is 4.0h.

According to above-mentioned measuring method, electrolytic process and the magnesium lithium lanthanum alloy obtained are characterized.Its result is as follows:

Be 0.08 % by weight containing content of magnesia in the electrolyte melt of Magnesium Chloride Anhydrous, Lithium chloride (anhydrous) and anhydrous lanthanum chloride.The lithium content difference 7.95%, 8.06%, 7.86% of sample ecto-entad three positions, the content of lanthanum element is respectively 29.35%, 29.83%, 29.36%, and visible sample is uniform macroscopically elemental lithium and lanthanum element distribute.The current efficiency of electrolytic process is 80.3%.The thing of the XRD figure spectrum display alloy of alloy is Mg, Li mutually _0.92mg _4.08, LaMg ₂.

Above with hydrated magnesium chloride and seventy flavors pearl pill, a water lithium chloride, tetrahydrate manganese chloride, zinc chloride, calcium chloride, lanthanum trioxide, calcium oxide, manganese oxide, hydrated lanthanum chloride, chloride hydrate lithium, chloride hydrate manganese etc. for raw material, the magnesium alloy of Mg-Li, Mg-La, Mg-Zn, Mg-Mn, Mg-Ca, Mg-Zn-Ca, Mg-Li-La has been prepared by the inventive method, having good uniformity of alloying elements distribution, in electrolytic preparation process, current efficiency is all more than 80%.

It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, can multiple amendment and change be carried out.Such amendment and change are intended to fall into as defined in the appended claims within scope of the present invention.

Claims (13)

1. utilize hydrated magnesium chloride for a method for raw material electrolytic preparation magnesium alloy, described method comprises the following steps:

A (), by the compound of other metallic element in hydrated magnesium chloride, magnesium alloy, ammonium chloride, Repone K and additive Homogeneous phase mixing to prepare mixture, in wherein said magnesium alloy, the compound of other metallic element is selected from the one in the group be made up of the following: the muriate of other metallic element in described magnesium alloy; The oxide compound of other metallic element in described magnesium alloy; With muriate and the oxide compound of other metallic element in described magnesium alloy;

B the described mixture of preparation in step (a) is heated to molten state, to prepare the electrolyte melt containing other metal ion in Magnesium Chloride Anhydrous and described magnesium alloy by (); With

C () is by the described electrolyte melt electrolysis of preparation in step (b) thus obtained described magnesium alloy.

2. method according to claim 1, wherein in step (a), in described magnesium alloy, other metallic element is selected from one or more in following elements: rare earth element, zinc, aluminium, manganese, lithium, calcium, zirconium, silver, strontium, antimony, cadmium, thorium, beryllium, lead and gallium.

3. method according to claim 1, wherein in step (a), in described magnesium alloy, the muriate of other metallic element is selected from one or more in following muriate: rare earth element muriate, zinc chloride, aluminum chloride, Manganous chloride tetrahydrate, lithium chloride, calcium chloride, zirconium chloride, silver chloride, strontium chloride, antimony chloride, Cadmium chloride fine powder, Thorium tetrachloride, beryllium chloride, lead chloride and gallium chloride.

4. method according to claim 1, wherein in step (a), in described magnesium alloy, the oxide compound of other metallic element is selected from one or more in following oxide compound: rare earth oxide, calcium oxide, manganese oxide and weisspiessglanz.

5. method according to claim 1, wherein in step (a), described additive be selected from the following one or more: CaF ₂, KF, NaF, LiF, MgF ₂, CaCl ₂, BaCl ₂and NaCl.

6. method according to claim 1, wherein said hydrated magnesium chloride is expressed from the next: MgCl ₂mH ₂o, wherein m > 0.

