CN103906861A

CN103906861A - Molten salt electrolysis metal fabrication method and apparatus for use in same

Info

Publication number: CN103906861A
Application number: CN201280054132.1A
Authority: CN
Inventors: 粟津知之; 真岛正利
Original assignee: Sumitomo Electric Industries Ltd
Current assignee: Sumitomo Electric Industries Ltd
Priority date: 2011-11-04
Filing date: 2012-10-22
Publication date: 2014-07-02
Also published as: WO2013065511A1; US20140291161A1

Abstract

Provided is a method for obtaining safely and at low cost a specific metal of high purity from a material to be processed that contains two or more metal elements. The molten salt electrolysis metal fabrication method of the present invention is characterized by having a step in which two or more metal elements contained within a material to be processed are dissolved in molten salt, and a step in which, by disposing a pair of electrode members in the molten salt in which the metal elements have been dissolved and controlling the electrical potential of the electrode members to a given value, a specific metal element present in the molten salt is precipitated onto, or made to form an alloy on, one of the electrode members.

Description

By the metal fabrication methods of fusion electrolysis and for the device of this manufacture method

Technical field

The present invention relates to manufacture by fusion electrolysis the method for metal; And for the device of this manufacture method.

Background technology

There are pyrometallurgy and hydrometallurgy by smelting ore with the currently known methods of manufacturing special metal.

Pyrometallurgical smelting is, in high-temperature smelting pot, ore is melted to the method with separate target metal.For example, concentrate, roasted ore or agglomerate are melted in high-temperature smelting pot, being condensed into bullion (1, the 46 page of non-patent literature) in separating using gangue, impurity etc. as slag.

When smelting, owing to utilizing the difference in specific gravity between molten metal that metal is separated from ore, so the difference in specific gravity between metal to be separated must be larger.In addition, separate targets thing solubleness each other must be lower.Owing to meeting, the element of these conditions between metallic substance is limited, and the object element therefore separating by pyrometallurgy is limited, and this becomes a problem.

Hydrometallurgy is the method that ore is dissolved in for example, in () alkalescence or acidic solution and separates and extract metal target from this solution.The method that separates and extract metal target from this aqueous solution has (for example) to utilize the method for ion-exchange, utilize the method for solvent extraction or utilize the method for aqueous electrolysis.

In the method for utilizing ion-exchange, use part to there is the solid matter that can carry out the ionic group of ion-exchange and be known as ion-exchanger and carried out reversible ionic exchange (1, the 194 page of non-patent literature).

Utilizing the adsorptive power of ion exchange resin and ion-exchange that exchange capacity carries out is excellent treatment process.But problem is, because this processing is by repeatedly the adsorbing and dissociate and carry out of ion, therefore ion-exchange is not suitable for and processes cost-effectively large quantity of material.

The method of utilizing solvent extraction is to utilize the separation method (1, the 199 page of non-patent literature) of the distribution difference of different solutes in immiscible two kinds of solvents each other.

In this solvent extraction, for example, carry out acid treatment to realize ionization; And in the time separating, need to carry out a large amount for the treatment of process.Problem is, in these operations, needs a large amount of bronsted lowry acids and bases bronsted lowries and produces a large amount of waste water.

In the electrolysis for production method of utilizing aqueous electrolysis, utilize and existingly between element tended to the difference of anode dissolution or cathodic deposition and manufacture pure metal.Meanwhile, in the electrolytic solution using, also utilized the reaction (1, the 219 page of non-patent literature) that is generated slightly soluble salt by foreign ion.

But, thereby can be limited by the metallic element that utilizes aqueous electrolysis to carry out purifying separation and to deposit.For example, there is this problem of deposition that can not realize in theory rare earth material.

About Al, the electrolysis for production that utilizes fusion electrolysis is also known.In this method, form three layers that formed by Al (purification of target material, thereby it is had lower fusing point by alloying), melting salt and recovery metal, and utilized difference in specific gravity to smelt.Owing to so having utilized difference in specific gravity, so need to smelt (1, the 254 page of non-patent literature) in the time that three layers all melt.

The metal target of the method is Al.In addition, when the current potential of the impurity coexisting with purification of target metal is during close to the current potential of purification of target metal, there is such problem, will occur in metal target that this impurity enters deposition.

On the other hand, the method for recovery tungsten for example, has following description in () patent documentation 2.

Make hard waste material or soft waste material and the SODIUMNITRATE molten salt reaction of carbamide tool, thus the sodium wolframate aqueous solution that makes soluble in water then.Utilize ion exchange resin and by ion exchange method, the sodium wolframate aqueous solution processed, thereby making ammonium tungstate aqueous solution.Ammonium paratungstate (APT) is crystallized out from ammonium tungstate aqueous solution.After this, to the ammonium paratungstate of crystallization thus calcine, reduction and carbonization, thereby obtain wolfram varbide.

Hard waste material general reference still has the waste material sheet of shape of product.Soft waste material represents powdery waste, as the powder bits and the smear metal that produce in the course of processing of manufacture carbamide tool.

When patent documentation 1 has proposed in molten salt bath to manufacture sodium wolframate by oxidation waste hand alloy material and/or heavy metal waste material, can use the melting salt of the sodium sulfate of the sodium hydroxide that contains 60 % by weight to 90 % by weight and 10 % by weight to 40 % by weight.Patent documentation 1 also proposes reaction between these waste materials and melting salt with intermittent mode operation and can carry out in direct-fired rotary kiln.

But in the aforesaid method of describing in non-patent literature 2, reacting between the hard waste material of carbamide tool or soft waste material and SODIUMNITRATE melting salt is very violent.Therefore, this reaction is difficult to control and operates and has safety problem.In addition, in the time making the hard waste material of carbamide tool or soft waste material and SODIUMNITRATE molten salt reaction, the metal (as vanadium and chromium) being contained in hard waste material or the soft waste material of carbamide tool presents the form of water-soluble metal oxide ion and enters in the aqueous solution of sodium wolframate.Therefore, because these metals exist as impurity, thereby be difficult to realize high purity, this becomes a problem.

In the aforesaid method of describing, there is the high-melting-point of 884 DEG C as the sodium sulfate melting salt of oxygenant in patent documentation 1.Therefore, the temperature setting in reaction process need to be set to 884 DEG C of above high temperature.Therefore the problem that, exists metallic substance to be corroded.In addition, reaction is carried out slowly, therefore exists reaction time consumption to grow and produce the problem of a large amount of power losses.

On the other hand, lithium mainly from containing lithium ore (as triphane, amblygonite, petalite and lithionite) and there is the salt lake of high lithium concentration and saline groundwater extract.But Japan is not containing lithium ore or salt lake.Therefore, in fact the total amount of lithium is nearly all to depend on import.

Thereby, started recently about for example, from () such as lithium cell containing produce the manufacturing step of lithium product containing lithium waste or with the research that separates and reclaim lithium in the waste of lithium product that contains of crossing.

The method of following recovery lithium has been proposed: the cobalt acid lithium as the positive electrode material of lithium secondary battery and metallic lithium one are coexisted in lithium chloride melting salt and carry out reduction reaction, thereby produce Lithium Oxide 98min and by precipitation by cobalt or cobalt oxide separation; After this, in lithium chloride melting salt, by Lithium Oxide 98min electrolysis, thereby being deposited on negative electrode, metallic lithium also reclaims (patent documentation 2: the open No.2005-011698 of Japanese unexamined patent).

But, in the method, in order to go out to be contained in the cobalt in handling object thing by Reduced separating, need to add metallic lithium.In order to reclaim metallic lithium, the method has adopted the step of adding metallic lithium, therefore has inefficient problem.

The method of following recovery lithium has been proposed, wherein by roasting under the carbon of positive electrode material as lithium secondary battery and the mixture of lithium manganate any one atmosphere in air atmosphere, oxidizing atmosphere, inert atmosphere and reducing atmosphere, so that lithium is converted into Lithium Oxide 98min; Make lithium leach (patent documentation 3) with the form of lithium hydroxide and Quilonum Retard thereby then this calcining matter is immersed in the water

But in the method, because lithium hydroxide and Quilonum Retard do not have high-dissolvability, therefore organic efficiency is low.In addition, lithium hydroxide and Quilonum Retard are leached in water and need a large amount of water, therefore this processing can produce a large amount of waste water, and this becomes a problem.

In addition, tantalum (Ta) is mainly used in tantalum capacitor, and can from tantalum capacitor waste material, reclaim tantalum.Particularly, can pass through the method that oxide treatment, magneticseparation, screening, mobile moisture process and leach from, pulverizing, screening, leaching, oxide treatment, reduction and reclaim tantalum (with reference to 3, the 319 to 326 pages of non-patent literatures).

Desulfurization catalyst when vanadium (V) is used as steel additive agent or oil refining.Steel is collected and be recovered as to vanadium as steel additive agent with the form of steel waste material.Can carry out successively classification, roasting, pulverizing, leaching, filtration, leach liquor, dehydration, thermolysis and fusing step to spent catalyst, thereby can obtain Vanadium Pentoxide in FLAKES (3, the 391 to 396 pages of non-patent literatures).

Desulfurization catalyst when molybdenum (Mo) is also used as additive, the alloy of steel or refines oil.As the molybdenum of steel additive or alloying element be collected with the form of steel or alloy and the in the situation that of un-extracted the form with steel or alloy use.Can carry out successively roasting to spent catalyst, leach and recycling step except deoiling, under water and sulphur, alkaline condition, thereby can obtain Mo (3, the 301 to 303 pages of non-patent literatures).

Niobium (Nb) is mainly used as the additive of steel.Niobium as steel additive is collected with the form of steel waste material.But the very low and niobium of the content of niobium in high tension steel, stainless steel etc. itself can not reclaim (3, the 339 pages of non-patent literatures).

Manganese (Mn) is mainly used in steel and aluminium alloy, and is collected with the form of steel waste material and aluminium alloy scrap respectively.In the situation that reclaiming steel, a high proportion of manganese remains in various slags and this dvimanganese of formation slag is not suitable for reclaiming.Manganese part in slag for example, for () manganese-Calucium Silicate powder fertilizer.

The aluminium pot that contains this aluminium alloy is collected and then reclaims (3, the 343 to 344 pages of non-patent literatures).

Then chromium (Cr) for steel (stainless steel) and superalloy be collected and reclaim with the form of steel waste material and superalloy waste material respectively; And do not carry out extraction and the recovery (3, the 219 to 221 pages of non-patent literatures) of elemental chromium.

In above-mentioned recovery technology, reclaim and relate to multiple processes such as roasting (heating), pulverizing, leaching and reduction.And these process complexity, therefore there is length consuming time and the high problem of cost processed.

In addition, this processing needs roasting, and non-extraction target substance is also processed in processing, and this has caused unnecessary energy expenditure.And, by non-processing target material is carried out to calcination process, generating unnecessary oxide compound, this has produced a large amount of wastes.In addition, owing to having carried out acid treatment or alkaline purification, this processing has produced acid waste water or alkaline waste water, and this has increased environmental pressure.

In a word, there is following problem in current metal recovery technology: for example, processing cost is high, power loss is large, the amount of waste large and environmental pressure weight.In addition,, due to the problem of cost or technical elements, some metals can not reclaim with simple substance form.

Reference listing

Non-patent literature

Patent documentation 1: the open No.11-505801 of Japanese unexamined patent

(translation of PCT application)

Patent documentation 2: the open No.2005-011698 of Japanese unexamined patent

Patent documentation 3: the open No.2011-094227 of Japanese unexamined patent

Non-patent literature 1:Courses of Contemporary Metallurgy, Smelting part, the 2nd volume, Nonferrous Metal Smelting, The Japan Institute of Metals and Materials writes (1980), the 46th, 194,199,219 and 254 pages

Non-patent literature 2:Rare-Metal High-Efficiency-Recovery-System Development Project " Recovery of tungsten etc.from waste cemented carbide tools ", Metal Resource Report, the 38th volume, the 4th phase, 407-413 page, in November, 2008

Non-patent literature 3:Compilation of Noble Metal and Rare Metal Recycling Techniques, NTS company publishes, and Bookers Ltd. plans and writes, the first version first impression, on October 19th, 2007

Summary of the invention

Technical problem

In view of the above problems, the object of this invention is to provide a kind of metal fabrication methods, and for the device of this manufacture method, wherein the method is applicable to any ore and can be with low cost fabrication high purity metal.The object of this invention is to provide a kind of handling object thing by containing two or more metallic elements with safety manufacture the method for highly purified special metal; And for the device of this manufacture method.

The scheme of dealing with problems

One embodiment of the invention are a kind of methods of manufacturing metal by fusion electrolysis, and the method comprises: the metallic element being contained in handling object thing is dissolved in to the step in melting salt, and wherein this handling object thing contains two or more metallic elements; And by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in melting salt, thereby make to be present in the step of deposition in special metal in the melting salt one in described pair of electrodes parts or alloying, the metallic element that wherein this melting salt contains described dissolving.

In another embodiment of the invention, handling object thing is ore or the bullion that obtained by this ore.

Another embodiment of the invention is a kind of method of manufacturing tungsten, the metallic element being wherein contained in described handling object thing is tungsten, metallic element is dissolved into by handling object thing in the described step in melting salt, tungsten is dissolved out from described handling object thing, and making in the described step of special metal deposition or alloying, by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in described melting salt, thereby the tungsten that makes to be present in described melting salt is deposited in the one in described pair of electrodes parts, the tungsten that wherein said melting salt contains dissolving.

In another embodiment of the invention, handling object thing is the metallic substance that contains tungsten.

In another embodiment of the invention, handling object thing is the metallic substance that contains tungsten and transition metal.

In another embodiment of the invention, handling object thing is hard metal article.

Another embodiment of the invention is a kind of method of manufacturing lithium, the metallic element being wherein contained in described handling object thing is lithium, metallic element is dissolved into by handling object thing in the described step in melting salt, lithium is dissolved out from described handling object thing, and making in the described step of special metal deposition or alloying, by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in described melting salt, thereby the lithium that makes to be present in described melting salt is deposited in the one in described pair of electrodes parts, the lithium that wherein said melting salt contains dissolving.

In another embodiment of the invention, handling object thing is the material that contains lithium and transition metal.

In another embodiment of the invention, handling object thing is the battery electrode material that contains lithium.

In another embodiment of the invention, handling object thing contains transition metal or rare earth metal.

In another embodiment of the invention, handling object thing contains one or more metals in the group of selecting free V, Nb, Mo, Ti, Ta, Zr and Hf formation.

In another embodiment of the invention, handling object thing contains Sr and/or Ba.

In another embodiment of the invention, handling object thing contains one or more metals in the group of selecting free Zn, Cd, Ga, In, Ge, Sn, Pb, Sb and Bi formation.

In another embodiment of the invention, select so described melting salt, make making in the described step of special metal deposition or alloying, the difference of the simple substance of special metal described in described melting salt or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.

In another embodiment of the invention, in the described step of special metal deposition or alloying, be described preset value by the control of Electric potentials of described electrod assembly, thereby optionally make described special metal element deposition or alloying in described melting salt making.

In another embodiment of the invention, the metallic element being contained in handling object thing is dissolved in the described step in melting salt, described metal is dissolved in described melting salt by chemical process.

In another embodiment of the invention, the metallic element being contained in handling object thing is dissolved in the described step in melting salt, the anode that negative electrode is set in described melting salt and is formed by the anode material that contains described handling object thing, and be preset value by the control of Electric potentials of described anode, thereby make to be dissolved in described melting salt by described handling object thing corresponding to the metallic element of this current potential through controlling.

In another embodiment of the invention, select so described melting salt, make the metallic element being contained in handling object thing is dissolved in the described step in melting salt, the difference of the simple substance of special metal described in described melting salt or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.

In another embodiment of the invention, the metallic element being contained in handling object thing is dissolved in the described step in melting salt, be preset value by the control of Electric potentials of described anode, thereby optionally make described special metal element be dissolved in described melting salt.

In another embodiment of the invention, the metallic element being contained in handling object thing is dissolved in the described step in melting salt, be all dissolved in described melting salt as one or more metals of described special metal.

