CN102325911B - Method for recovering rare earth elements from RE-TM-based mixture - Google Patents
Method for recovering rare earth elements from RE-TM-based mixture Download PDFInfo
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- CN102325911B CN102325911B CN201080008784.2A CN201080008784A CN102325911B CN 102325911 B CN102325911 B CN 102325911B CN 201080008784 A CN201080008784 A CN 201080008784A CN 102325911 B CN102325911 B CN 102325911B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
- C22B7/003—Dry processes only remelting, e.g. of chips, borings, turnings; apparatus used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
Disclosed is a method for recovering rare earth elements and transition metals whereby rare earth elements and transition metals are efficiently separated from an RE-TM-based mixture, which comprises compounds and/or a mixture containing rare earth elements and transition metals including Fe, to thereby conveniently and economically recover recycled materials having high purity, comprising: a loading step for loading an RE-TM-based mixture in a graphite crucible; a separation step for heating the graphite crucible containing the RE-TM-based mixture loaded therein to separate the RE-TM-based mixture into an oxide phase comprising the rare earth elements as the major components and a metal phase containing the transition metals, and to melt the RE-TM-based mixture; and a recovery step for separating the RE-TM-based mixture into oxides comprising the rare earth elements as the major components and metals or alloys containing the transition metals, and separately recovering the same.
Description
Technical field
The present invention relates to be compound and/or the mixture that residue of producing in the processing/forming process of magnetite etc. comprises rare earth element and transition metal to Nd-Fe-B in plumbago crucible, under atmosphere of inert gases, heat, melting treatment, thus by take oxide compound that rare earth element is main component, be separated with the Fe alloy that comprises Fe and other transition metal, and they are carried out to indivedual methods that reclaim.
In the present invention, RE-TM is compound and/or the mixture that mixture refers to the transition metal that contains rare earth element and comprise Fe.It should be noted that, " RE " refers to the one kind or two or more element in rare earth elements such as being selected from Nd, Dy, Pr, Tb, Sm, Ce, and " TM " refers to the Fe that comprises the transition metal such as Co.
Rare earth element refers to group of the lanthanides from La to Lu, added after Sc and Y totally 17 kinds of elements.
In the present invention, " transition metal " refers in the element existing between periodictable Cong 3 element～11 family of family elements, the element except above-mentioned rare earth element.
Rare metal refers to the metallic element beyond Fe, Al, particularly, and can illustration rare earth element, Co, W etc.
Processing/the cutting swarf producing in the manufacturing process of the parts containing metallic element is called to " residue ".Especially by Nd-Fe-B, be that the residue producing in the processing/forming process of magnetite is called " Nd-Fe-B is residue ".
Background technology
In recent years, in a lot of industries, the usage quantity of the rare metal in vitals increases by leaps and bounds.
As the parts and the material that contain such rare metal composition, the Nd-Fe-B of can illustration hard disk drive, using in the motor of hybrid vehicle etc., MRI, sound machine etc. is magnetite, as other magnetite, can illustration Sm-Fe-N is that magnetite, La-Co are magnetite, except magnetite, photomagneto disk, the YAG laser apparatus that contains Y, Fe, Co etc., the some flint that contains La, Ce, Nd, Fe etc. that can illustration contains Tb, Dy, Fe, Co etc. and the hydrogen adsorbing alloy that contains La, Ce, Nd, Ni, Co, Al, Mn etc.
But, because the Domestic Product amount of rare metal is limited, thus its stability guarantee to become national important topic.As the resolution policy of one of this problem, can enumerate contained rare metal composition in the processing/formed scrap in the past having gone out of use in the waste of parts to containing rare metal composition, material or these manufacturing processed and carry out separation/recovery.
If the Nd-Fe-B of take is magnetite, describe as example, in the residue producing in its processing/forming process, not only, containing Nd, also contain in a large number the rare earth elements such as Dy, Pr, Tb, and not only containing Fe, also contain in a large number other the transition metal such as Co.If can from this Nd-Fe-B be residue with high yield, highly selective and low-cost separation and reclaim rare metal composition, can contribute to widely the stable supplying of rare metal.Therefore, wish consumingly the establishment of this separation, recovery technology.