7. method according to claim 1, wherein in step (a), when in described magnesium alloy, the compound of other metallic element is the muriate of other metallic element in described magnesium alloy, in described hydrated magnesium chloride, magnesium alloy, the muriate of other metallic element, ammonium chloride, Repone K and additive add with amount as described below:

The amount not containing the magnesium chloride of crystal water corresponding to described hydrated magnesium chloride is 1.00 weight parts;

With the amount of the described hydrated magnesium chloride of parts by weight

With the muriatic amount of other metallic element in the described magnesium alloy of parts by weight ${W_i}^c=0.25\&times;Z_i^c\&times;\frac{{\mathrm{\&alpha;}}_i^c\&times;(M_{\mathrm{ic}}+35.5n_i^c)}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_i^c)\&times;M_{\mathrm{ic}}};$

With the amount of the described ammonium chloride of parts by weight be greater than (0.10 × β+0.08 × ∑ β _i× W _i ^c);

With the amount of the described Repone K of parts by weight

With the amount of the described additive of parts by weight $W_{\mathrm{ad}}^c=Z2\&times;(1.00+\mathrm{\&Sigma;}{W_i}^c+W_{\mathrm{KCl}}^c);$

Wherein, m represents the number of the crystal water contained in hydrated magnesium chloride described in per molecule; in the scope of 0.1 to 145.0; for the weight percentage of other metallic element in magnesium alloy; M _icfor the nucleidic mass of other metallic element in magnesium alloy; for the valency of the metallic element in the muriate of other metallic element in magnesium alloy; β is the weight ratio of water and Magnesium Chloride Anhydrous in described hydrated magnesium chloride; β _ifor the weight ratio of water and anhydrous chloride in the muriate of other metallic element in magnesium alloy; Z1 is in the scope of 0.05 to 150.00; And Z2 is in the scope of 0.005 to 0.500.

8. method according to claim 1, wherein in step (a), when in described magnesium alloy, the compound of other metallic element is the oxide compound of other metallic element in described magnesium alloy, in described hydrated magnesium chloride, magnesium alloy, the oxide compound of other metallic element, ammonium chloride, Repone K and additive add with amount as described below:

The amount not containing the magnesium chloride of crystal water corresponding to described hydrated magnesium chloride is 1.00 weight parts;

With the amount of the described hydrated magnesium chloride of parts by weight

With the amount of the oxide compound of other metallic element in the described magnesium alloy of parts by weight $W_j^o=0.25\&times;Z_j^o\&times;\frac{{\mathrm{\&alpha;}}_j^0}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)}\&times;\frac{(M_{\mathrm{jo}}+{8n}_j^o)}{M_{\mathrm{jo}}};$

With the amount of the described ammonium chloride of parts by weight be greater than $(0.10\&times;\mathrm{\&beta;}+\mathrm{\&Sigma;}\frac{13.37\&times;Z_j^o\&times;n_j^o\&times;{\mathrm{\&alpha;}}_j^o}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)\&times;M_{\mathrm{jo}}});$

With the amount of the described Repone K of parts by weight $W_{\mathrm{KCl}}^o=0.78+Z3\&times;\mathrm{\&Sigma;}(0.25\&times;Z_j^o\&times;\frac{{\mathrm{\&alpha;}}_j^o\&times;(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)\&times;M_{\mathrm{jo}}});$

With the amount of the described additive of parts by weight

$W_{\mathrm{ad}}^o=Z4\&times;(1.00+\mathrm{\&Sigma;}(0.25\&times;Z_j^o\&times;\frac{{\mathrm{\&alpha;}}_j^o\&times;(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)\&times;M_{\mathrm{jo}}})+W_{\mathrm{KCl}}^o);$

Wherein, m represents the number of the crystal water contained in hydrated magnesium chloride described in per molecule; in the scope of 0.05 to 100.00; for the weight percentage of other metallic element in magnesium alloy; M _jofor the nucleidic mass of other metallic element in magnesium alloy; for the valency of the metallic element in the oxide compound of other metallic element in magnesium alloy; β is the weight ratio of water and Magnesium Chloride Anhydrous in described hydrated magnesium chloride; Z3 is in the scope of 0.05 to 150.00; And Z4 is in the scope of 0.005 to 0.500.