In another embodiment of the invention, be deposited or the described special metal of alloying is transition metal.

In another embodiment of the invention, be deposited or the special metal of alloying is rare earth metal.

In another embodiment of the invention, be deposited or the special metal of alloying is V, Nb, Mo, Ti, Ta, Zr or Hf.

In another embodiment of the invention, be deposited or the special metal of alloying is Sr or Ba.

In another embodiment of the invention, be deposited or the special metal of alloying is Zn, Cd, Ga, In, Ge, Sn, Pb, Sb or Bi.

In another embodiment of the invention, melting salt is muriate melting salt or fluorochemical melting salt.

In another embodiment of the invention, melting salt is the fused salt mixture that contains muriate melting salt and fluorochemical melting salt.

In another embodiment of the invention, handling object thing is particulate state or Powdered.

In another embodiment of the invention, be particulate state or pulverous handling object thing is formed as anode through extruding.

Another embodiment of the invention is a kind of method of manufacturing metal by fusion electrolysis, thereby the method is to be manufactured the method for special metal by the handling object thing that contains two or more metallic elements by fusion electrolysis, the anode that negative electrode is wherein set in melting salt and is formed by the anode material that contains described handling object thing, and be preset value by the control of Electric potentials of this anode, thereby make to be dissolved in described melting salt by described handling object thing corresponding to the metallic element of this current potential through controlling, and special metal is retained in described anode.

Thereby another embodiment of the invention is a kind of method of being manufactured tungsten by fusion electrolysis by the handling object thing that contains tungsten, the anode that negative electrode is wherein set in melting salt and is formed by the anode material that contains described handling object thing, and be preset value by the control of Electric potentials of this anode, thereby make to be dissolved in described melting salt by described handling object thing corresponding to the metallic element of this current potential through controlling, and tungsten is retained in described anode.

In another embodiment of the invention, select so described melting salt, make metallic element is dissolved in the described step in described melting salt by described handling object thing, the difference of the simple substance of special metal described in described melting salt or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.

Another embodiment of the invention is a kind of for manufacture the device of the method for metal by fusion electrolysis, and this device comprises: the container that accommodates melting salt; Negative electrode, it is immersed in the described melting salt being contained in described container; And anode, it is immersed in the described melting salt being contained in described container and comprises handling object thing, this handling object thing contains two or more metallic elements, wherein said melting salt can flow between described anode interior and outside, described device also comprises control unit, it is preset value that this control unit is constructed to the control of Electric potentials of described negative electrode and described anode, and in described control unit, the value of described current potential can change.

Another embodiment of the invention is a kind of for manufacture the device of the method for metal by fusion electrolysis, and this device comprises: accommodate the container of melting salt, the metallic element that this melting salt comprises two or more dissolvings; Negative electrode and anode, it is immersed in the described melting salt being contained in described container; And control unit, it is constructed to the control of Electric potentials of described negative electrode and described anode is preset value, wherein, in described control unit, the value of described current potential can change.

In another embodiment of the invention, described two or more metallic elements comprise at least one in tungsten and lithium.

Beneficial effect of the present invention

Be applicable to any ore according to metal fabrication methods of the present invention with for the device of this manufacture method.Use manufacturing method according to the invention or can and manufacture at low cost highly purified special metal by the handling object thing safety that contains two or more metallic elements for the device of this manufacture method.

Brief Description Of Drawings

Fig. 1 is the schema of explanation embodiment of the present invention.

Fig. 2 is the schematic diagram of describing the example of the sedimentation potential of melting salt middle-weight rare earths metal.

Fig. 3 shows the graphic representation of the example of the relation between treatment time and the melting salt Rare Earth Metal Ions concentration in embodiment of the present invention.

Fig. 4 illustrates the schematic cross-section of device structure according to embodiments of the present invention.

Fig. 5 illustrates the schematic cross-section of device structure according to embodiments of the present invention.

Fig. 6 is the schema of explanation another embodiment of the invention.

Fig. 7 is the schematic cross-section of explanation another embodiment of the invention.

Fig. 8 is the schematic cross-section of explanation another embodiment of the invention.

Fig. 9 is the schematic cross-section of explanation another embodiment of the invention.

Figure 10 is the schematic cross-section of explanation another embodiment of the invention.

Figure 11 is the schematic cross-section of the modification of explanation another embodiment of the invention.

Figure 12 is the schematic cross-section of the modification of explanation another embodiment of the invention.

Figure 13 is the schematic cross-section of the modification of explanation another embodiment of the invention.

Figure 14 is that explanation is according to the photo of the anode using in embodiments of the invention.

Figure 15 is that explanation is according to the figure of the anodic current value in the embodiment of the present invention and the relation between the time.

Figure 16 is according to the electron scanning micrograph of the cathode surface part using in the electrolysis step in the embodiment of the present invention.The bottom-right yardstick of this microphotograph represents the length of 8 μ m.

Figure 17 is the electron scanning micrograph of explanation Dy distribution in the region of the microphotograph shown in Figure 16.

Figure 18 illustrates the schematic cross-section of device structure example according to embodiments of the present invention.

Figure 19 illustrates the schematic cross-section of device structure example according to embodiments of the present invention.

Embodiment

One embodiment of the invention are to manufacture the method for metal by fusion electrolysis, and the method comprises: the metallic element being contained in handling object thing is dissolved in to the step in melting salt, and wherein this handling object thing contains two or more metallic elements; And by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in described melting salt, thereby make to be present in the step of deposition in special metal in the described melting salt one in described pair of electrodes parts or alloying, the metallic element that wherein said melting salt contains described dissolving.

[the first embodiment]

In the first embodiment, handling object thing is the ore that contains two or more metallic elements or the bullion being obtained by this ore (hereinafter sometimes referred to as bullion).

; say roughly; this embodiment comprises and will be contained in dissolving metal in object (ore or the bullion) process in melting salt; and by fusion electrolysis, the metal or alloy that separates-extract object element is deposited in the one (negative electrode) in electrode from melting salt to the metal that wherein this melting salt contains dissolving.The present embodiment is characterised in that: by the current potential of control electrode, thereby optionally make specific objective element dissolve or deposition, separate and smelt to realize.

First by describing, the metallic element being contained in object is dissolved in to the process in melting salt.

The process that the metallic element being contained in ore or bullion is dissolved in melting salt is (for example) chemical dissolution process.Particularly, ore or bullion are ground to form to particle or powder, mix with salt and heat.Thereby, the two or more metallic elements that are contained in ore or bullion can be dissolved in melting salt.Or, handling object thing can be placed in to melting salt and make it and dissolve.

Another process is electrochemical process.Particularly, object is arranged in melting salt as anode, and the potential value of control object thing, thereby the element that optionally makes to be contained in object dissolves: fusion electrolysis is characterised in that: different elements dissolves under different current potentials; And utilize this feature optionally to separate the metal of corresponding current potential.Like this, by object is used as to anode and controls current potential in dissolution process, thereby can optionally will be dissolved in melting salt as the metallic element of smelting target.

The metallic element being contained in object is dissolved in the process of melting salt, preferably control like this current potential, remain and do not dissolve thereby make to be contained in impurity in object.Can reduce like this entering of impurity in subsequent deposition process.

For this reason, preferably select like this melting salt, make the metallic element being contained in ore or bullion is dissolved in the step in melting salt, the difference of the simple substance of special metal in melting salt (metallic element to be dissolved) or the standard potential of the standard potential of alloy and the simple substance of another kind of metal or alloy is more than 0.05V.Thereby the metallic element that can make to be dissolved in melting salt fully separates with the metallic element being retained in anode.The difference of standard potential is more preferably more than 0.1V, also more preferably more than 0.25V.

On anode, can calculate by this spy of following energy (Nernst) equation through the potential value of controlling.

In the case of use ore or bullion in contain plurality of target special metal, can control current potential like this so that each metal is dissolved in respectively in melting salt.Or, after a kind of special metal dissolves therein, the ore that contains residual metallic or bullion (anode) can be moved in another melting salt, and be preset value by control of Electric potentials in a similar manner, so that remaining special metal is dissolved in this melting salt.

Some metals are easier to separate by following deposition.In this case, whole handling object things can be dissolved, or can be only by special metal and some other dissolving metals.

The viewpoint entering from reducing impurity, the metallic element being contained in ore or bullion is dissolved in the step in melting salt, is preferably preset value by the control of Electric potentials of anode, thereby optionally makes special metal element be dissolved in melting salt.

Melting salt can be selected from muriate and fluorochemical.The example of muriate melting salt comprises KCl, NaCl, CaCl2, LiCl, RbCl, CsCl, SrCl ₂, BaCl ₂and MgCl ₂.The example of fluorochemical melting salt comprises LiF, NaF, KF, RbF, CsF, MgF ₂, CaF ₂, SrF ₂and BaF ₂.In the situation that rare earth element is carried out to fusion electrolysis, consider that efficiency is preferably used muriate melting salt; Particularly, KCl, NaCl and CaCl ₂because it is cheap and be easy to obtain preferably use.

In these melting salts, multiple melting salt can be combined and be used as the melting salt with required composition.For example, can use and have such as KCl-CaCl ₂, LiCl-KCl or NaCl-KCl and so on composition melting salt.

Negative electrode is by carbon or tend to form with the material that forms cationic basic metal in melting salt (as Li or Na) and form alloy.For example, can use aluminium (Al), zinc (Zn), gallium (Ga), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), plumbous (Pb) or bismuth (Bi).

For example, when ore or bullion during as anode,, can be arranged on the ore or the bullion that are contained in the electroconductibility basketry (basket) being formed by metal etc. in melting salt.Can form opening on the top of basketry, thereby make it possible to ore or bullion as handling object thing to insert in basketry by this opening; And can on the sidewall of basketry and diapire, form a large amount of holes, so that melting salt can flow in basketry.Basketry can be made up of material requested, the mesh members for example being woven by metal wire or for having the sheet member of sheet metal plate of large metering-orifice.Particularly, the material being formed by C, Pt, Mo etc. is effective.

Be ore etc. and have in high-resistance situation at object, preferably increase the contact area between object and conductive material.For example, by wrapping up object or object is filled in the space in metal porous parts with wire netting parts, thereby can effectively object be used as to electrode.

When negative electrode and the basketry that accommodates ore or bullion being arranged in melting salt and during as mentioned above from the current potential of external control anode (basketry), can making metal target be dissolved in melting salt by ore or bullion.

In deposition process subsequently, carry out fusion electrolysis by the pair of electrodes parts that are arranged in melting salt, so that the metallic element being dissolved in melting salt is deposited in the one (negative electrode) in electrod assembly.In this case, the potential value during by control fusion electrolysis, can optionally be deposited on negative electrode special metal element as metal or alloy.

Identical with dissolution process, in this deposition process, fusion electrolysis is characterised in that: different elements is deposited on negative electrode as metal or alloy under different current potentials; And utilize this feature to carry out separating metal.Therefore,, even if contain plurality of target special metal in melting salt, also can these metals be deposited on respectively on negative electrode by controlling current potential.

Electrod assembly can for example, be formed by () nickel (Ni), molybdenum (Mo) or vitreous carbon (C).

In the present embodiment, use two processes described above to separate and to extract the special metal element as melting target from object.In the present embodiment, owing to having used melting salt, therefore need system heating so that in this process the temperature of system be equal to or higher than the fusing point of melting salt.

The feature of these two processes is to have used melting salt.Thereby, utilize different melting salts to there is different this facts of dissolution-deposition current potential to element, and can carry out design process by such selection melting salt, so that can make this process easily carry out as the numerical value of the special metal element of object element and the dissolution-deposition current potential of other impurity metallic elements.Particularly, preferably select like this melting salt, make in the deposition or alloying step of special metal, in melting salt, the difference of the simple substance of this special metal or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.In melting salt, the difference of the simple substance of this special metal or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more preferably more than 0.1V, also more preferably more than 0.25V.

Like this, by the step of special metal deposition or alloying, be preferably preset value by the control of Electric potentials of electrod assembly, thereby optionally make special metal element deposition or alloying in melting salt.

The simple substance of the metal on negative electrode to be deposited on or the sedimentation potential of alloy can be calculated and be determined by electrochemistry.Particularly, calculate by Nernst equation.

The current potential of the Pr simple substance for example, being deposited by trivalent praseodymium (Pr) ion (using below Pr (III) to represent) can be determined by following equation.

E _pr=E ⁰ _pr+ RT/3Fln (a _{pr (III)}/ a _{pr (0)}) equation (1)

In equation (1), E ⁰ _prrepresent standard potential, R represents gas law constant, and T represents absolute temperature, and F represents Faraday's number, a _{pr (III)}represent the activity of Pr (III) ion, a _{pr (0)}represent the activity of Pr simple substance.

Consider activity quotient γ _{pr (III)}and rewrite in the situation of equation (1), due to a _{pr (0)}=1, thus following equation obtained.

E _pr=E ⁰ _pr+ RT/3Flna _{pr (III)}=E ⁰ _pr+ RT/3Fln (γ _{pr (III)}c _{pr (III)}) equation (2)

E _pr=E ⁰' _pr+ RT/3FlnC _{pr (III)}equation (3)

In equation (3), C _{pr (III)}represent the concentration of trivalent Pr ion, E ⁰' _prexpression condition electropotential (formal electrode potential) (equals E here, ⁰ _pr+ RT/3Fln γ _{pr (III)}).

Similarly, make the current potential (sedimentation potential: E of PrNi alloy deposition on electrode surface _prNi) can determine by following equation.

E _prNi=E ⁰' _prNi+ RT/3FlnC _{pr (III)}equation (4)

In equation (4), E ⁰' _prNiexpression condition electropotential (equals E here, ⁰ _prNi+ RT/3Fln γ _{pr (III)}).

Similarly, by utilizing above-mentioned equation, can determine all sedimental sedimentation potential corresponding to different melting salts.Special metal is deposited on negative electrode or the process of alloying in, consider the sedimentation potential value of this special metal or its alloy, select to there is the settling of potential difference with respect to another kind of metal or its alloy, or determine the order of deposition.

Voltage and current in operating process changes according to the size of electrode or position relationship.Therefore, determine the benchmark value of voltage and current based on these conditions, the potential value based on being determined by aforesaid method and order are determined the voltage and current in each step subsequently.

As mentioned above, according to the manufacturing in the method for metal by fusion electrolysis of the present embodiment, thereby potential value is controlled with electrochemical means and dissolved and deposit metal target.Therefore, with (for example) comprise repeatedly use acid etc. dissolving and the existing wet processing of leaching process compare, can simplify step; And can optionally separate and reclaim element-specific.In addition, without the proportion of adjusting melting salt; And, can be therein with the solid-state low temperature molten salt of processing by alternative thing, can adopt simple device structure.In addition, operator scheme also can be simplified.Therefore, can effectively carry out these steps with low cost.

Or, can be based on special metal being deposited on negative electrode or special metal is smelted in the antipodal conception of idea of alloying with above-mentioned.

That is to say, thereby be the method that the bullion that obtains by the ore that contains two or more metallic elements or by this ore by fusion electrolysis is manufactured special metal according to the metal fabrication methods of the present embodiment, the anode that is wherein provided with negative electrode and is formed by the anode material that contains ore or bullion in melting salt, and be preset value by the control of Electric potentials of this anode, thereby make metallic element corresponding to this current potential by being dissolved in melting salt in ore or bullion, and special metal is retained in anode.

In the method, object (ore or bullion) is used as to anode, and the metallic element except special metal element (, only as the metallic element of impurity) is dissolved in melting salt, so that special metal is retained in anode.In this case, similarly by controlling the current potential of anode, thereby cause such phenomenon: the metallic element as melting target is retained in anode, and impurity element is dissolved in melting salt.Thus, on anode, obtained the metallic substance after smelting.

In the method, the same melting salt of preferably selecting like this, make metallic element being dissolved into from ore or bullion in the step in melting salt, in melting salt, the difference of the simple substance of special metal or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.Thus, special metal fully can be separated and only special metal is retained in anode with other metal.The difference of standard potential is more preferably more than 0.1V, also more preferably more than 0.25V.

The potential value through controlling on anode can calculate by above-mentioned Nernst equation.