As the residue from containing above-mentioned rare metal composition, especially contain one of method of Separation and Recovery rare earth element and transition metal in the compound of rare earth element and transition metal and/or mixture, there is damp process.The Nd-Fe-B of take is that residue is example, and this damp process is described.Nd-Fe-B is that the rare earth elements such as Nd in residue, Dy, Pr form oxide compound.Therefore, by Nd-Fe-B, be residue while being impregnated in aqueous acid, although Fe is dissolved in acid, above-mentioned rare earth element is not dissolved in acid, so Fe is in liquid phase, rare earth class is separated in solid phase.If by the separated solid-liquid separation of the means such as filtration, can reclaim the rare-earth element compound of solid phase.
Yet damp process is the method with following problem in practice.While only dissolving Fe the fine mixed tissue of the element beyond rare earth element and rare earth element (Fe and other transition metal), need a large amount of time.In addition, for being dissolved, Fe needs a large amount of acid.And then, in order to process this acidic solution, otherwise discarded, or reclaim the compositions such as Fe, need to process accordingly.
Other method as Separation and Recovery rare earth element and transition metal the compound from comprising rare earth element and transition metal and/or mixture, has high-temperature dry-type method.An example as the method, patent documentation 1 discloses, for the residue that contains rare earth element, by adding the solid debris, magnetite waste or the rare earth metal that contain rare earth element, consider and make its dissolving to be worth doing, be separated into thus and using rare earth element as the compound of main component and the alloy that comprises rare earth element element in addition, and the method for recovering rare earth dvielement.
Yet, in the method, owing to utilizing solid debris such material or the so very high material of value of rare earth element itself that can guarantee regeneration in other operation, so from economic viewpoint existing problems.
On the other hand, about Sm-Co, be the chip of magnetite, known have dissolved after chip, be blown into the dividing potential drop O that makes rare earth class selective oxidation
2, the method (for example patent documentation 2) of recovering rare earth dvielement from the oxide compound slag of the rare earth element that generates this processing.
Yet, in the method, in order to carry out stable separation, recovery, need to carry out O
2be blown into and control the O after being blown into
2the equipment of dividing potential drop, and then need to carry out maintenance and management to them.Therefore, separated, reclaim needed facility load and increase, from calculating the viewpoint of property, be actually the method that can not adopt.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-60863 communique
Patent documentation 2: Japanese kokai publication hei 2-22426 communique
Non-patent literature
Non-patent literature 1:S.C.Parida, S.Dash, Z.Singh, R.Prasad, K.T.Jacob andV.Venugopal:Journal of Solid Sate Chemistry, 164 (2002), 34-41.
Non-patent literature 2:S.C.Parida, K.T.Jacob and V.Venugopal:Solid StateScience, 4 (2002), 1245-1255.
Non-patent literature 3:Yu.D.Tretyakov, V.V.Sorokin and A.P.Erastova:Journal of Solid Sate Chemistry, 18 (1976), 263-269.
Non-patent literature 4:Yu.D.Tretyakov, V.V.Sorokin, A.R.Kaul and A.P.Erastova:Journal of Solid Sate Chemistry, 18 (1976), 253-261.
Non-patent literature 5:S.C.Parida, K.T.Jacob and V.Venugopal:Journal ofPhase Equilibria, 24 (2003), 431-440.
Summary of the invention
The problem that invention will solve
The present invention is in order to solve above-mentioned economy problems, it is that residue is as the member that contains rare metal composition shown in typical case that its object is to provide from Nd-Fe-B, especially RE-TM is rare-earth separating dvielement and transition metal effectively in mixture, easy and reclaim economically the method for the regenerative raw materials that purity is high.
For the method for dealing with problems
The inventor is on being that detailed investigation has been carried out in the impact of the phase that exists while being mixture with respect to heating RE-TM of oxygen partial pressure in the atmosphere of mixture around RE-TM.The opinion that this result obtains is, rare earth element, under solid state, can be separated into 2 phases (Fig. 1) with the alloy of the Fe that comprises Fe or other transition metal.
That is, it is that rare earth element in the ingredients of a mixture is oxidized that the atmosphere gas control that around RE-TM is mixture is only made as forming RE-TM, and not oxidation package containing the oxygen partial pressure of the alloy of the Fe of Fe or other transition metal.By controlling in this wise, RE-TM is that mixture separation is the phase of take phase that oxide compound that rare earth element is main component forms and consisting of the alloy of the Fe that comprises Fe or other transition metal.