9. method according to claim 1, wherein in step (a), when in described magnesium alloy, the compound of other metallic element is muriate and the oxide compound of other metallic element in described magnesium alloy, in described hydrated magnesium chloride, magnesium alloy, in the muriate of other metallic element, magnesium alloy, the oxide compound of other metallic element, ammonium chloride, Repone K and additive add with amount as described below:

The amount not containing the magnesium chloride of crystal water corresponding to described hydrated magnesium chloride is 1.00 weight parts;

With the amount of the described hydrated magnesium chloride of parts by weight

With the muriatic amount of other metallic element in the described magnesium alloy of parts by weight ${W_i}^c=0.25\&times;Z_i^c\&times;\frac{{\mathrm{\&alpha;}}_i^c\&times;(M_{\mathrm{ic}}+35.5n_i^c)}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_i^c-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)\&times;M_{\mathrm{ic}}};$

With the amount of the oxide compound of other metallic element in the described magnesium alloy of parts by weight $W_j^o=0.25\&times;Z_j^o\&times;\frac{{\mathrm{\&alpha;}}_j^0}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)}\&times;\frac{(M_{\mathrm{jo}}+{8n}_j^o)}{M_{\mathrm{jo}}};$

With the amount of the described ammonium chloride of parts by weight be greater than $(0.10\&times;\mathrm{\&beta;}+$ $0.08\&times;\mathrm{\&Sigma;}({\mathrm{\&beta;}}_i\&CenterDot;{W_i}^c)+\mathrm{\&Sigma;}\frac{13.37\&times;Z_j^o\&times;n_j^o\&times;{\mathrm{\&alpha;}}_j^o}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_i^c-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)\&times;M_{\mathrm{jo}}});$

With the amount of the described Repone K of parts by weight $W_{\mathrm{KCl}}^{\mathrm{co}}=0.78+Z5\&CenterDot;(\mathrm{\&Sigma;}{W_i}^c+\mathrm{\&Sigma;}(0.25\&times;Z_j^o\&times;\frac{{\mathrm{\&alpha;}}_j^o\&times;(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_i^c-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)\&times;M_{\mathrm{jo}}}));$

With the amount of the described additive of parts by weight

$W_{\mathrm{ad}}^{\mathrm{co}}=Z6\&times;(1.00+\mathrm{\&Sigma;}{W_i}^c+\mathrm{\&Sigma;}(0.25\&times;Z_j^o\&times;\frac{{\mathrm{\&alpha;}}_j^o\&times;(M_{\mathrm{jo}}+35.5n_j^o)}{(1-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_i^c-\mathrm{\&Sigma;}{\mathrm{\&alpha;}}_j^o)\&times;M_{\mathrm{jo}}})+W_{\mathrm{KCl}}^{\mathrm{co}});$

Wherein, m represents the number of the crystal water contained in hydrated magnesium chloride described in per molecule; in the scope of 0.1 to 145.0; for the weight percentage of other metallic element in the muriate of other metallic element in described magnesium alloy; for the weight percentage of other metallic element in the oxide compound of other metallic element in described magnesium alloy; M _icfor the nucleidic mass of other metallic element in the muriate of other metallic element in described magnesium alloy; for the valency of other metallic element in anhydrous chloride in the muriate of other metallic element in described magnesium alloy; in the scope of 0.05 to 100.00; M _jofor the nucleidic mass of other metallic element in the oxide compound of other metallic element in described magnesium alloy; for the valency of the metallic element in the oxide compound of other metallic element in described magnesium alloy; β is the weight ratio of water and Magnesium Chloride Anhydrous in described hydrated magnesium chloride; β _ifor the weight ratio of water and anhydrous chloride in the muriate of other metallic element in magnesium alloy; Z5 is in the scope of 0.05 to 150.00; And Z6 is in the scope of 0.005 to 0.500.

10. method according to claim 1, wherein in step (b), described heat-processed is: first 200 ~ 550 DEG C of insulations 0.5 ~ 4.5 hour, then 400 ~ 850 DEG C of insulations 0.2 ~ 4.0 hour, with the obtained electrolyte melt containing other metal ion in anhydrous chlorides of rase magnesium and its alloys.

11. methods according to claim 1, wherein in step (c), the condition of described electrolysis is: anode is made up of graphite material, and negative electrode is made up of steel; During electrolysis, temperature is 400 ~ 850 DEG C, and electrolysis voltage is 5 ~ 10V, and cathode current density is greater than 3A/cm ².

12. methods according to claim 1, the ammonia nitrogen recovery wherein step (b) discharged turning back in step (a) recycles, and the Ammonia recovery that will discharge utilizes.

13. methods according to claim 1, wherein turn back to the waste cell melt melt of discharging in the electrolytic process of step (c) in step (a) and recycle, and utilized through Recovery Purifying by the chlorine of generation.