The ore of manufacturing in the method for metal by fusion electrolysis that can be used for the present embodiment is the ore that contains target special metal.The example of this ore comprises Gold Ore, silver ore, Copper Ores, iron ore, aluminum ore, lead ore, zinc ore, tin ore, mercury ore stone, sulphur ore, Rock Phosphate (72Min BPL), nickel ores, cobalt ore, manganese ore, chrome ore, molybdenum ore, tungsten ore, antimony ore, arsenic ore, bismuth mineral stone, strontium ore, beryllium, magnesium ore, barium ore and calcium ore.For example, can from hamartite, monazite, loparite, phosphatic rock, xenotime, sipylite and eudialite, obtain rare earth metal.

The bullion being obtained by ore represents the metal of the target special metal that contains low-purity, as the metal obtaining by smelting ore.

According to the present embodiment manufacture by fusion electrolysis the bullion that the method for metal is applicable to ore or is obtained by this ore, wherein this ore is used as anode and contains transition metal or rare earth metal.

Transition metal is not particularly limited, and can be the arbitrary element in the 3rd family (IIIA family) to the 11st family (IB family) in periodictable.Rare earth metal is also not particularly limited, and can be the arbitrary element in scandium (Sc), yttrium (Y) and 15 kinds of lanthanon of the 3rd family (IIIA family) in periodictable.

Also be applicable to according to the method for manufacturing metal by fusion electrolysis of the present embodiment the situation that the special metal of on negative electrode deposition or alloying is rare earth metal.In the present embodiment, suitably select by the composition to melting salt, even if can make the rare earth metal that can not deposit by aqueous electrolysis by uniform deposition.Thereby, can easily obtain being difficult to the rare earth metal as resource exploitation acquisition.

In the present embodiment, ore or the bullion being obtained by this ore are preferably particulate state or Powdered.When preparing pending ore or bullion so that it is particulate state or when Powdered, its surface-area increases and can improve processing efficiency.From this viewpoint, the maximum particle diameter of ore or bullion is preferably 0.01mm to 2mm, more preferably 0.01mm to 1mm, also 0.01mm to 0.2mm more preferably.

In addition, preferably will be particulate state or pulverous ore or bullion and push to be formed as anode.Can push being pulverous ore or bullion, thereby can be used as anode.In this case, the favourable space that exists melting salt easily to enter between particle.

The present embodiment is described with reference to the accompanying drawings below.In accompanying drawing below, identical or corresponding part marks and omits being repeated in this description it by identical reference symbol.

[the first embodiment-1]

To describe an example of the present embodiment, thereby it is by the method that obtains Nd, Dy and Pr in the ore that contains neodymium (Nd), dysprosium (Dy) and praseodymium (Pr) by fusion electrolysis.The example of this ore comprises monazite, phosphatic rock, xenotime, sipylite and eudialite.

As shown in Figure 1, first carry out preparation step (S10).

In this step, for example, prepare as the ore of handling object thing, melting salt to be used and comprise (for example) electrode and hold the device of the container of melting salt.Optionally, in order to promote the dissolving of handling object thing in melting salt, can be by handling object thing fine grinding to increase the contact area between handling object thing and melting salt.

The ore that contains Nd, Dy and Pr can be (for example) xenotime stone.For example, consist of the xenotime stone of 3.0%Nd, 7.9%Dy and 0.5%Pr.

Then, carry out the dissolving step (S20) in melting salt.

In this step (S20), ore and (another) electrod assembly are immersed in ready melting salt; This ore is connected by power supply with electrod assembly, to control the current potential of ore and electrod assembly.By controlling the current potential of ore, can optionally the rare earth element in ore (Nd, Dy and Pr) be dissolved in melting salt.The melting salt using can be the melting salt with required composition.

For example, melting salt can be LiF-NaF-KF; Another electrod assembly can be the electrode being formed by vitreous carbon; And above-mentioned ore can be used as handling object thing.

In this case, for example, when melting salt heating at 700 DEG C, can optionally Nd, Dy and Pr be dissolved in melting salt by ore.Be such value by control of Electric potentials, make under this potential value, other elements except Nd, Dy and Pr are dissolved in melting salt hardly, and Nd, Dy and Pr can be dissolved in melting salt.

Then, as shown in Figure 1, carry out separation and Extraction step (S30).

Particularly, in the melting salt that is wherein dissolved with Nd, Dy and Pr as above, insert pair of electrodes, and be preset value by the control of Electric potentials of this electrod assembly.For example, in the situation that using LiCl-KCl melting salt, as shown in Figure 2, by potential value control be with for the corresponding current potential of the determined sedimentation potential of each rare earth metal.Therefore,, by controlling current potential, can select to be deposited on the rare earth metal on electrode.Therefore, element ground selective recovery rare earth metal one by one.

For example, as shown in Figure 2, for the rare earth element such as Nd, Dy and Pr, each element all has different sedimentation potential values.Particularly, as shown in Figure 2, the sedimentation potential of Nd is that about 0.40V is (with respect to Li ⁺/ Li); The sedimentation potential of Pr and Dy is that about 0.47V is (with respect to Li ⁺/ Li); And the sedimentation potential of the Compound D yNi2 of Dy is that about 0.77V is (with respect to Li ⁺/ Li).

Sedimentation potential in Fig. 2 (with reference to Li) is described.In Fig. 2, the longitudinal axis represents sedimentation potential (unit: V).The value when temperature that these sedimentation potentials are is LiCl-KCl and melting salt at melting salt is made as 450 DEG C.

As mentioned above, element and compound have different sedimentation potentials.Therefore, by pair of electrodes is immersed in the melting salt that is dissolved with special metal, and by control cathode current potential so that its corresponding to above-mentioned sedimentation potential, thereby can optionally special rare earth elements be deposited on negative electrode.For example, by changing the potential value (, changing successively current potential) of negative electrode, can select special metal to be deposited.

For example, as shown in Figure 3, between the pair of electrodes being immersed in the melting salt that has dissolved Nd, Dy and Pr, apply successively different voltage.In melting salt, the concentration of Nd, Dy and Pr (ionic concn) is 0.5 % by mole.

In the time that the data described in Fig. 2 are used as to sedimentation potential value, for example, LiCl-KCl are used as to melting salt and the temperature setting of this melting salt is set to 450 DEG C.In Fig. 3, transverse axis represents the treatment time, and the longitudinal axis represents the ionic concn of melting salt rare earth elements.The unit of the longitudinal axis is % by mole.

In step 1, when first Ni being used as to cathode material and the current potential of negative electrode is made as lower than 0.77V (with respect to Li ⁺/ Li) and a little higher than 0.63V (with respect to Li ⁺/ Li) value time (for example, potential difference is made as to 0.631V (with respect to Li ⁺/ Li)), Dy ion and cathode material Ni alloying, DyNi thus ₂be deposited on cathode surface.Therefore, as shown in Figure 3, in melting salt, Dy ionic concn sharply reduces.Can reclaim thus Dy, until the Dy ionic concn in melting salt becomes approximately 3.6 × 10 ^-4till % by mole.

Then, in step 2, for example, when another electrode (, Mo electrode) is used as to negative electrode and the current potential of negative electrode is made as to a little higher than 0.40V (with respect to Li ⁺/ Li) value (for example, potential difference is made as to 0.401V (with respect to Li ⁺/ Li)) time, Pr is deposited in the one (negative electrode) in electrode.Therefore, as shown in Figure 3, in melting salt, Pr ionic concn sharply reduces.Can reclaim like this Pr, until the Pr ionic concn in melting salt becomes approximately 0.017 % by mole.

The electrode using in step 2 is not in step 1, to have deposited DyNi ₂electrode.For example, can before starting, step 2 will in step 1, deposit DyNi ₂electrode remove, then another electrode can be immersed in melting salt; Or, deposit DyNi ₂electrode can not shift out and retain, then, in step 2, can control the current potential of another electrode.

Then, in step 3, for example, when the current potential of another electrode (, Mo electrode) is made as to 0.10V (with respect to Li ⁺/ Li) time, Nd is deposited on this electrode (negative electrode).Therefore, as shown in Figure 3, the Nd ionic concn in melting salt sharply reduces.Can reclaim like this Nd, for example, until the Nd ionic concn in melting salt becomes () approximately 2.7 × 10 ^-7till % by mole.

Can before step 3 starts, the electrode that has deposited Pr in step 2 be removed from melting salt, then another electrode can be immersed in melting salt; Or, the electrode that has deposited Pr in step 2 can be continued to be immersed in melting salt, then in step 3, can use another electrode.

The DyNi reclaiming in treatment step 1 in step 4 ₂: will on surface, deposit DyNi ₂electrode and another electrode (for example, Mo electrode) be immersed in melting salt; Then the current potential of DyNi2 electrode is located in such potential range: in this potential range, Dy can dissolve, but Ni does not dissolve, (the above 2.6V of 0.77V is following (with respect to Li ⁺/ Li)), thus can make Dy be dissolved in melting salt, and only have Dy to be deposited on the surface of another electrode.

As mentioned above, can from melting salt, reclaim separately target special metal.

(for the device of the method for the present embodiment)

The device of the method for the present embodiment that is used for Fig. 1 is described with reference to Figure 4 and 5 below.Retrieving arrangement shown in Fig. 4 comprises the container 1 that holds melting salt, be contained in the melting salt 2 in container 1, hold the basketry 4 of handling object thing (ore or bullion) 3, electrode 6 to 8, for the well heater 10 of heating and melting salt 2, and the control unit 9 being electrically connected with basketry 4 and electrode 6 to 8 by wire 5.Control unit 9 is configured to control the current potential (change current potential) an of electrode (being basketry 4) and another electrode (being the one in electrode 6 to 8).In control unit 9, controlled potential value can change.Arrange that well heater 10 is looped around around container 1 it.Electrode 6 to 8 can be formed by required material.For example, electrode 6 can be formed by nickel (Ni).For example,

electrode

7 and 8 can be formed by carbon (C).Container 1 can have ringwise or polygonal bottom surface.Basketry 4 can be above-mentioned basketry.

Be predetermined potential value by control unit 9 by basketry 4 and electrode 6 to 8 controls.As described below, by being different current potentials by electrode 6 to 8 controls, the different special metal corresponding from controlled potential value can be deposited on the surface of electrode 6 to 8.For example, as described below, can regulate the setting potential value of electrode 6, thereby by DyNi ₂film 11 is deposited on the surface of electrode 6.By regulating the setting current potential of electrode 7, Pr film 12 can be deposited on the surface of electrode 7.By regulating the setting current potential of electrode 8, Nd film 13 can be deposited on the surface of electrode 8.

Afterwards the electrode 6 that has deposited DyNi2 film 11 is placed in the container that accommodates melting salt 21 as shown in Figure 5.In addition, another electrode is placed in melting salt 2, make it with surface on deposited DyNi ₂the electrode 6 of film 11 is

relative.Electrode

6 and 15 is connected to control unit 9 by wire 5.In the time of well heater 10 heating and melting salt 2 with being arranged to around container 1, using control unit 9 is preset value by the control of Electric potentials of electrode 6 and 15.Now, control like this current potential, the sedimentation potential that the current potential that makes negative electrode (electrode 15) is Dy.

Thus, by Dy from being deposited on the lip-deep DyNi of electrode 6 ₂in film 11, be dissolved in melting salt 2, and Dy film 16 be deposited on the surface of electrode 15.Using in twice processing of the device shown in Figure 4 and 5, utilize the Heating temperature of the melting salt 2 of well heater 10 all to can be (for example) 800 DEG C.Like this, special metal can be deposited on the surface of

electrode

7,8 and 15 with simple substance form.

The method of the present embodiment, for example, can implement in the following manner the method in the case of implementing with the device shown in Figure 4 and 5.

First prepare as the ore (9kg) of handling object thing 3 with as the LiF-NaF-KF of melting salt 2.For example, this ore can contain Nd, the Pr of 0.5 % by weight and the Dy of 7.9 % by weight of 3.0 % by weight.This ore is ground and puts into basketry 4.From improving the angle of processing efficiency, thereby preferably by grinding, the size as the ore of handling object thing 3 is down to minimum.For example, ore is ground to maximum particle diameter be 2mm following, be preferably that 1mm is following, the particle below 0.2mm more preferably.The amount of melting salt 2 is approximately 16 liters (quality: 25kg).

One in the handling object thing 3 and the electrode 6 to 8 that are contained in basketry 4, as pair of electrodes, is then carried out with reference to the step 1 in the method for Fig. 2 and 3 the present embodiment of describing to step 3.Particularly, in above-mentioned steps 1, the handling object thing 3 and the electrode 6 that are contained in basketry 4 are used as to pair of electrodes, and are preset value by the control of Electric potentials of electrode.Thus, DyNi2 is deposited on the surface of electrode 6.In above-mentioned steps 2, the handling object thing 3 and the electrode 7 that are contained in basketry 4 are used as to pair of electrodes, and are preset value by the control of Electric potentials of electrode.Thus, Pr is deposited on the surface of electrode 7.The quality that is deposited on the lip-deep Pr film of electrode 7 in Fig. 4 is extremely about 50g of (for example) about 30g.

In above-mentioned steps 3, the handling object thing 3 and the electrode 8 that are contained in basketry 4 are used as to pair of electrodes, and are preset value by the control of Electric potentials of electrode.Thus, Nd is deposited on the surface of electrode 8.The quality that is deposited on the lip-deep Nd film of electrode 8 is extremely about 300g of (for example) about 200g.

In above-mentioned steps 4, electrode 6 and electrode 15 are placed in the device shown in Fig. 5, and are preset value by the electropotential control in melting salt.Thus, Dy is deposited on the surface of electrode 15.The quality that is deposited on the lip-deep Dy film 16 of electrode 15 is (for example) 600g to 800g.

As described in reference to Fig. 4, the lip-deep step that metal target is dissolved in to the step in melting salt 2 and special metal is deposited on to

electrode

7,8 etc. with simple substance form can be carried out in identical device (accommodating identical melting salt 2).On the other hand, from the different device of the described device that dissolving metal is used in the step in melting salt 2 (device shown in Fig. 4) with reference to Fig. 4, described in carry out step 4 by Dy from DyNi ₂the step of middle separation extraction.

As mentioned above, can from the ore as handling object thing 3 or bullion, reclaim special metal (for example, Dy, Pr and Nd).

[the first embodiment-2]

To an example of the present embodiment be described, thereby it is for being obtained the method for neodymium (Nd), dysprosium (Dy) and praseodymium (Pr) by bullion by fusion electrolysis, wherein this bullion is by the ore that contains Nd, Dy and Pr is smelted and obtained.

The bullion that contains Nd, Dy and Pr can be (for example) norium (didymium).The smelting process that obtains norium is not particularly limited, can be selected from known method.

As shown in Figure 6, first carry out the preparation step (S11) as the bullion of handling object thing.Particularly, as shown in Figure 7, will be immersed in as the bullion of handling object thing 3 in the melting salt 2 being contained in container 1; Then wire 5 is connected to handling object thing 3, wire 5 is for being connected to the power supply of control unit 9.The salt using is LiCl-KCl.

In melting salt 2, in being contained in basketry 24 and as electrode materials 25 and the basketry 24 of another electrode, together immerse.Electrode materials 25 is for tending to and the material that forms cationic basic metal (as Li and Na) the formation alloy in melting salt.The example of electrode materials 25 comprises aluminium (Al), zinc (Zn), gallium (Ga), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), plumbous (Pb) and bismuth (Bi).

Then, as shown in Figure 6, carry out Nd, Dy and Pr to be dissolved in the step (S21) in melting salt.

Particularly, as shown in Figure 7, utilize control unit 9 to control handling object thing 3 and the current potential that is contained in the electrode materials 25 in basketry 24, thereby the current potential of handling object thing 3 is adjusted into preset value.Thus, using the rare earth element such as Nd, Dy and Pr by being dissolved in melting salt 2 in the bullion of handling object thing 3.