In addition, under various conditions, meticulously repeat experimental study, result has obtained following opinion.That is, in plumbago crucible, to RE-TM, be that mixture heats while keeping, form the carbon and the oxygen rapid reaction that should form the equilibrium state of regulation of plumbago crucible.That is to say, in plumbago crucible, to RE-TM, be that mixture heats while keeping, even if strictly do not control the oxygen partial pressure that imports to the gas in crucible, by forming the carbon of plumbago crucible, be oxidized the reaction that forms carbon monoxide, the oxygen partial pressure in the atmosphere in plumbago crucible also can autorhymicity be controlled.In oxygen partial pressure after this autorhymicity is controlled, RE-TM is that the rare earth class in mixture is oxidized, and the metallic state of the transition metal such as Fe is maintained.Consequently, RE-TM is that mixture is separated into and take the oxide compound that rare earth element is main component and the Fe alloy that comprises Fe or other transition metal.Therefore, in plumbago crucible, to RE-TM, be only that mixture heats maintenance, just can reclaim respectively.
About this point, further describe.
The thermodynamic (al) balanced reaction through type (3) of carbon and oxygen shows.
2C+O
2＝2CO
ΔG
0＝-223532-175.4T (3)
Herein, Δ G
0for the variation (J) of standard free energy, T is temperature (K).
Formula below equilibrium state (4) is set up.
ΔG
0＝-RTln{P
CO 2/(a
C 2·P
O2)} (4)
Herein, R is gas law constant, P
cOfor the dividing potential drop of CO, a
cfor the activity of carbon, and P
o2dividing potential drop for oxygen.
Carbon is pure solid state, so its activity a
cbe 1.O
2amount of substance be that (herein, n is initial O before referring to and utilizing formula (3) to generate CO to n (1-α) mol
2amount of substance.) time, the amount of substance of CO is 2n α, it adds up to n (1+ α) mol.When stagnation pressure is P, dividing potential drop separately with
P
O2＝P·(1-α)/(1+α) (5)
P
CO＝P·2α/(1+α) (6)
Provide.Total head P is 1atm, at each temperature, by formula (3), (5), (6) substitution formula (4), obtains the value of α, then by this α substitution (5) formula, the P calculating
o2be shown on Fig. 1.As shown in Figure 1, the autorhymicity control when equilibrium state of the oxygen partial pressure in plumbago crucible is 10
-15～10
-18atm left and right.
On the other hand, about rare earth element (specifically can illustration Nd, Pr, Dy, Ce and Sm.) with transition metal (specifically can illustration Fe.) the equilibrium state of mixture under the state of oxidation, while studying based on non-patent literature 1～5 (particularly, with reference to non-patent literature 1Fig.5, Eq.[15], non-patent literature 2Fig.9, Eq. (15), non-patent literature 3Fig.2, Eq. (2), non-patent literature 4Fig.3, Eq. (8), and non-patent literature 5Fig.9, Eq. (14).), as shown in Figure 1, when ambient oxygen dividing potential drop is high, rare earth element, transition metal all exist as oxide compound.Ambient oxygen is divided while forcing down and is existed with the two not oxidized state.Ambient oxygen dividing potential drop between these time, form rare earth element oxidized, but transition metal is not oxidized state.
And according to Fig. 1, the oxygen partial pressure under the equilibrium state in plumbago crucible is equivalent to bring the oxidized but oxygen partial pressure of the state that transition metal is not oxidized of this rare earth element.Therefore, in plumbago crucible, heated RE-TM is that mixture becomes the state of oxide compound at rare earth element, and transition metal becomes metal or alloy state and is issued to stable.Therefore both are separated in plumbago crucible.
It should be noted that, although the oxygen partial pressure shown in Fig. 1 is the situation in equilibrium state, owing to importing in actual system, the situation that oxygen concentration in plumbago crucible is high is a lot, therefore also has the situation that does not reach equilibrium state.Yet even if such situation, when plumbago crucible is heated, the oxygen of the environment in crucible is fast by carbon consumption.Consequently, the oxygen concentration in plumbago crucible declines rapidly, easily reaches 10
-10below atm.Therefore, can stably obtain the RE-TM being loaded in plumbago crucible is the condition that mixture can be separated into oxide compound phase and metal or alloy phase.