Then, as shown in Figure 6, deposit DyNi by electrolysis ₂step (S31).Particularly, as shown in Figure 8, use the electrode 6 being formed by nickel to replace and in Fig. 7, be contained in the electrode materials 25 in basketry 24, and be immersed in melting salt 2.This electrode 6 is connected to control unit 9 by wire 5.In this state, control unit 9 is for using as the handling object thing 3 of an electrode be preset value as the control of Electric potentials of the electrode 6 of another electrode.

Thus, rare earth element (as Dy) is dissolved in melting salt 2 by handling object thing 3, and DyNi2 is deposited on the surface of electrode 6 from melting salt 2.

Then, as shown in Figure 6, reclaim the step (S32) of Pr by electrolysis.Particularly, as shown in Figure 9, use the electrode 27 being formed by carbon to replace handling object thing 3, to be immersed in melting salt 2 as an electrode.In addition, use the electrode 7 being formed by carbon to replace the electrode 6 in Fig. 8, electrode 7 is placed on towards the position of electrode 27 and is immersed in melting salt 2.Electrode 27 and electrode 7 are electrically connected to control unit 9 by wire 5.In this state, be preset value by the control of Electric potentials of an electrode 27 and another electrode 7.

Thus, the Pr that makes to be dissolved in melting salt 2 is deposited on the surface of electrode 7.In the time that muriate is used as to melting salt 2, from the region around electrode 27, discharge chlorine (Cl2).

Then, as shown in Figure 6, carry out the step (S33) by electrolytic recovery Nd.Particularly, as shown in figure 10, use the electrode 8 being formed by carbon to replace electrode 7, electrode 8 is placed as towards electrode 27 and is immersed in melting salt 2.This electrode 8 is connected to control unit 9 by wire 5.Control unit 9 is for being preset value by the control of Electric potentials of electrode 8 and electrode 27.Thus, Nd is deposited on the surface of electrode 8.Now, from the region around electrode 27, discharge chlorine.

Then, undertaken from DyNi by electrolysis ₂the step (S34) of middle recovery Dy, wherein DyNi ₂reclaim in step (S31).Particularly, as shown in Figure 5, DyNi will have been deposited on surface ₂electrode 6 (with reference to Fig. 8) be immersed in melting salt 2; Place another electrode 15, it is immersed in melting salt 2; And to use control unit 9 be preset value by the control of Electric potentials of electrode 6 and 15.Thus, by Dy from being deposited on the lip-deep DyNi of electrode 6 ₂in be temporarily dissolved in melting salt 2, then Dy film 16 is deposited on the surface of electrode 15.Thus, recovering rare earth metal Nd, Dy and Pr separately.

Above-mentioned steps (S21 to S32) can be utilized with lower device structure and carry out.For example, above-mentioned steps (S31) can utilize the device structure shown in Figure 11 to carry out.

Particularly, replace the handling object thing 3 in the device structure of Fig. 8 with the basketry 24 that accommodates material 26, and be immersed in melting salt 2, wherein material 26 by the step shown in Fig. 7 alloying.As shown in figure 11, basketry 24 is electrically connected to control unit 9 by wire 5.By electrode 6 and to be contained in the control of Electric potentials of the material 26 of alloying in basketry 24 and by the step shown in Fig. 7 be preset value.Thus, the Dy that makes to be dissolved in melting salt 2 is deposited on the surface of electrode 6 with the form of DyNi2.By the step identical with step in Fig. 6 (S34), can from be deposited on the lip-deep DyNi2 of electrode 6, reclaim the Dy of simple substance form.

Then, can process by utilizing the device shown in Figure 12 to construct, thereby implement above-mentioned steps (S32).Particularly, as shown in figure 12, use the electrode 7 being formed by carbon to replace the electrode 6 in Figure 11, place it in the face of the position of basketry 24 and be immersed in melting salt 2.Electrode 7 is electrically connected to control unit 9 by wire 5.This control unit is for being preset value by electrode 7 and the control of Electric potentials that is contained in the alloy 26 of basketry 24.Thus, the Pr that makes to be dissolved in melting salt 2 is deposited on the surface of electrode 7.

Then, can, by utilizing the device structure shown in Figure 13 to process, implement thus above-mentioned steps (S33).Particularly, as shown in figure 13, use the electrode 8 being formed by carbon to replace the electrode 7 in Figure 12, place it in the face of the position of basketry 24 and be immersed in melting salt 2.Electrode 8 is electrically connected to control unit 9 by wire 5.Control unit 9 is for being preset value by electrode 8 and the control of Electric potentials that is placed in the alloy 26 in basketry 24.Thus, Nd is deposited on the surface of electrode 8.

By using described method, can reclaim separately successively the special metal being contained in bullion.Compared with existing wet separation etc., can simplification device structure according to the method for the present embodiment, and can shorten the treatment time.Thereby, can reduce the cost that elements such as obtaining rare earth element produces.In addition,, by the current potential of suitable setting electrode, can make special metal be deposited on electrode surface with simple substance form, thereby can obtain high purity metal.Can deposit by above-mentioned calculative determination the current potential of each metal and alloy.

[the second embodiment]

A kind of method of being manufactured tungsten by fusion electrolysis by the handling object thing of tungstenic according to the method for manufacturing tungsten by fusion electrolysis of the present embodiment, the method comprises: tungsten is dissolved into from handling object thing to the step in melting salt, and by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in melting salt, thereby the tungsten that makes to be present in melting salt is deposited on the step in the one in pair of electrodes parts, the tungsten that wherein this melting salt contains dissolving.

; say roughly; this embodiment comprises the tungsten being contained in handling object thing is dissolved in to the process in melting salt, and by fusion electrolysis, tungsten is deposited on to the process in the one (negative electrode) in electrode from the melting salt of the tungsten that contains dissolving.This embodiment is characterised in that: by the current potential of control electrode, thereby optionally make tungsten deposit from handling object thing, to manufacture highly purified tungsten.

First by describing, the tungsten being contained in handling object thing is dissolved in to the process in melting salt.

The process that the tungsten being contained in handling object thing is dissolved in melting salt is (for example) chemical dissolution process.Particularly, handling object thing is ground to form to particle or powder, mix with salt and heat.Thus, the tungsten being contained in handling object thing can be dissolved in melting salt.Or, handling object thing can be placed in to melting salt and make it and dissolve.

Another process is electrochemical process.Particularly, the anode being formed by the anode material that contains handling object thing is placed in melting salt, and the potential value of the handling object thing that is set to anode is controlled, thereby the tungsten that optionally makes to be contained in handling object thing dissolves.Fusion electrolysis is characterised in that: different elements dissolves under different current potentials.Can utilize this feature by tungsten and other metal separation.Like this, by handling object thing is used as to anode and controls the current potential in dissolution process, thereby can optionally tungsten be dissolved in melting salt.

In this step, can make whole handling object thing dissolve, or tungstenic part that can dissolution process object or only make tungsten dissolve.Can adopt the condition that makes to be contained in the non-tungsten dissolving metal in handling object thing; But, if can, preferably control current potential only to make tungsten dissolve.,, tungsten being dissolved in the step of melting salt, be preferably preset value by the control of Electric potentials of anode and negative electrode, thereby optionally tungsten be dissolved in melting salt.Thereby, can reduce entering of impurity in subsequent deposition process.

For this reason, preferably select like this melting salt, make tungsten being dissolved into from handling object thing in the step in melting salt, in melting salt, the difference of the simple substance of tungsten or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.Thereby the tungsten that can make to be dissolved in melting salt fully separates with the metallic element being retained in anode.The difference of standard potential is more preferably more than 0.1V, also more preferably more than 0.25V.

The potential value of controlling on anode can calculate by following Nernst equation.

For the negative electrode of dissolving step by carbon or tend to form with the material that forms cationic basic metal (as Li or Na) in melting salt and form alloy.For example, can use aluminium (Al), zinc (Zn), gallium (Ga), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), plumbous (Pb) or bismuth (Bi).

In the time that the handling object thing of tungstenic is used as to anode, for example, the handling object thing being contained in the electroconductibility basketry (anode material) being formed by metal etc. can be arranged in melting salt.Handling object thing can form opening on the top of basketry so that can insert in basketry by this opening; And can on the sidewall of basketry and diapire, form a large amount of holes so that melting salt can flow in basketry.Basketry can be made up of material requested, the mesh members for example being woven by metal wire or have the sheet member of the sheet metal plate of large metering-orifice.Particularly, the material being formed by C, Pt, Mo etc. is effective.

Be oxide compound etc. and have in high-resistance situation at object, preferably increase the contact area between object and electro-conductive material.For example, by wrapping up object or object is packed into the space in metal porous parts with wire netting parts, thereby object is used as to electrode effectively.

The anode (for example, holding the metal basketry of handling object thing) forming by negative electrode with by the anode material that contains handling object thing is arranged in melting salt; Connection control unit, this control unit is constructed to from the current potential of external control electrode; And control as mentioned above current potential.Thus, tungsten can be dissolved in melting salt from handling object thing.

In deposition process subsequently, utilize the pair of electrodes parts in the melting salt that is arranged on the tungsten that contains dissolving to carry out fusion electrolysis, so that tungsten is deposited in the one (negative electrode) in electrod assembly.In this case, the potential value during by control fusion electrolysis, can optionally be deposited on tungsten on negative electrode with metal or alloy form.

Identical with dissolution process, in this deposition process, utilize following characteristic by tungsten and other metal separation: in the time of fusion electrolysis, different elements is deposited on negative electrode with metal or alloy form under different current potentials.Thereby, even if contain other metals except tungsten in melting salt, thereby also can tungsten be deposited on separately on negative electrode by controlling current potential.Therefore, can obtain highly purified tungsten.

In the time of deposits tungsten, when the dissolution-deposition current potential of tungsten and the difference of dissolution-deposition current potential that is contained in the another kind of metal in melting salt too little to such an extent as to while being difficult to tungsten and this metal separation, can select cathode material and can control current potential, thereby depositing the alloy of this cathode material and tungsten.Thus, the tungsten in melting salt can be separated with other foreign metal with the form of tungstenalloy; And after this, for example, can in another kind of melting salt, utilize with the cathode material of tungstenalloy and carry out dissolving step and deposition step, thereby manufacture highly purified tungsten.

Electrod assembly for deposition step can for example, be formed by () nickel (Ni), molybdenum (Mo) or vitreous carbon (C).

In the present embodiment, use two processes described above separation and extraction tungsten from handling object thing.In the present embodiment, owing to having used melting salt, therefore need system to heat so that the system temperature in this process is equal to or higher than the fusing point of melting salt.

Or, can in this process, smelt based on antipodal idea.That is to say, handling object thing is used as to anode and only makes to be dissolved in melting salt as the metallic element of impurity.In this case, similarly by being preset value by the control of Electric potentials of anode, to cause such phenomenon: tungsten is retained in anode, and impurity element dissolves.Thereby, on anode, obtained tungsten.

The feature of these two processes is uses of melting salt.Thereby, utilize different melting salt in fusion electrolysis element to be there is to the characteristic of different dissolution-deposition current potentials; And can design like this this process, that is: select melting salt so that the difference between the dissolution-deposition current potential of tungsten and the dissolution-deposition of non-tungsten inclusion metal is enough large differences that can make that this process easily carries out.

Particularly, preferably like this select melting salt, make making in the step of tungsten deposition or alloying, in melting salt, the difference of the simple substance of tungsten or the simple substance of the standard potential of alloy and another kind of foreign metal or the standard potential of alloy is more than 0.05V.In melting salt, the difference of the simple substance of tungsten or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more preferably more than 0.1V, also more preferably more than 0.25V.

Like this, making in the step of tungsten deposition or alloying, be preferably preset value by the control of Electric potentials of electrod assembly, optionally to make tungsten deposition or the alloying in melting salt.

The sedimentation potential of the tungsten on negative electrode to be deposited on can be calculated and be determined by electrochemistry.Particularly, calculate by Nernst equation.

For example, can determine the current potential by divalence W ion (using below W (II) to represent) deposits tungsten (W) simple substance by following equation.

E _w=E ⁰ _w+ RT/3Fln (a _{w (II})/a _{w (0)}) equation (1)

In equation (1), E ⁰ _wrepresent standard potential, R represents gas law constant, and T represents absolute temperature, and F represents Faraday's number, a _{w (II)}represent the activity of W (II) ion, a _{w (0)}represent the activity of W simple substance.

When considering activity quotient γ _{w (II)}and rewrite equation when (1), due to a _{w (0)}=1, thus following equation obtained.

E _wr=E ⁰ _w+ RT/3Flna _{w (II)}=E ⁰ _w+ RT/3Fln (γ _{w (II)}c _{w (II)}) equation (2)

E _w=E ⁰' _w+ RT/3FlnC _{w (II)}equation (3)

In equation (3), C _{w (II)}represent the concentration of divalence W ion, E ⁰' _wexpression condition electropotential (equals E here, ⁰ _w+ RT/3Fln γ _{w (II)}).

Similarly, by using above equation, can determine all sedimental sedimentation potential corresponding to different melting salts.Also can similarly calculate in the situation that makes tungsten be deposited as alloy.Tungsten is deposited on negative electrode or the process of alloying in, consider the sedimentation potential value of tungsten simple substance or tungstenalloy, select like this melting salt and cathode material, so that it reaches sufficiently high potential difference with respect to the simple substance of another kind of metal or the sedimentation potential of alloy, and determine to make tungsten deposition still to make tungstenalloy deposition.

Voltage and current in operating process changes according to the size of electrode or position relationship.Therefore, determine the reference value of voltage and current based on condition, the potential value based on being determined by aforesaid method and order are determined the voltage and current in each step subsequently.

As mentioned above, according to the manufacturing in the method for tungsten by fusion electrolysis of the present embodiment, thereby potential value is controlled with electrochemical means and dissolved and deposits tungsten.Therefore, with (for example) comprise repeatedly use acid etc. dissolving and the existing wet processing of leaching process compare, can simplify step; And can optionally separate and reclaim element-specific.In addition, without the proportion of adjusting melting salt; And, can be therein with the solid-state low temperature molten salt of processing by alternative thing, can adopt simple device structure.In addition, operator scheme also can be simplified.Therefore, can effectively carry out these steps with low cost.

Or, as mentioned above, can based on tungsten is deposited on negative electrode or the antipodal idea of idea of alloying is smelted tungsten.

That is to say, thereby be to manufacture tungsten method by fusion electrolysis by the handling object thing that contains tungsten according to the method for the manufacture metal of the present embodiment, the anode that negative electrode is wherein set in melting salt and is formed by the anode material that contains handling object thing, and control the current potential of anode, thereby make metallic element corresponding to this potential value by being dissolved in melting salt in handling object thing, and tungsten is retained in anode.

In the method, the anode material that contains handling object thing is dissolved in melting salt as anode and by the metallic element except tungsten (, only as the metallic element of impurity), so that tungsten is retained in anode.In this case, similarly by controlling the current potential of anode, to cause such phenomenon: be wherein retained in anode as the tungsten of smelting target, and impurity element is dissolved in melting salt.Thereby, on anode, obtained the tungsten after smelting.

In the method, also preferably select like this melting salt, make metallic element is dissolved in the step in melting salt in by handling object thing, in melting salt, the difference of the simple substance of tungsten or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.Therefore, tungsten fully can be separated and only tungsten is retained in anode with other metal.The difference of standard potential is more preferably more than 0.1V, also more preferably more than 0.25V.

The potential value of controlling on anode can calculate by above-mentioned Nernst equation.

According to the manufacturing in the method for tungsten by fusion electrolysis of the present embodiment, the handling object thing that contains tungsten is preferably the metallic substance that (for example) contains tungsten.The example of the metallic substance that contains tungsten comprises tungsten well heater.

The present embodiment is also applicable to the situation that handling object thing is the metallic substance that contains tungsten and transition metal.This transition metal is not particularly limited, and can be the arbitrary element in the 3rd family (IIIA family) to the 11st family (IB family) of periodictable.The example of the metallic substance that contains tungsten and transition metal comprises Wimet.

Handling object thing can be (for example) hard metal article.Here the goods that the overall expression of hard metal article comprises Hardmetal materials, as the cutting tool that comprises Hardmetal materials, fixture, punch die and mould.

Melting salt can be selected from muriate melting salt and fluorochemical melting salt.Can use the fused salt mixture that contains muriate melting salt and fluorochemical melting salt.

The example of muriate melting salt comprises KCl, NaCl, CaCl ₂, LiCl, RbCl, CsCl, SrCl ₂, BaCl ₂and MgCl ₂.The example of fluorochemical melting salt comprises LiF, NaF, KF, RbF, CsF, MgF ₂, CaF ₂, SrF ₂and BaF ₂.Consider that efficiency is preferably used muriate melting salt; Particularly, KCl, NaCl and CaCl ₂because it is cheap and easily obtain but preferably use.

According to the manufacturing by fusion electrolysis in the method for tungsten of the present embodiment, can preferably use with lower device., comprise for the device of manufacturing the method for tungsten by fusion electrolysis according to the present embodiment: the container that accommodates melting salt; Negative electrode, it is immersed in the melting salt being contained in container; And anode, it is immersed in the melting salt being contained in container and comprises handling object thing, this handling object thing contains tungsten, wherein melting salt can flow between anode interior and outside, this device also comprises control unit, it is preset value that this control unit is constructed to the control of Electric potentials of negative electrode and anode, and in this control unit, the value of current potential can change.Comprise for the device of manufacturing the method for tungsten by fusion electrolysis according to the present embodiment: accommodate the container of melting salt, the tungsten that this melting salt contains dissolving; And negative electrode and anode, it is immersed in the melting salt being contained in container, and wherein this device comprises control unit, and it is preset value that this control unit is constructed to the control of Electric potentials of negative electrode and anode, and the value of current potential can change in this control unit.

With reference to Figure 18 and 19 devices of describing for the present embodiment.Device shown in Figure 18 comprises the container 1 that holds melting salt, be contained in the melting salt 2 in container 1, hold the basketry 4 of the handling object thing 3 that contains tungsten, electrode 6, for the well heater 10 of heating and melting salt 2, and the control unit 9 being electrically connected with basketry 4 and electrode 6 by wire 5.

It is preset value that control unit 9 is configured to the control of Electric potentials an of electrode (anode, i.e. basketry 4) and another electrode (negative electrode, i.e. electrode 6).In control unit 9, controlled potential value can change.Well heater 10 is set so that it is looped around around container 1.Electrode 6 can be formed by required material, for example carbon.The bottom shape of container 1 can be annular or Polygons.Basketry 4 can be above-mentioned basketry.

Be predetermined potential value by control unit 9 by the control of Electric potentials of basketry 4 and electrode 6.Thus, tungsten is dissolved in melting salt 2 from handling object thing 3.

After abundant stripping, remove basketry 4 and electrode 6 and another electrode 7 (negative electrode) and another electrode 8 (anode) are placed in melting salt 2 from handling object thing 3 at tungsten.These electrodes 7 are connected with control unit 9 by wire 5 with 8.Using control unit 9 is preset value by the control of Electric potentials of electrode 7 and 8.Now, control like this current potential, to make the current potential of electrode 7 as the sedimentation potential of tungsten.Therefore the tungsten that, makes to be dissolved in melting salt 2 is deposited on the surface of electrode 7 (negative electrode).

Electrode

7 and 8 can be formed by the material such as vitreous carbon (C).

In two kinds of processing of the device shown in use Figure 18 and 19, the Heating temperature of utilizing the melting salt 2 of well heater 10 can be all (for example) 800 DEG C.Like this, tungsten can be deposited on the surface of electrode 7 with simple substance form.

Current potential that can control

electrode

7 and 8 so that the alloy deposition of tungsten and cathode material on the surface of electrode 7 (negative electrode).In this case, can utilize the electrode 7 of alloying to carry out above-mentioned dissolving step and deposition step.That is, again prepare the device shown in Figure 18, and use with the electrode 7 of tungstenalloy and replace above-mentioned handling object thing 3.

The tungsten manufacture method of the present embodiment, for example, can implement in the following manner the method in the case of implementing with the device shown in Figure 18 and 19.

First prepare as the carbide alloy cutting tool (9kg) of handling object thing 3 with as the KCl-NaCl of melting salt 2.For example, carbide alloy cutting tool can contain the wolfram varbide (WC) of 90 % by weight and the cobalt (Co) of 10 % by weight.This carbide alloy cutting tool is ground and puts into basketry 4.From improving the angle of processing efficiency, preferably by grinding, the size as the carbide alloy cutting tool of handling object thing 3 is reduced to minimum size.For example, carbide alloy cutting tool is ground to form maximum particle diameter be 5mm following, be preferably that 3mm is following, the particle below 1mm more preferably.The amount of melting salt 2 is about 16 liters (quality: 25kg).

Above-mentioned dissolving step can be by carrying out as the carbon dioxide process carbon electrode of electrode 6.Subsequently, can utilize by vitreous carbon and form and carry out deposition step as the electrode of

electrode

7 and 8.

As described in, can be from as reclaiming tungsten the carbide alloy cutting tool of handling object thing 3.Compared with existing method for wet separation etc., according to the present embodiment manufacture the method for tungsten by fusion electrolysis can simplification device structure and also can shorten the treatment time.Thereby, can reduce spent cost.In addition,, by the current potential of suitable setting electrode, can make tungsten be deposited on electrode surface with simple substance form, thereby can obtain highly purified tungsten.Can be by the current potential of above-mentioned calculative determination deposits tungsten and tungstenalloy.

[the 3rd embodiment]

According to the method for manufacturing lithium by fusion electrolysis of the present embodiment be a kind of by fusion electrolysis by the method for manufacturing lithium containing lithium handling object thing, the method comprises: lithium is dissolved into from handling object thing to the step in melting salt, and by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in melting salt, thereby the lithium that makes to be present in melting salt is deposited on this to the step in the one in electrod assembly, the lithium that wherein this melting salt contains dissolving.

; the lithium manufacture method of this embodiment comprises the lithium being contained in handling object thing is dissolved in to the process in melting salt, and by fusion electrolysis, lithium is deposited on to the step in the one (negative electrode) in electrode from the melting salt of the lithium that contains dissolving.This embodiment is characterised in that: by controlling the electropotential in the step of dissolving lithium, thus dissolving lithium from handling object thing optionally; And by being preset value by electropotential control in the step of lithium deposition, can optionally lithium be deposited on negative electrode from melting salt, thereby manufacture highly purified lithium.

First describe the lithium being contained in handling object thing is dissolved in to the step in melting salt.

The process that the lithium being contained in handling object thing is dissolved in melting salt is (for example) chemical dissolution process.Particularly, handling object thing is ground to form to particle or powder, mix with salt and heat.Thus, the lithium being contained in handling object thing can be dissolved in melting salt.Or, handling object thing can be placed in to melting salt and make it and dissolve.

Another process is electrochemical process.Particularly, the anode being formed by the anode material that contains handling object thing is placed in melting salt, and the potential value of the handling object thing that is placed as anode is controlled, thereby the lithium that optionally makes to be contained in handling object thing dissolves.Fusion electrolysis is characterised in that: different elements dissolves under different current potentials.Therefore, by handling object thing is used as to anode and controls the current potential in dissolution process, can optionally lithium be dissolved in melting salt by this way, thereby by lithium and other metal separation.

In this step, can make whole handling object thing dissolve, or in can dissolution process object containing lithium part or only make lithium dissolve.Also can be by the non-lithium dissolving metal being contained in handling object thing; But, if can, preferably control current potential and only make lithium dissolve.,, lithium being dissolved in the step of melting salt, be preferably preset value by the control of Electric potentials of anode and negative electrode, thereby optionally lithium be dissolved in melting salt.Thus, can reduce entering of impurity in subsequent deposition process.

For this reason, preferably select like this melting salt, make lithium being dissolved into from handling object thing in the step in melting salt, in melting salt, the difference of the simple substance of lithium or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.Thereby the lithium that can make to be dissolved in melting salt fully separates with the metallic element being retained in anode.The difference of standard potential is more preferably more than 0.1V, also more preferably more than 0.25V.

For the negative electrode of dissolving step by carbon or tend to form with the material that forms cationic basic metal in melting salt (as Li or Na) and form alloy.For example, can use aluminium (Al), zinc (Zn), gallium (Ga), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), plumbous (Pb) or bismuth (Bi).

In the time that the handling object thing containing lithium is used as to anode, for example, the handling object thing being contained in the electroconductibility basketry (anode material) being formed by metal etc. can be arranged in melting salt.Handling object thing can form opening on the top of basketry so that can insert in basketry by this opening; And can on the sidewall of basketry and diapire, form a large amount of holes so that melting salt can flow in basketry.Basketry can be made up of material requested, the mesh members for example being woven by metal wire or have the sheet member of the sheet metal plate of large metering-orifice.Particularly, the material being formed by C, Pt, Mo etc. is effective.

Be oxide compound etc. and have in high-resistance situation at object, preferably increase the contact area between object and electro-conductive material.For example, by with wire netting parts parcels object or object is packed into the space in metal porous parts, thus by object effectively as electrode.

The anode (for example, holding the metal basketry of handling object thing) forming by negative electrode with by the anode material that contains handling object thing is arranged in melting salt; Connection control unit, this control unit is constructed to from the current potential of external control electrode; And control as mentioned above current potential.Thus, lithium can be dissolved in melting salt from handling object thing.

In deposition step subsequently, utilize the pair of electrodes parts in the melting salt that is arranged on the lithium that contains dissolving to carry out fusion electrolysis, so that lithium is deposited in the one (negative electrode) in electrod assembly.In this case, the potential value during by control fusion electrolysis, can optionally be deposited on lithium on negative electrode with metal or alloy form.

Identical with dissolving step, in this deposition step, utilize following characteristic by lithium and other metal separation: in the time of fusion electrolysis, different elements is deposited on negative electrode with metal or alloy form under different current potentials.Thereby, even if contain other metals except lithium in melting salt, also can lithium be deposited on separately on negative electrode by controlling current potential.Therefore, can obtain highly purified lithium.

In the time of lithium deposition, when the dissolution-deposition current potential of lithium and the difference of dissolution-deposition current potential that is contained in the another kind of metal in melting salt too little to such an extent as to while being difficult to lithium and this metal separation, can select cathode material and can control current potential, thereby depositing the alloy of this cathode material and lithium.Thus, the lithium in melting salt can be separated with other foreign metal with the form of lithium alloy; And after this, for example, can in another kind of melting salt, utilize with the cathode material of lithium alloyage and carry out dissolving step and deposition step, thereby manufacture highly purified lithium.

In the present embodiment, use two steps described above to separate and to reclaim lithium from handling object thing.

In the present embodiment, owing to having used melting salt, therefore need system heating so that in these steps the temperature of system be equal to or higher than the fusing point of melting salt.

The feature of these two steps is to have utilized melting salt as electrolytic solution.Thereby, utilize different melting salt in fusion electrolysis element to be there is to the characteristic of different dissolution-deposition current potentials; And can design like this these steps, that is: select melting salt so that the difference between the dissolution-deposition current potential of lithium and the dissolution-deposition of non-lithium foreign metal is enough large differences that can make that this step easily carries out.

Particularly, preferably like this select melting salt, make making in the step of lithium deposition or alloying, in melting salt, the difference of the simple substance of lithium or the simple substance of the standard potential of alloy and another kind of foreign metal or the standard potential of alloy is more than 0.05V.The difference of the simple substance of the simple substance of the lithium in melting salt or the standard potential of alloy and another kind of metal or the standard potential of alloy is more preferably more than 0.1V, also more preferably more than 0.25V.

Like this, making in the step of lithium deposition or alloying, be preferably preset value by the control of Electric potentials of electrod assembly, optionally to make lithium deposition or the alloying in melting salt.

The sedimentation potential of the lithium on negative electrode to be deposited on can be calculated and be determined by electrochemistry.Particularly, calculate by Nernst equation.

For example, can determine by Li ion (Li by following equation ⁺) current potential of Li simple substance of deposition.

E _li=E ⁰ _li+ RT/3Fln (a _{li (I)}/ a _{li (0)}) equation (1)

In equation (1), E ⁰ _lirepresent standard potential, R represents gas law constant, and T represents absolute temperature, and F represents Faraday's number, a _{li (I)}represent the activity of Li ion, a _{li (0)}represent the activity of Li simple substance.

When considering activity quotient γ _{li (I)}and rewrite equation when (1), due to a _{li (0)}=1, thus following equation obtained.

E _li=E ⁰ _li+ RT/3Flna _{li (I)}=E ⁰ _li+ RT/3Fln (γ _{li (I)}c _{li (I)}) equation (2)

E _li=E ⁰' _li+ RT/3FlnC _{li (I)}equation (3)

In equation (3), C _{li (I)}represent the concentration of Li ion, E ⁰' _liexpression condition electropotential (equals E here, ⁰ _li+ RT/3Fln γ _{li (I)}).

Similarly, in the situation that LiM alloy (M represents alloyed metal (AM)) is deposited on electrode surface, this current potential (sedimentation potential: E _liM) can determine by following equation.

E _liM=E ⁰' _liM+ RT/3FlnC _{li (I)}equation (4)

In equation (4), E ⁰' _liMexpression condition electropotential (equals E here, ⁰' _liM+ RT/3Fln γ _{li (I)}).

Similarly, by using above-mentioned equation, can determine all sedimental sedimentation potential corresponding to different melting salts.Lithium is deposited on negative electrode or the step of alloying in, consider the sedimentation potential value of lithium simple substance and lithium alloy, select like this melting salt and cathode material, so that it reaches sufficiently high potential difference with respect to the simple substance of another kind of metal or the sedimentation potential of alloy, and determine to make lithium deposition still to make lithium alloy deposition.

As mentioned above, according to the manufacturing in the method for lithium by fusion electrolysis of the present embodiment, thereby potential value is controlled with electrochemical means and dissolved and lithium deposition.Therefore, with (for example) comprise repeatedly use acid etc. dissolving and the existing wet processing of leaching process compare, can simplify step; And can optionally separate and reclaim element-specific.In addition, without the proportion of adjusting melting salt; And, can be therein with the solid-state low temperature molten salt of processing by selection lithium, can adopt simple device structure.In addition, operator scheme also can be simplified.Therefore, can effectively carry out these steps with low cost.

According to the manufacturing by fusion electrolysis in the method for lithium of the present embodiment, handling object thing is not limited, as long as it is the material containing lithium.The preferred example of handling object thing comprises the negative material of lithium primary cell and the positive electrode material of lithium-ion secondary cell.

In lithium-ion secondary cell, the example of the positive electrode active materials of positive electrode material comprises cobalt acid lithium (LiCoO ₂), lithium nickelate (LiNiO ₂), lithium nickel cobalt dioxide (LiCo _0.3ni _0.7o ₂), lithium manganate (LiMn ₂o ₄), lithium titanate (Li ₄ti ₅o ₁₂), lithium manganese composite oxide ((LiM _ymn _2-yo ₄); M=Cr, Co, Ni) and lithium acid (lithium acid).

The example of muriate melting salt comprises KCl, NaCl, CaCl ₂, LiCl, RbCl, CsCl, SrCl ₂, BaCl ₂and MgCl ₂.The example of fluorochemical melting salt comprises LiF, NaF, KF, RbF, CsF, MgF ₂, CaF ₂, SrF ₂and BaF ₂.Consider that efficiency is preferably used muriate melting salt; Particularly, KCl, NaCl and CaCl ₂preferably use due to its cheap and easy acquisition.

According to the manufacturing by fusion electrolysis in the method for lithium of the present embodiment, can preferably use with lower device., comprise for the device of manufacturing the method for lithium by fusion electrolysis according to the present embodiment: the container that accommodates melting salt; Negative electrode, it is immersed in the melting salt being contained in container; And anode, it is immersed in the melting salt being contained in container and comprises electroconductibility handling object thing, this electroconductibility handling object thing contains lithium, wherein melting salt can flow between anode interior and outside, this device also comprises control unit, it is preset value that this control unit is constructed to the control of Electric potentials of negative electrode and anode, and in this control unit, the value of current potential can change.