In addition, in Fig. 1, show the profile of equilibrium while coexisting about 5 kinds of rare earth elements and Fe, but the transition metal of other beyond other rare earth element and Fe is also roughly identical with the profile of equilibrium shown in Fig. 1 while coexisting with Fe, under oxygen partial pressure during equilibrium state in plumbago crucible, although become the not oxidized state of the oxidized transition metal of rare earth element.Therefore,, even if when the transition metal of other beyond other rare earth element and Fe coexists with Fe, in plumbago crucible, also produce and be separated.
The invention provides a kind of is the phenomenon that mixture autorhymicity is separated based on RE-TM in this plumbago crucible, preferably the alloy molten, separated of take the rare earth element oxide compound that is main component and the Fe that comprises Fe metal or other transition metal after 1623～1973K makes to be separated, reclaims the method for phase separately.
That is, the present invention is as follows.
(1) recovery method for rare earth element and transition metal, described method possesses following step: by containing rare earth element, be that RE-TM is that mixture packs the step that packs in plumbago crucible into compound and/or the mixture of the transition metal that comprises Fe; To packed this RE-TM in inside, be that the plumbago crucible of mixture heats, making described RE-TM is that mixture separation is to using rare earth element as the oxide compound phase of main component and the metallographic phase that comprises transition metal, and make described RE-TM is the separating step of mixture melting simultaneously; And to make described RE-TM be that mixture separation is to take the oxide compound that rare earth element is main component and the metal or alloy that comprises transition metal, and to the recycling step reclaiming separately.
(2) recovery method as described in above-mentioned (1), wherein, in separating step, the gas forming to the rare gas element importing in plumbago crucible by the oxygen that comprises 1ppm～1% while making described RE-TM be mixture melting.
(3) recovery method as described in above-mentioned (1), wherein, packing step into, to be encased in described RE-TM in plumbago crucible be that the median size of mixture is 10～20 μ m.
(4) recovery method as described in above-mentioned (1), is characterized in that, in separating step, making described RE-TM is mixture melting together with carbonaceous material.
(5) recovery method as described in above-mentioned (4), wherein, in packing step into, be encased in the contained carbon amount Wc of described carbonaceous material in plumbago crucible (unit: scope g) provides with formula (i) with (ii):
0＜W
C≤W
Fe×M
C×N
C/(M
C×N
C+M
Fe×N
Fe) (i)
N
C≤10
12.728/T+0.7271×1ogT-3.049 (ii)
Herein, W
fe(g): for being encased in the Fe amount of plumbago crucible, T (K): for temperature in the plumbago crucible in separating step, change M in the scope higher than 1623K and not enough 1973K
fe(g): be the nucleidic mass 55.85 of Fe, M
c(g): be the nucleidic mass 12 of C, N
c: the saturation solubility converting for the mole fraction of carbon in the Fe in Fe-C system, and N
fe=1-N
c.
(6) recovery method as described in above-mentioned (5), in packing step into, the Fe that the carbon amount that described carbonaceous material is contained and plumbago crucible pack into measures to meet the mode of following formula (iii), packs described carbonaceous material in plumbago crucible into.
0.017W
Fe＜W
C＜0.048W
Fe (iii)
The effect of invention
According to the present invention, by in plumbago crucible, under atmosphere of inert gases, to RE-TM, be that mixture heats so easy and economy few method of loading, can be by RE-TM rare earth element in mixture make oxide compound, containing the metal or alloy of the transition metal of Fe etc., with high purity, carry out respectively separation, and reclaim.
Accompanying drawing explanation
Fig. 1 carries out the figure of separated oxygen partial pressure for representing Fe and oxide compound.
Fig. 2 is for representing the sample cooled section observations figure relevant with embodiment 1.
Fig. 3 is for representing the sample cooled section observations figure relevant with embodiment 2.
Fig. 4 is for representing the sample cooled outward appearance observations figure relevant with embodiment 3.
Fig. 5 is for representing to have with embodiment 4 the cooled outward appearance observations of each sample figure of sight.