Comprise for the device of manufacturing the method for lithium by fusion electrolysis according to the present embodiment: accommodate the container of melting salt, the lithium that this melting salt contains dissolving; And negative electrode and anode, it is immersed in the melting salt being contained in container, and wherein this device comprises control unit, and it is preset value that this control unit is constructed to the control of Electric potentials of negative electrode and anode, and potential value in this control unit can change.

With reference to Figure 18 and 19 devices of describing for the present embodiment.Device shown in Figure 18 comprises the container 1 that holds melting salt, be contained in the melting salt 2 in container 1, hold the basketry 4 of the handling object thing 3 that contains lithium, electrode 6, for the well heater 10 of heating and melting salt 2, and the control unit 9 being electrically connected with basketry 4 and electrode 6 by wire 5.

It is preset value that control unit 9 is configured to the control of Electric potentials an of electrode (anode, i.e. basketry 4) and another electrode (negative electrode, i.e. electrode 6).In control unit 9, controlled potential value can change.Well heater 10 is set so that it is looped around around container 1.Electrode 6 can be formed by required material, for example aluminium.The bottom surface of container 1 can be ringwise or Polygons.Basketry 4 can be above-mentioned basketry.

Be predetermined potential value by control unit 9 by the control of Electric potentials of basketry 4 and electrode 6.Therefore, lithium is dissolved in melting salt 2 from handling object thing 3.

From handling object thing 3 fully after stripping, remove basketry 4 and electrode 6 and as shown in figure 19 at lithium, another electrode 7 (negative electrode) and another electrode 8 (anode) are placed in melting salt 2.These electrodes 7 are connected with control unit 9 by wire 5 with 8.Using control unit 9 is preset value by the control of Electric potentials of electrode 7 and 8.Now, control current potential to make the current potential of electrode 7 as the sedimentation potential of lithium.Therefore, the lithium being dissolved in melting salt 2 is deposited on the surface of electrode 7 (negative electrode).

Electrode

7 and 8 can be formed by the material such as vitreous carbon (C).

In two kinds of processing of the device shown in use Figure 18 and 19, the Heating temperature of utilizing the melting salt 2 of well heater 10 can be (for example) 800 DEG C.Like this, lithium can be deposited on the surface of electrode 7 with simple substance form.

Current potential that can control

electrode

7 and 8 so that the alloy deposition of lithium and cathode material on the surface of electrode 7 (negative electrode).In this case, can utilize the electrode 7 of alloying to carry out above-mentioned dissolving step and deposition step.That is, again prepare the device shown in Figure 18, and use with the electrode 7 of lithium alloyage and replace above-mentioned handling object thing 3.

The lithium manufacture method of the present embodiment, for example, can implement in the following manner the method in the case of implementing with the device shown in Figure 18 and 19.

First prepare as the lithium anode material that contains in the lithium ion battery of handling object thing 3, and prepare the KCl-NaCl as melting salt 2.For example, positive electrode material is containing cobalt acid lithium (LiCoO ₂) or the powder of lithium manganate.This carbide alloy cutting tool is ground and puts into basketry 4.From improving the angle of processing efficiency, preferably by grinding, the size as the positive electrode material of handling object thing 3 is reduced to minimum size.For example, positive electrode material is ground to maximum particle diameter be 5mm following, be preferably that 3mm is following, the particle below 1mm more preferably.Can utilize as the carbon dioxide process carbon electrode of electrode 6 and carry out above-mentioned dissolving step.Subsequently, can utilize by vitreous carbon and form and carry out deposition step as the electrode of

electrode

7 and 8.

As described in, can be from as reclaiming lithium the positive electrode material of handling object thing 3.

Compared with existing method for wet separation etc., according to the present embodiment manufacture the method for lithium by fusion electrolysis can simplification device structure and also can shorten the treatment time.Thereby, can reduce spent cost.In addition,, by the current potential of suitable setting electrode, can make lithium be deposited on electrode surface with simple substance form, thereby can obtain highly purified lithium.

[the 4th embodiment]

The present embodiment is to manufacture the method for metal by fusion electrolysis, and the method comprises: the metallic element being contained in handling object thing is dissolved in to the step in melting salt, and wherein this handling object thing contains two or more metallic elements; And by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in melting salt, thereby make to be present in special metal in melting salt this to the one in electrod assembly on the step of deposition or alloying, the metallic element that wherein this melting salt contains dissolving.

Say roughly, this embodiment comprises the special metal being contained in handling object thing is dissolved in to the process in melting salt, and by fusion electrolysis, special metal is deposited on to the process in the one (negative electrode) in electrode from the melting salt of the special metal that contains dissolving.This embodiment is characterised in that: by being preset value by the control of Electric potentials of electrode, can optionally special metal be deposited from handling object thing, thereby obtain highly purified special metal.

First by describing, the special metal being contained in handling object thing is dissolved in to the process in melting salt.

The process that the special metal being contained in handling object thing is dissolved in melting salt is (for example) chemical dissolution process.Particularly, handling object thing is ground to form to particle or powder, mix with salt and heat.Thus, the special metal being contained in handling object thing can be dissolved in melting salt.Or, handling object thing can be placed in to melting salt and make it and dissolve.

Another process is electrochemical process.Particularly, the anode forming by negative electrode with by the anode material that contains handling object thing is placed in melting salt; And the current potential of controlling anode is preset value, thereby the special metal of the potential value corresponding to controlling is dissolved in melting salt from handling object thing.Fusion electrolysis is characterised in that: different elements dissolves under different current potentials; And utilize this feature by special metal and other metal separation.Like this, by handling object thing is used as to anode and controls the current potential in dissolution process, thereby can optionally special metal be dissolved in melting salt.

In this step, can make to be contained in the whole dissolving metals in handling object thing.Or, can make to be contained in special metal and other dissolving metals in handling object thing.The special metal that preferably only makes to be contained in handling object thing dissolves.Can adopt the condition of the special metal that makes to be contained in handling object thing and other kind of dissolving metal; But, if can, preferably control current potential and only make special metal dissolve.,, special metal being dissolved in the step of melting salt, be preferably preset value by the control of Electric potentials of anode, thereby optionally special metal be dissolved in melting salt.Thus, can reduce entering of impurity in subsequent deposition process.

For this reason, preferably select like this melting salt, make special metal being dissolved into from handling object thing in the step in melting salt, in melting salt, the difference of the simple substance of special metal or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.Thereby the special metal that can make to be dissolved in melting salt fully separates with the metallic element being retained in anode.The difference of standard potential is more preferably more than 0.1V, also more preferably more than 0.25V.

When in handling object thing, contain more than one target special metal time, in dissolving step, more than one special metal is dissolved in melting salt.

In the time that handling object thing only contains a kind of special metal, as mentioned above, this special metal is dissolved and then carries out deposition step, with manufacturing objective metal.In the time that handling object thing contains two or more target special metal, can only the one in these metals be dissolved in melting salt; Carry out subsequently deposition step; Afterwards, can carry out another dissolving step, so that remaining special metal is dissolved in this melting salt.In this case, can be by used handling object thing in dissolving step first from moving in another melting salt for the melting salt of this dissolving step, and carry out dissolving step, thus remaining special metal is dissolved.

When being contained in two or more special metals in handling object thing while being dissolved in melting salt, can carry out deposition step subsequently, so that be present in special metal deposition or the alloying on electrode materials one by one in melting salt, thereby can manufacture required special metal.In this case, deposit on electrode materials at a kind of special metal or alloying after, can replace this electrode materials with another kind of electrode materials, and the another kind of special metal being dissolved in melting salt can be deposited or alloying on this electrode materials.

In the time that the handling object thing containing special metal is used as to anode, for example, the handling object thing being contained in the electroconductibility basketry (anode material) being formed by metal etc. can be arranged in melting salt.Handling object thing can form opening on the top of basketry so that can insert in basketry by this opening; And can on the sidewall of basketry and diapire, form a large amount of holes so that melting salt can flow in basketry.Basketry can be made up of material requested, the mesh members for example being woven by metal wire or have the sheet member of the sheet metal plate of large metering-orifice.Particularly, the material being formed by C, Pt, Mo etc. is effective.

The anode (for example, holding the metal basketry of handling object thing) forming by negative electrode with by the anode material that contains handling object thing is arranged in melting salt; And the current potential of controlling anode is preset value.Therefore, special metal can be dissolved in melting salt from handling object thing.

In deposition process subsequently, utilize the pair of electrodes parts in the melting salt that is arranged on the special metal that contains dissolving to carry out fusion electrolysis, so that special metal is deposited in the one (negative electrode) in electrod assembly.In this case, the potential value during by control fusion electrolysis, can optionally be deposited on special metal on negative electrode with the form of metal or alloy.

Identical with dissolving step, in this deposition step, utilize following characteristic by special metal and other metal separation: in the time of fusion electrolysis, different elements is deposited on negative electrode with metal or alloy form under different current potentials.Thereby, even if contain other metals except special metal in melting salt, also can optionally special metal be deposited or alloying on negative electrode by controlling current potential.Therefore, can obtain highly purified special metal.

In the time of deposition special metal, when the dissolution-deposition current potential of special metal and the difference of dissolution-deposition current potential that is contained in the another kind of metal in melting salt too little to such an extent as to while being difficult to special metal and other metal separation, can select cathode material and can control current potential, thereby depositing the alloy of this cathode material and special metal.Thus, the special metal in melting salt can be separated with other foreign metal with the form of alloy; And after this, for example, can in another kind of melting salt, utilize with the cathode material of special metal alloying and carry out dissolving step and deposition step, thereby manufacture highly purified special metal.

In the present embodiment, use two processes described above separation and extraction special metal from handling object thing.In the present embodiment, owing to having used melting salt, therefore need system heating so that in this process the temperature of system be equal to or higher than the fusing point of melting salt.

Or, as described below, can be based on smelting with the antipodal idea of this process.That is to say, handling object thing is used as to anode and only the metallic element as impurity is dissolved in melting salt.In this case, similarly by controlling the current potential of anode, to cause such phenomenon: special metal is retained in anode, and impurity element dissolves.Thereby, on anode, obtained special metal.

The feature of these two processes is uses of melting salt.Thereby, utilize different melting salt in fusion electrolysis element to be there is to the characteristic of different dissolution-deposition current potentials; And can design like this this process, that is: select melting salt so that the difference between the dissolution-deposition of the dissolution-deposition current potential of special metal and other foreign metals except special metal is enough large differences that can make that this process easily carries out.

Particularly, preferably select like this melting salt, make making in the step of special metal deposition or alloying, in melting salt, the difference of the simple substance of special metal or the simple substance of the standard potential of alloy and another kind of foreign metal or the standard potential of alloy is more than 0.05V.

In melting salt, the difference of the simple substance of special metal or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more preferably more than 0.1V, also more preferably more than 0.25V.

Like this, making in the step of special metal deposition or alloying, be preferably preset value by the control of Electric potentials of electrod assembly, optionally to make special metal element deposition or the alloying in melting salt.

The sedimentation potential of the special metal on negative electrode to be deposited on can be calculated and be determined by electrochemistry.Particularly, calculate by Nernst equation.

For example, the current potential depositing from melting salt as molybdenum (Mo) simple substance of special metal can be definite in order to lower equation, and in this melting salt, molybdenum is dissolved as tetravalence Mo ion (using below Mo (IV) to represent).

E _mo=E ⁰ _mo+ RT/3Fln (a _{mo (IV)}/ a _{mo (0)}) equation (1)

In equation (1), E ⁰ _morepresent standard potential, R represents gas law constant, and T represents absolute temperature, and F represents Faraday's number, a _{mo (IV)}represent the activity of Mo (IV) ion, a _{mo (0)}represent the activity of Mo simple substance.

When considering activity quotient γ _{mo (IV)}and rewrite equation when (1), due to a _{mo (0)}=1, thus following equation obtained.

E _mo=E ⁰ _mo+ RT/3Flna _{mo (IV)}=E ⁰ _mo+ RT/3Fln (γ _{mo (IV)}c _{mo (IV)}) equation (2)

E _mo=E ⁰' _mo+ RT/3FlnC _{mo (IV)}equation (3)

In equation (3), C _{mo (IV)}represent the concentration of tetravalence Mo ion, E ⁰' _moexpression condition electropotential (equals E here, ⁰ _mo+ RT/3Fln γ _{mo (IV)}).

Similarly, by using above equation, can determine all sedimental sedimentation potential corresponding to different melting salts.

With alloy form deposition molybdenum in the situation that, also can carry out similar calculating.

Molybdenum is deposited on negative electrode or the process of alloying in, consider the sedimentation potential value of molybdenum simple substance and molybdenum alloy, select like this melting salt and cathode material, so that it reaches fully high potential difference with respect to the simple substance of another kind of metal or the sedimentation potential of alloy, and determine to make molybdenum simple substance deposition still to make molybdenum alloy deposition.

As mentioned above, according to the manufacturing in the method for special metal by fusion electrolysis of the present embodiment, thereby potential value is controlled with electrochemical means and dissolved and deposit special metal.Therefore, with (for example) comprise repeatedly use acid etc. dissolving and the existing wet processing of leaching process compare, can simplify step; And can optionally separate and reclaim special metal.In addition, without the proportion of adjusting melting salt; And, can be therein with the solid-state low temperature molten salt of processing by selection special metal, can adopt simple device structure.In addition, operator scheme also can be simplified.Therefore, can effectively carry out these steps with low cost.

Or, as mentioned above, can based on special metal is deposited on negative electrode or the antipodal idea melting of the idea special metal of alloying.

That is to say, to manufacture the method for special metal from the handling object thing that contains two or more metallic elements by fusion electrolysis according to the method for manufacturing metal by fusion electrolysis of the present embodiment, the anode that negative electrode is wherein set in melting salt and is formed by the anode material that comprises handling object thing, and be preset value by the control of Electric potentials of this anode, thereby make to be dissolved into melting salt from handling object thing corresponding to the metallic element of this current potential, and special metal is retained in anode.

In this manufacture method, by the anode material that contains handling object thing as anode and by other metallic elements except special metal element (, only as the metallic element of impurity) be dissolved in melting salt, so that special metal is retained in anode.In this case, similarly by controlling the current potential of anode, to cause such phenomenon: be retained in anode as the metallic element of smelting target, and impurity element is dissolved in melting salt.Thereby, on anode, obtained the special metal after smelting.

In this method, also preferably select like this melting salt, make metallic element being dissolved into from handling object in the step melting salt, in melting salt, the difference of the simple substance of this special metal or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.Therefore, special metal fully can be separated and only special metal is retained in anode with other metal.The difference of standard potential is more preferably more than 0.1V, also more preferably more than 0.25V.

According to the manufacturing by fusion electrolysis in the method for metal of the present embodiment, the handling object thing that contains two or more metallic elements is not limited, as long as it is the metallic substance that contains target special metal.For example, can from the battery material of collecting, obtain Mn, Co, Sb etc.; Can from metal superconducting material, obtain Nb etc.; Can from oxide superconducting materials, obtain Bi, Sr etc.; Can from ferro-vanadium, obtain V; Can from Mo-Cu scatterer, obtain Mo etc.; And can from fiber optic materials, obtain Ge etc.

The present embodiment is also applicable to the situation that handling object thing is the metallic substance that contains transition metal or rare earth metal.This transition metal is not particularly limited, and can be the arbitrary element in the 3rd family (IIIA family) to the 11st family (IB family) of periodictable.The present embodiment is also applicable to handling object thing and contains one or more metals of selecting in the group that free V, Nb, Mo, Ti, Ta, Zr and Hf form situation as transition metal.

In addition, the present embodiment is also applicable to the situation that handling object thing contains a kind of in Sr and Ba or contains these two kinds of metals simultaneously.And the present embodiment is also applicable to the situation that handling object thing contains one or more metals in the group of selecting free Zn, Cd, Ga, In, Ge, Sn, Pb, Sb and Bi formation.

Manufacturing by fusion electrolysis in the method for metal of the present embodiment, by selecting transition metal or rare earth metal as waiting to deposit or the special metal of alloying, can obtain transition metal or rare earth metal.This transition metal is not particularly limited, and can be the arbitrary element in the 3rd family (IIIA family) to the 11st family (IB family) of periodictable.