Embodiment
To being that the method for mixture recovering rare earth dvielement describes below from RE-TM of the present invention.
In the present invention, by RE-TM, be that mixture packs in plumbago crucible, this plumbago crucible is heated, it is separated into and usings rare earth element as the oxide compound phase of main component and the metallographic phase that comprises transition metal, make RE-TM is mixture melting simultaneously.Herein, no matter be separated, the order of melting.Like this, by be separated/melting, be separated into and take oxide compound that rare earth element is main component and contain metal Fe or the alloy of the Fe of other transition metal.
That is, the method relevant with the present invention, it possesses following step: in plumbago crucible, packing into and containing rare earth element is that RE-TM is the step that packs into of mixture with compound and/or the mixture of the transition metal that comprises Fe; To packed this RE-TM in inside, be that the plumbago crucible of mixture heats, making described RE-TM is that mixture separation is to using rare earth element as the oxide compound phase of main component and the metallographic phase that comprises transition metal, and make described RE-TM is the separating step of mixture melting simultaneously; And to make described RE-TM be that mixture separation is to take the oxide compound that rare earth element is main component and the metal or alloy that comprises transition metal, and to the recycling step reclaiming separately.
Because the atmosphere gas in plumbago crucible as above can autorhymicity be controlled, so must not need for controlling the external operation of atmosphere gas in essence.But, in fact, according to following reason, wish to plumbago crucible import by oxygenous concentration be more than 1ppm below 1% and surplus be Ar, N
2the gas forming Deng rare gas element, in this atmosphere gas, is that mixture heats together with plumbago crucible to RE-TM, and carries out separation, recycling.
That is,, when the oxygen partial pressure in atmosphere excessively increases, there is the oxidizing reaction of plumbago crucible to become fierce, the misgivings that plumbago crucible significantly consumes.Therefore, oxygen concentration 1% is preferably the upper limit.In addition, oxygen partial pressure is excessive when low, have following misgivings: because the amount of oxygen for making rare earth class be oxidized to oxide compound reduces, so process the needed time, increase, and from crucible surface separation part partial oxygen dividing potential drop too low and be separated and do not carry out well.From the viewpoint of economy, quality, preferably these.Therefore, more than the oxygen concentration in atmosphere is preferably 1ppm.
When controlled atmosphere, the method for supplying with above-mentioned rare gas element has no particular limits.By appropriate means, with above-mentioned scope, adjust oxygen concentration.The oxygen that conventionally can contain 1～10ppm left and right in industrial rare gas element is as impurity.Therefore, obtain and conventionally can buy rare gas element, as long as confirm that wherein contained oxygen concentration is above-mentioned scope, can directly supply with this rare gas element, implement thus the present invention.
In addition, when heating RE-TM being mixture in plumbago crucible, because the carbon from plumbago crucible immerses Fe, think the melting point depression of the Fe of 1811K.Therefore, melting separation temperature reduces, and is also favourable on cost of energy.
The melt temperature of rare-earth oxide is about 1623K, and this is separated lower limit temperature.In addition, surpass being melted in to add and hankering a large amount of energy of needs of 1973K, from the viewpoint of cost of energy, preferred molten temperature is below 1973K.
There is no particular limitation to be encased in RE-TM in plumbago crucible and to be the shape of mixture.Because the oxygen partial pressure in the atmosphere of utilization of the present invention in plumbago crucible approaches specific equilibrium state, such autorhymicity is controlled phenomenon, utilize rare earth element in this oxygen partial pressure and the steady state difference of transition metal to be separated, so the surface-area that the RE-TM dropping into is mixture per unit mass is the bigger the better, the interaction of so easy generation rare earth element and transition metal and oxygen, consequently, easily there is phenomenon of phase separation.That is,, from the easy viewpoint being separated, RE-TM is the shape small particle size if of mixture, is being favourable to a certain degree.Therefore, after being mixture while being bulk, preferably its pulverizing being made to powder, processes RE-TM.
But, in order to make RE-TM, be mixture small particle size and need to be for this operation (pulverizing process), the needed time of the less operation of particle diameter is more, and worries to occur other the problem such as dust generation.Therefore the RE-TM dropping into is that the median size of mixture is preferably 5～100 μ m, more preferably 5～50 μ m, particularly preferably 10～20 μ m.
While making RE-TM be mixture mixing carbonaceous material, except the atmosphere control that the carbon in plumbago crucible carries out, also can carry out atmosphere control from mixture inside herein.Therefore,, in the time of the carrying out that promote to be separated, also effectively produce and soak charcoal, the needed time shorten of technique.
But the combined amount of carbonaceous material is excessive when many, worry to take to sneak into carbon in oxide compound that rare earth element is main component.Although no problem when in the purposes of recycling, this carbon can not have influence on quality, sneaking into carbon likely has while impact to the quality of goods, preferably controls the combined amount of carbonaceous material according to its purposes.
For example, in the situation that the raw material that is magnetite as Nd-Fe-B recycles, in rare-earth oxide, sneaking into carbon may have on the characteristic as magnetite bad impact.Therefore, make the contained carbon amount of carbonaceous material of its mixing (be designated hereinafter simply as " adding carbon amount ".) be preferably no more than and be dissolved in the higher limit that Nd-Fe-B is the carbon amount of the Fe in residue, be no more than saturated carbon amount.To sum up, preferably add the scope of carbon amount Wc for providing with formula (1), unit is g.
0＜W
C≤W
Fe×M
C×N
C/(M
C×N
C+M
Fe×N
Fe) (1)
N
C≤10
12.728/T+0.7271×1ogT-3.049 (2)
Herein, W
fe(g): for being encased in Fe amount, the T (K) of plumbago crucible: be temperature in the plumbago crucible in separating step, at the range that surpasses 1623K and not enough 1973K, M
fe(g): be the nucleidic mass 55.85 of Fe, M
c(g): be the nucleidic mass 12 of C, N
c: the saturation solubility converting for the mole fraction of carbon in the Fe in Fe-C system, and N
fe=1-N
c.
It should be noted that, add carbon amount in the above-mentioned scope providing with formula (1), (2), and then more preferably at 0.017W
fe< W
c< 0.048W
fescope.It is the reasons are as follows.When interpolation carbon amount is few, time shorten effect reduces, so the meaning of adding reduces.The contrary detrimentally affect of adding the uneven generating portion that carbon amount likely adds due to carbon when many.
It should be noted that, although also comprise organic reagent of using when preserving residue etc. in residue itself, can think the composition as carbonaceous material, can remove by water washing, so there is no need it to consider as carbonaceous material.
So, the raw material that the rare-earth oxide reclaiming by the method relevant with the present invention can be used as Ca reduction and fusion electrolysis salt recycles, and then the metal or alloy of transition metal can be used as for example raw material of Fe and regenerates.
Embodiment
Embodiment is below shown, the present invention is specifically described, but the present invention is not limited by following embodiment.
The sample using in embodiment is all that the Nd-Fe-B producing in processing, cutting process is residue.It forms in quality %, is Nd:19.91%, Pr:5.65%, Dy:4.41%, Tb:0.01%, Fe:53.87%, B:0.77%, Co:0.08%, C:1.36%, Al:0.19% and surplus impurity.This Nd-Fe-B, after residue washs with ultrapure water, at air drying, fully removes after moisture, and being crushed to median size is 10～20 μ m, for experiment.By the Nd-Fe-B that has applied this pre-treatment, be that residue is called " Nd-Fe-B is residue sample " below.
(embodiment 1)
By Nd-Fe-B, be that residue sample 21.2g packs in plumbago crucible, use electric furnace, import industrial Ar (purity 99.99 volume %, oxygen concentration 10ppm) with 50mL/min. (standard state conversion), with 300K/h, be heated to 1823K, keep 3 hours.Then, sample is taken out in stove, be blown into Ar gas and make it cooling.
By gas-chromatography to the contained CO of expellant gas from stove, CO
2analyze, obtain CO dividing potential drop and CO
2dividing potential drop.
2CO+O
2＝2CO
2
ΔG
0＝-568000+175.48T (7)
By CO dividing potential drop and CO after measuring
2dividing potential drop is applied to formula (7), and it is 5 * 10 that result is calculated at 1823K as the oxygen partial pressure of balance
-11atm.This value and the oxygen partial pressure equal extent being determined by the balance of formula (3), in Fig. 1, Nd, Pr, Dy are in the scope of the oxygen partial pressure of oxidation, and Fe is in the scope of non-oxidizing oxygen partial pressure.