Similarly, by from V, Nb, Mo, Ti, Ta, Zr and Hf, or Sr and Ba, or in Zn, Cd, Ga, In, Ge, Sn, Pb, Sb and Bi, select to wait to deposit or the special metal of alloying, can obtain these metals.

As mentioned above, in dissolving step, one or more in these metals that are contained in handling object thing can be dissolved in melting salt, and can make successively special metal deposit from melting salt or alloying on electrod assembly.

Handling object thing is preferably particulate state or Powdered.When preparing handling object thing so that its be particulate state or when Powdered, can improve processing efficiency thereby increase its surface-area.

In addition, can to prepare be particle or pulverous handling object thing pushes and is used as anode.In this case, the favourable space that exists melting salt easily to enter between particle.

According to the manufacturing by fusion electrolysis in the method for metal of the present embodiment, can preferably use with lower device., this device preferably includes: the container that accommodates melting salt; Negative electrode, it is immersed in the melting salt being contained in container; And anode, it is immersed in the melting salt being contained in container and comprises handling object thing, this handling object thing contains two or more metallic elements, wherein melting salt can flow between anode interior and outside, this device also comprises control unit, it is preset value that this control unit is constructed to the control of Electric potentials of negative electrode and anode, and in this control unit, the value of current potential can change.Be preferably for the device of manufacturing the method for metal by fusion electrolysis according to the present embodiment the device that comprises following part: accommodate the container of melting salt, the special metal that this melting salt comprises dissolving; And negative electrode and anode, it is immersed in the melting salt being contained in container, and wherein this device comprises control unit, and it is preset value that this control unit is constructed to the control of Electric potentials of negative electrode and anode, and the value of current potential can change in this control unit.

With reference to Figure 18 and 19, this device is described.Device shown in Figure 18 comprises the container 1 that holds melting salt, be contained in the melting salt 2 in container 1, hold the basketry 4 of the handling object thing 3 that contains two or more metallic elements, electrode 6, for the well heater 10 of heating and melting salt 2, and the control unit 9 being electrically connected with basketry 4 and electrode 6 by wire 5.

It is preset value that control unit 9 is configured to the control of Electric potentials an of electrode (anode, i.e. basketry 4) and another electrode (negative electrode, i.e. electrode 6).In control unit 9, controlled potential value can change.Arrange that well heater 10 makes it be surrounded on container 1 around.Electrode 6 can be formed by required material, for example carbon.The bottom surface of container 1 can be annular or Polygons.Basketry 4 can be above-mentioned basketry.

By control unit 9 by the control of Electric potentials position predetermined potential value of basketry 4 and electrode 6.Therefore, special metal is dissolved in melting salt 2 from handling object thing 3.

After special metal is fully dissolved from handling object thing 3, remove basketry 4 and electrode 6 and another electrode 7 (negative electrode) and another electrode 8 (anode) are placed in melting salt 2.These electrodes 7 are connected with control unit 9 by wire 5 with 8.Using control unit 9 is preset value by the control of Electric potentials of electrode 7 and 8.Now, control current potential to make the current potential of electrode 7 as the sedimentation potential of special metal.Therefore, the special metal being dissolved in melting salt 2 is deposited on the surface of electrode 7 (negative electrode).

Electrode

7 and 8 can be formed by the material such as vitreous carbon (C).

In two kinds of processing of the device shown in use Figure 18 and 19, the Heating temperature of utilizing the melting salt 2 of well heater 10 can be (for example) 800 DEG C.Like this, special metal can be deposited on the surface of electrode 7 with simple substance form.

Current potential that can control

electrode

7 and 8, so that the alloy deposition of special metal and cathode material is on the surface of electrode 7 (negative electrode).In this case, can utilize the electrode 7 of alloying to carry out above-mentioned dissolving step and deposition step.That is, again prepare the device shown in Figure 18, and the electrode 7 of utilization and special metal alloying replaces above-mentioned handling object thing 3.

In the case of implement the method for manufacture metal of the present embodiment with the device shown in Figure 18 and 19, for example, can implement in the following manner the method.Below, by the example of describing about vanadium, molybdenum, strontium and germanium.

(vanadium)

For example, obtain vanadium by the metal fabrication methods of the present embodiment.First prepare the ferro-vanadium (1kg) as handling object thing 3, and prepare the NaCl-KCl as melting salt 2.For example, the vanadium (V) that ferro-vanadium contains 75 % by weight and the iron (Fe) of 25 % by weight.Ferro-vanadium is ground and is placed in basketry 4.The amount of melting salt 2 is about 15 liters.

Can utilize carbon dioxide process carbon electrode to carry out above-mentioned dissolving step as electrode 6.Then, can utilize by vitreous carbon and form and carry out deposition step as the electrode of

electrode

7 and 8.

(molybdenum)

Obtain molybdenum by the method for the manufacture metal of the present embodiment.First prepare the Mo-Cu scatterer (1kg) as handling object thing 3, and prepare the LiCl-KCl as melting salt 2.For example, the molybdenum (Mo) that Mo-Cu scatterer contains 50 % by weight and the copper (Cu) of 50 % by weight.Mo-Cu scatterer is ground and is placed in basketry 4.The amount of melting salt 2 is about 5 liters.

Can utilize as the carbon dioxide process carbon electrode of electrode 6 and carry out above-mentioned dissolving step.Then, can be by being formed by vitreous carbon and carrying out deposition step as the electrode of

electrode

7 and 8.

(strontium)

Obtain molybdenum by the method for the manufacture metal of the present embodiment.First prepare the oxide superconducting materials (1kg) as handling object thing 3, and prepare the LiF-CaF as melting salt 2 ₂.For example, the strontium (Sr) that oxide superconducting materials contains 17 % by weight and the calcium (Ca) of 8 % by weight.Oxide superconducting materials is ground and is placed in basketry 4.The amount of melting salt 2 is about 4 liters.

electrode

7 and 8.

(germanium)

Obtain germanium by the method for the manufacture metal of the present embodiment.First prepare the fiber optic materials (1kg) as handling object thing 3, and prepare the LiF-CaF as melting salt 2 ₂.For example, the germanium (Ge) that fiber optic materials contains 3 % by weight.Fiber optic materials is ground and is placed in basketry 4.The amount of melting salt 2 is about 4 liters.

electrode

7 and 8.

As described in, by using ferro-vanadium, Mo-Cu scatterer, oxide superconducting materials and fiber optic materials as handling object thing 3, can obtain respectively vanadium, molybdenum, strontium and germanium.From improving the angle of processing efficiency, thereby preferably by grinding, the size as ferro-vanadium, Mo-Cu scatterer, oxide superconducting materials and the fiber optic materials of handling object thing 3 is reduced to minimum size: for example, preferably handling object thing 3 is ground to form to maximum particle diameter and be that 5mm is following, following, the particle below 1mm more preferably also of 3mm more preferably.

Compared with existing recovery method etc., according to the present embodiment manufacture the method for metal by fusion electrolysis can simplification device structure, and also can shorten the treatment time.Thereby, can reduce spent cost.In addition,, by the current potential of suitable setting electrode, can make special metal be deposited on the surface of electrode with simple substance form, thereby can obtain highly purified metal.

Can be by above-mentioned calculative determination for depositing the current potential of vanadium, vanadium alloy, molybdenum, molybdenum alloy, strontium, strontium alloy, germanium and germanium alloy.

Each self-described so far first to fourth embodiment.But, for example, in order to obtain tungsten, lithium, transition metal and the rare earth metal in the second to the 4th embodiment, the method in can other embodiment of all or part of employing.

Embodiment

[the first embodiment (embodiment)]

Manufacture Nd, Dy and Pr by fusion electrolysis by the ore containing rare earth metal.

(sample)

Xenotime stone as the ore of handling object thing.With grinding mill or ball mill grinding xenotime stone so that its particle diameter is about 2mm.By sample (xenotime stone) molybdenum (Mo) net (50 order) parcel after grinding.

As shown in figure 14, the sample powder being contained in net is used as to anode (anode electrode).(experimental detail)

Adopt LiF-NaF-KF eutectic melting salt as melting salt.This salt heats melting completely at 700 DEG C.Above-mentioned anode is connected with electric wire with negative electrode and is immersed in this melting salt.Negative electrode is formed by vitreous carbon.

Dissolving step:

In the time that anode and negative electrode are so immersed in melting salt, anode is maintained to predetermined potential.After approximately 4 hours, sample is taken out from melting salt and utilize inductively coupled plasma-atomic emission spectrum (ICP-AES) to carry out compositional analysis to sample.

Electrolysis step:

After dissolving step, the negative electrode being formed by Ni and the anode that formed by vitreous carbon are immersed in melting salt.Cathode potential is maintained to predetermined potential.Particularly, maintain like this current potential to make forming Dy-Ni alloy in LiF-NaF-KF melting salt.After the scheduled time, observe the condition of surface of negative electrode.

(result)

About dissolving step:

Observe dissolving step Anodic electric current over time as shown in figure 15.

In Figure 15, transverse axis represents the time (unit: minute), and the longitudinal axis represents anodic current value (unit: mA).As shown in figure 15, prolongation in time of current value and reducing.Current value is following trend with respect to the velocity of variation of time: in the time measuring beginning, (while starting to apply electric current) velocity of variation is the highest, and afterwards, this velocity of variation reduces gradually.

By ICP-AES, the sample taking out is carried out to compositional analysis from melting salt.Result confirmation, Nd and Dy dissolve in melting salt.

About electrolysis step:

Figure 16 and 17 shows the observations in the cross section that utilizes scanning electronic microscope (SEM) anticathode upper layer.As shown in FIG. 16 and 17, Dy-Ni alloy 32 is deposited on the surface of electrode body portion 31, and electrode body portion 31 forms negative electrode and formed by Ni.This Dy-Ni alloy 32 may be to form by being present in Dy in melting salt and forming reacting between the Ni of negative electrode, and is deposited on the surface of negative electrode.Like this, can by being contained in Dy in xenotime stone, with the form of Dy-Ni alloy, from this ore, separation and extraction be out.

Figure 16 shows the backscattered electron image of observing by SEM.Figure 17 has shown the carrying out shown in Figure 16 the Dy atom in the region of X-ray analysis and has distributed.As shown in figure 17, in the region 33 corresponding to electrode body portion 31, almost can't detect Dy; But, in the region 34 corresponding to Dy-Ni alloy 32, Dy detected.

[the second embodiment (embodiment)]

Carbamide tool is used as to the metallic substance of tungstenic and manufactures tungsten by fusion electrolysis.

(sample)

It is the cutting tool of the cobalt (it is as binding agent) of the wolfram varbide that contains 90 % by weight and 10 % by weight as the carbamide tool of handling object thing.With ball mill or masher grinding cutting instrument so that its particle diameter is about 2mm.By sample (cutting tool) molybdenum (Mo) net (50 order) parcel after grinding.As shown in figure 14, the sample powder (handling object thing) being contained in Mo net is used as to anode (anode electrode).

(experimental detail)

Adopt NaCl-KCl eutectic melting salt as melting salt.This salt heats melting completely at 700 DEG C.Above-mentioned anode is connected with electric wire with negative electrode and is immersed in this melting salt.Negative electrode is formed by vitreous carbon.

Dissolving step:

In the time that anode and negative electrode are so immersed in melting salt, anode is maintained to predetermined potential.After the scheduled time, sample is taken out from melting salt and by ICP-AES, sample is carried out to compositional analysis.

Electrolysis step:

After dissolving step, the negative electrode being formed by vitreous carbon and the anode that formed by vitreous carbon are immersed in melting salt.Cathode potential is maintained to predetermined potential.Particularly, maintain current potential like this so that tungsten deposits in NaCl-KCl melting salt.After the scheduled time, observe the condition of surface of negative electrode.

(result)

About dissolving step:

Viewed dissolving step Anodic electric current over time with identical (Figure 15) in the first embodiment (embodiment).In Figure 15, transverse axis represents the time (unit: minute), and the longitudinal axis represents anodic current value (unit: mA).As shown in figure 15, current value reduces in time.Current value is following trend with respect to the velocity of variation of time: in the time measuring beginning, (while starting to apply electric current) velocity of variation is the highest, and afterwards, this velocity of variation reduces gradually.

By ICP-AES, the sample taking out is carried out to compositional analysis from melting salt.Result has confirmed the dissolving of tungsten in melting salt.

About electrolysis (deposition) step:

The observation in the cross section by scanning electronic microscope (SEM) anticathode upper layer shows: tungsten is deposited on the surface of electrode body portion, and this electrode body portion forms negative electrode and also formed by vitreous carbon.

Like this, can from the carbide alloy cutting tool of tungstenic, obtain highly purified tungsten.

[the 3rd embodiment (embodiment)]

Commercially available lithium-ion secondary cell is used as containing lithium handling object thing, and manufactures lithium by fusion electrolysis.

(sample)

Commercially available lithium-ion secondary cell (positive pole is formed by cobalt acid lithium and negative pole is formed by graphite, cobalt acid lithium content: quality %).

(separation of anode material of lithium battery)

Lithium-ion secondary cell is immersed in electrolytic solution (5%NaCl) and is discharged until voltage becomes 0.1mV.Then, by hand disassembly, positive electrode material is taken out, and grind to obtain the positive electrode material powder that median size is 0.1mm with cutting type shredder.The composition of this powder is described in Table I.Analytical results confirmation, the powder obtaining by separation is cobalt acid lithium.

[Table I]

?	Composition (quality %)
		Li	7
Co	60

By this molybdenum (Mo) net (200 order) parcel for powder.As shown in figure 14, the sample powder being contained in Mo net is used as to anode (positive electrode).

(preparation of electrolyzer)

Adopt NaCl-KCl eutectic melting salt as melting salt.This salt heats melting completely at 700 DEG C.Above-mentioned anode is connected with electric wire with negative electrode and is immersed in this melting salt.Negative electrode (cathode electrode) is formed by carbon.

(electrolytic dissolution step)

By ICP-AES, the sample taking out is carried out to compositional analysis from melting salt.Result has confirmed the dissolving of lithium in melting salt.

(electrolytic deposition step)

After dissolving step, the negative electrode being formed by vitreous carbon and the anode that formed by vitreous carbon are immersed in melting salt.Cathode potential is maintained to predetermined potential.Particularly, maintain current potential like this so that lithium deposits in NaCl-KCl melting salt.After the scheduled time, observe the cross section of cathode surface layer by scanning electronic microscope (SEM).

Observation has shown the lip-deep deposition of lithium in electrode body portion, and wherein this electrode body portion has formed negative electrode and formed by vitreous carbon.

Like this, can be from reclaiming lithium containing the positive electrode material of lithium.

[the 4th embodiment (embodiment)-1]

Ferro-vanadium is used as and contains the metallic substance of vanadium and manufacture vanadium by fusion electrolysis.

(sample)

The iron of the vanadium that contains 75 % by weight as the ferro-vanadium of handling object thing and 25 % by weight.Grind ferro-vanadium so that its particle diameter is about 2mm with ball mill or masher.By sample (ferro-vanadium) molybdenum (Mo) net (50 order) parcel after grinding.As shown in figure 14, the sample powder (handling object thing) being contained in Mo net is used as to anode (anode electrode).(experimental detail)

Dissolving step:

In the time that anode and negative electrode are so immersed in melting salt, anode is maintained to predetermined potential.Now, current potential being set only optionally makes vanadium dissolve so that iron is not dissolved.After the scheduled time, sample is taken out from melting salt and by ICP-AES, sample is carried out to compositional analysis.

Electrolysis step:

After dissolving step, the negative electrode being formed by vitreous carbon and the anode that formed by vitreous carbon are immersed in melting salt.Cathode potential is maintained to predetermined potential.Particularly, maintain current potential like this so that vanadium deposits in NaCl-KCl melting salt.After the scheduled time, observe the condition of surface of negative electrode.

(result)

About dissolving step:

Viewed dissolving step Anodic electric current over time with identical (Figure 15) in the first embodiment (embodiment).In Figure 15, transverse axis represents the time (unit: minute), and the longitudinal axis represents anodic current value.As shown in figure 15, current value reduces in time.Current value is following trend with respect to the velocity of variation of time: in the time measuring beginning, (while starting to apply electric current) velocity of variation is the highest, and afterwards, this velocity of variation reduces gradually.

By ICP-AES, the sample taking out is carried out to compositional analysis from melting salt.Result has confirmed the dissolving of vanadium in melting salt.

About electrolysis (deposition) step:

The observation in the cross section by scanning electronic microscope (SEM) anticathode upper layer shows: vanadium is deposited on the surface of electrode body portion, and wherein this electrode body portion is configured to negative electrode and is formed by vitreous carbon.

Like this, can be from obtaining highly purified vanadium containing the ferro-vanadium of vanadium.

[the 4th embodiment (embodiment)-2]

Mo-Cu scatterer is used as and contains the metallic substance of molybdenum and manufacture molybdenum by fusion electrolysis.

(sample)

The molybdenum that contains 50 % by weight as the Mo-Cu scatterer of handling object thing and the copper of 50 % by weight.Grind this scatterer so that its particle diameter is about 2mm with ball mill or masher.By sample (scatterer) platinum (Pt) net (50 order) parcel after grinding.The sample powder (handling object thing) being contained in Pt net is used as to anode (positive electrode).

(experimental detail)

Adopt LiCl-KCl eutectic melting salt as melting salt.This salt heats melting completely at 450 DEG C.Above-mentioned anode is connected with electric wire with negative electrode and is immersed in this melting salt.Negative electrode is formed by vitreous carbon.

Dissolving step:

In the time that anode and negative electrode are so immersed in melting salt, anode is maintained to predetermined potential.Now, current potential being set so only optionally makes molybdenum dissolve so that copper is not dissolved.After the scheduled time, sample is taken out from melting salt and by ICP-AES, sample is carried out to compositional analysis.

Electrolysis step:

After dissolving step, the negative electrode being formed by vitreous carbon and the anode that formed by vitreous carbon are immersed in melting salt.Cathode potential is maintained to predetermined potential.Particularly, maintain current potential like this so that molybdenum deposits in LiCl-KCl melting salt.After the scheduled time, observe the condition of surface of negative electrode.

(result)

About dissolving step:

Viewed identical with the situation of above-mentioned vanadium dissolving step Anodic current value reducing in time.Current value is following trend with respect to the velocity of variation of time: in the time measuring beginning, (while starting to apply electric current) velocity of variation is the highest, and afterwards, this velocity of variation reduces gradually.

By ICP-AES, the sample taking out is carried out to compositional analysis from melting salt.Result has confirmed the dissolving of molybdenum in melting salt.

About electrolysis (deposition) step:

Observation by scanning electronic microscope (SEM) anticathode upper layer cross section shows: molybdenum is deposited on the surface of electrode body portion, and wherein this electrode body portion is configured to negative electrode and is formed by vitreous carbon.

Like this, can be from obtaining highly purified molybdenum containing the scatterer of molybdenum.

[the 4th embodiment (embodiment)-3]

Oxide superconducting materials is used as and contains the metallic substance of strontium and manufacture strontium by fusion electrolysis.

(sample)

The calcium of the strontium that contains 17 % by weight as the oxide superconducting materials of handling object thing and 8 % by weight.Grind oxide superconducting materials so that its particle diameter is about 2mm with ball mill or masher.By sample (oxide superconducting materials) platinum (Pt) net (50 order) parcel after grinding.The sample powder (handling object thing) being contained in Pt net is used as to anode (anode electrode).

(experimental detail)

Adopt LiF-CaF2 eutectic melting salt as melting salt.This salt heats melting completely at 850 DEG C.Above-mentioned anode is connected with electric wire with negative electrode and is immersed in this melting salt.Negative electrode is formed by vitreous carbon.

Dissolving step:

In the time that anode and negative electrode are so immersed in melting salt, anode is maintained to predetermined potential.Now, current potential is set like this to make only optionally to make strontium and calcium dissolve, and other contained elements do not dissolve.After the scheduled time, sample is taken out from melting salt and by ICP-AES, sample is carried out to compositional analysis.

Electrolysis step:

After dissolving step, the negative electrode being formed by vitreous carbon and the anode that formed by vitreous carbon are immersed in melting salt.Cathode potential is maintained to predetermined potential.Particularly, maintain current potential like this so that strontium deposits in LiF-CaF2 melting salt.After the scheduled time, observe the condition of surface of negative electrode.

(result)

About dissolving step:

Viewed dissolving step Anodic current value reducing is in time identical with the situation of above-mentioned vanadium.Current value is following trend with respect to the velocity of variation of time: in the time measuring beginning, (while starting to apply electric current) velocity of variation is the highest, and afterwards, this velocity of variation reduces gradually.

By ICP-AES, the sample taking out is carried out to compositional analysis from melting salt.Result has confirmed the dissolving of strontium in melting salt.

About electrolysis (deposition) step:

The observation in the cross section by scanning electronic microscope (SEM) anticathode upper layer shows: strontium is deposited on the surface of electrode body portion, and this electrode body portion is configured to negative electrode and is formed by vitreous carbon.Because the fusing point of strontium is 768 DEG C, therefore strontium is liquid.When being attached to the quantitative change of the strontium on electrode body when large, due to the difference in specific gravity with respect to melting salt, strontium floats on surface.Therefore, be provided for collecting at the upside of electrode the fixture that floats up to surperficial strontium.

Like this, can be from obtaining highly purified strontium containing the oxide superconducting materials of strontium.

[the 4th embodiment (embodiment)-4]

Fiber optic materials is used as to germanic metallic substance and manufactures germanium by fusion electrolysis.

(sample)

The germanium that contains 3 % by weight as the fiber optic materials of handling object thing.Grind fiber optic materials so that its particle diameter is about 2mm with ball mill or masher.By sample (fiber optic materials) platinum (Pt) net (50 order) parcel after grinding.The sample powder (handling object thing) being contained in Pt net is used as to anode (anode electrode).

(experimental detail)

Dissolving step:

In the time that anode and negative electrode are so immersed in melting salt, anode is maintained to predetermined potential.Now, current potential is set to make only optionally to make germanium dissolve, and other contained elements do not dissolve.After the scheduled time, sample is taken out from melting salt and by ICP-AES, sample is carried out to compositional analysis.

Electrolysis step:

After dissolving step, the negative electrode being formed by vitreous carbon and the anode that formed by vitreous carbon are immersed in melting salt.Cathode potential is maintained to predetermined potential.Particularly, maintain current potential like this so that germanium deposits in LiF-CaF2 melting salt.After the scheduled time, observe the condition of surface of negative electrode.

(result)

About dissolving step:

Anodic current in viewed dissolving step reducing is in time identical with the situation of above-mentioned vanadium.Current value is following trend with respect to the velocity of variation of time: in the time measuring beginning, (while starting to apply electric current) velocity of variation is the highest, and afterwards, this velocity of variation reduces gradually.

By ICP-AES, the sample taking out is carried out to compositional analysis from melting salt.Result has confirmed the dissolving of germanium in melting salt.

About electrolysis (deposition) step:

The observation in the cross section by scanning electronic microscope (SEM) anticathode upper layer shows: germanium is deposited on the surface of electrode body portion, and wherein this electrode body portion is configured to negative electrode and is formed by vitreous carbon.

Like this, can from germanic fiber optic materials, obtain highly purified germanium.

Above disclosed embodiment and embodiment are illustrative aspect each, and should be understood to nonrestrictive.Scope of the present invention limits by claims instead of by above explanation, and intention be included in implication and the equivalency range of claims in all modification.

Industrial applicibility

The present invention is applicable to obtain the handling object thing from containing two or more metallic elements the method for highly purified special metal.The present invention is also applicable to obtain the method for required metal from ore or bullion.The present invention is also applicable to from contain tungsten and lithium to obtain at least one handling object thing the method for highly purified tungsten.

List of numerals

1 container; 2 melting salts; 3 handling object things; 4,24 basketrys; 5 wires; 6 to 8,15,27 electrodes; 9 control units; 10 well heaters; 11DyNi2 film; 12Pr film; 13Nd film; 16Dy film; 25 electrode materialss; 26 alloys; 31 electrode body portions; 32Dy-Ni alloy; 33,34 regions

Claims

1. a method of manufacturing metal by fusion electrolysis, the method comprises:

The metallic element being contained in handling object thing is dissolved in to the step in melting salt, and wherein this handling object thing contains two or more metallic elements; And

By being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in described melting salt, thereby make to be present in the step of deposition in special metal in the described melting salt one in described pair of electrodes parts or alloying, the metallic element that wherein said melting salt contains described dissolving.

2. the method for manufacturing metal by fusion electrolysis according to claim 1, wherein said handling object thing is ore or the bullion that obtained by this ore.

3. the method for manufacturing metal by fusion electrolysis according to claim 1 and 2,

Wherein said method is to manufacture the method for tungsten,

The metallic element being contained in described handling object thing is tungsten,

Metallic element is dissolved in the described step in melting salt by handling object thing, tungsten is dissolved out from described handling object thing, and

Making in the described step of special metal deposition or alloying, by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in described melting salt, thereby the tungsten that makes to be present in described melting salt is deposited in the one in described pair of electrodes parts, the tungsten that wherein said melting salt contains dissolving.

4. the method for manufacturing tungsten by fusion electrolysis according to claim 3, wherein said handling object thing is the metallic substance that contains tungsten.

5. according to manufacturing the method for tungsten by fusion electrolysis described in claim 3 or 4, wherein said handling object thing is the metallic substance that contains tungsten and transition metal.

6. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 3 to 6, wherein said handling object thing is hard metal article.

7. the method for manufacturing metal by fusion electrolysis according to claim 1 and 2,

Wherein said method is to manufacture the method for lithium,

The metallic element being contained in described handling object thing is lithium,

Metallic element is dissolved in the described step in melting salt by handling object thing, lithium is dissolved out from described handling object thing, and

Making in the described step of special metal deposition or alloying, by being preset value by the control of Electric potentials that is arranged at the pair of electrodes parts in described melting salt, thereby the lithium that makes to be present in described melting salt is deposited in the one in described pair of electrodes parts, the lithium that wherein said melting salt contains dissolving.

8. the method for manufacturing metal by fusion electrolysis according to claim 7, wherein said handling object thing is the material that contains lithium and transition metal.

9. according to manufacturing the method for metal by fusion electrolysis described in claim 7 or 8, wherein said handling object thing is the battery electrode material that contains lithium.

10. the method for manufacturing metal by fusion electrolysis according to claim 1 and 2, wherein said handling object thing contains transition metal or rare earth metal.

11. methods of manufacturing metal by fusion electrolysis according to claim 1 and 2, wherein said handling object thing contains one or more metals in the group of selecting free V, Nb, Mo, Ti, Ta, Zr and Hf formation.

12. methods of manufacturing metal by fusion electrolysis according to claim 1 and 2, wherein said handling object thing contains Sr and/or Ba.

13. methods of manufacturing metal by fusion electrolysis according to claim 1 and 2, wherein said handling object thing contains one or more metals in the group of selecting free Zn, Cd, Ga, In, Ge, Sn, Pb, Sb and Bi formation.

14. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 13, wherein select so described melting salt, make making in the described step of special metal deposition or alloying, the difference of the simple substance of special metal described in described melting salt or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.

15. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 14, wherein, making in the described step of special metal deposition or alloying, be described preset value by the control of Electric potentials of described electrod assembly, thereby optionally make described special metal element deposition or alloying in described melting salt.

16. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 15, wherein, and the metallic element being contained in handling object thing is dissolved in the described step in melting salt,

Described metal is dissolved in described melting salt by chemical process.

17. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 16, wherein, and the metallic element being contained in handling object thing is dissolved in the described step in melting salt,

The anode that negative electrode is set in described melting salt and is formed by the anode material that contains described handling object thing, and be preset value by the control of Electric potentials of described anode, thereby make to be dissolved in described melting salt by described handling object thing corresponding to the metallic element of this current potential through controlling.

18. methods of manufacturing metal by fusion electrolysis according to claim 17, wherein select so described melting salt, make the metallic element being contained in handling object thing is dissolved in the described step in melting salt, the difference of the simple substance of special metal described in described melting salt or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.

19. according to manufacturing the method for metal by fusion electrolysis described in claim 17 or 18, wherein, the metallic element being contained in handling object thing is dissolved in the described step in melting salt, be preset value by the control of Electric potentials of described anode, thereby optionally make described special metal element be dissolved in described melting salt.

20. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 19, wherein, the metallic element being contained in handling object thing is dissolved in the described step in melting salt, be all dissolved in described melting salt as one or more metals of described special metal.

21. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 6,10,11 and 14 to 20, is wherein deposited or the described special metal of alloying is transition metal.

22. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1,2,10 and 14 to 20, is wherein deposited or the described special metal of alloying is rare earth metal.

23. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1,2,10,11 and 14 to 20, is wherein deposited or the described special metal of alloying is V, Nb, Mo, Ti, Ta, Zr or Hf.

24. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1,2,12 and 14 to 20, is wherein deposited or the described special metal of alloying is Sr or Ba.

25. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1,2 and 13 to 20, is wherein deposited or the described special metal of alloying is Zn, Cd, Ga, In, Ge, Sn, Pb, Sb or Bi.

26. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 25, and wherein said melting salt is muriate melting salt or fluorochemical melting salt.

27. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 26, and wherein said melting salt is the fused salt mixture that contains muriate melting salt and fluorochemical melting salt.

28. according to manufacturing the method for metal by fusion electrolysis described in any one in claim 1 to 27, and wherein said handling object thing is particulate state or Powdered.

29. methods of manufacturing metal by fusion electrolysis according to claim 28, are wherein particulate state or pulverous described handling object thing is formed as described anode through extruding.

Manufacture the method for metal by fusion electrolysis for 30. 1 kinds, thereby the method is to be manufactured the method for special metal by the handling object thing that contains two or more metallic elements by fusion electrolysis,

The anode that negative electrode is wherein set in melting salt and is formed by the anode material that contains described handling object thing, and be preset value by the control of Electric potentials of this anode, thereby make to be dissolved in described melting salt by described handling object thing corresponding to the metallic element of this current potential through controlling, and special metal is retained in described anode.

31. methods of manufacturing metal by fusion electrolysis according to claim 30, wherein said handling object thing is ore or the bullion that obtained by this ore.

32. according to manufacturing the method for metal by fusion electrolysis described in claim 30 or 31, thereby wherein the method is to be manufactured the method for tungsten by the handling object thing that contains tungsten by fusion electrolysis,

The anode that negative electrode is set in melting salt and is formed by the anode material that contains described handling object thing, and be preset value by the control of Electric potentials of this anode, thereby make to be dissolved in described melting salt by described handling object thing corresponding to the metallic element of this current potential through controlling, and tungsten is retained in described anode.

33. according to manufacturing the method for metal by fusion electrolysis described in claim 30 to 32, wherein select so described melting salt, make metallic element is dissolved in the described step in described melting salt by described handling object thing, the difference of the simple substance of special metal described in described melting salt or the simple substance of the standard potential of alloy and another kind of metal or the standard potential of alloy is more than 0.05V.

34. 1 kinds for manufacturing the device of the method for metal by fusion electrolysis, this device comprises:

Accommodate the container of melting salt;

Negative electrode, it is immersed in the described melting salt being contained in described container; And

Anode, it is immersed in the described melting salt being contained in described container and comprises handling object thing, and this handling object thing contains two or more metallic elements,

Wherein said melting salt can flow between described anode interior and outside,

Described device also comprises control unit, and it is preset value that this control unit is constructed to the control of Electric potentials of described negative electrode and described anode, and

In described control unit, the value of described current potential can change.

35. 1 kinds for manufacturing the device of the method for metal by fusion electrolysis, this device comprises:

Accommodate the container of melting salt, the metallic element that this melting salt comprises two or more dissolvings; Negative electrode and anode, it is immersed in the described melting salt being contained in described container; And control unit, it is constructed to the control of Electric potentials of described negative electrode and described anode is preset value,

Wherein, in described control unit, the value of described current potential can change.

36. according to the device described in claim 34 or 35, and wherein said two or more metallic elements comprise at least one in tungsten and lithium.