Fig. 2 represents the cross sectional photograph of cooled sample.Can confirm to exist metallographic phase and oxide compound phase 2 phases.
Metallographic phase after reclaiming shown in table 1 (illustrates with " alloy Fe " in table.), oxide compound phase (illustrates with " rare-earth oxide " in table.) composition.Metallographic phase is for take the phase that Fe is main component, and oxide compound be take the phase that rare earth element Nd, Dy, Pr are main component.Numerical value in table 1 refers to the content (unit: quality %) of each element as 100% time using the quality of each phase.
[table 1]
(unit: quality %)
The concentration of transition metal in metallographic phase (Fe+Co) is 99.8%, and the concentration of oxide compound phase middle-weight rare earths dvielement (Nd+Dy+Pr) is 96.8% to be very high value.
On the other hand, table 2 and 3 is to have reprinted the table 1 of prior art patent documentation 1 and the form of table 2, the pure composition of the rare earth element in residue in interpolation and residue almost, with the expensive Nd scrap metal of amount (counting 0.75 or 1.1 with weight ratio), reclaims, and the results are shown in these tables.As shown in table 2 and 3, according to the disclosed technology of patent documentation 1, the concentration of the transition metal in alloy (Fe+Co) is 99.7 or 99.8%, and the concentration that reclaims the rare earth element (Nd+Dy+Pr) in slag is 88.9 or 95.9%.Compare with this result, in the recovery method relevant with the present invention, with equal or its above purity, reclaimed rare earth element (Nd, Dy, Pr), transition metal (Fe, Co).
[table 2]
[table 3]
In summary, although do not use the Nd scrap metal of high price, but utilize rare gas element, plumbago crucible to implement with economic cheap cost, present method is also can be easy and reclaim economically the rare earth element that purity is high, the method for transition metal.
(embodiment 2)
Remain in the electric furnace of 1823K, importing and having filled Nd-Fe-B is the Pt crucible of residue sample 0.15g, keeps 1 hour in air.Then, sample is taken out from stove, be blown into Ar gas and make it cooling.
Fig. 3 represents the cross sectional photograph of cooled sample.
Can be confirmed to be and not be separated into metallographic phase and the oxide compound uniform oxide compound phase of 2 phases mutually.
(embodiment 3)
Remain in the electric furnace of 1823K, importing and having filled 1g Nd-Fe-B is the plumbago crucible of residue sample, keeps 1 hour in air.Then sample is taken out from stove, be blown into Ar gas and make it cooling.
Fig. 4 shows the outward appearance of the sample having taken out from crucible after cooling.
Can confirm to be separated into metallographic phase and oxide compound 2 phases mutually.That is to say, though known in air atmosphere, also can be by graphite and oxygen in plumbago crucible react to control oxygen partial pressure.
(embodiment 4)
Use remains on the electric furnace of 1823K, importing industrial Ar, purity 99.99vol%, oxygen concentration 10ppm, 50mL/min (s.t.p. (standard temperature and pressure (STP))), is that residue sample is heat-treated in plumbago crucible by the condition of following (1)～(4) to each Nd-Fe-B.
(1) Nd-Fe-B is residue sample 1g, 2 minutes hold-times,
(2) to Nd-Fe-B, be to add powdered graphite 0.02g in residue sample 1g, 2 minutes hold-times,
(3) Nd-Fe-B is residue sample 1g, 10 minutes hold-times,
(4) to Nd-Fe-B, be to add powdered graphite 0.02g in residue sample 1g, 10 minutes hold-times,
After maintenance, sample is taken out from stove, it makes it cooling to be blown into Ar.
Fig. 5 illustrates the outward appearance of utilizing condition (1)～sample that (4) obtain of taking out from crucible after cooling.
Result is that the sample that utilizes condition (2) to obtain is separated into metallographic phase and oxide compound phase 2 phases.On the other hand, utilize the insufficient generation separation completely of sample melting of condition (1).
On the other hand, utilize the sample kept the condition (3) of 10 minutes and (4) to obtain to be all separated into metallographic phase and oxide compound phase 2 phases.In summary, the result difference of (1) and (2) causes by whether having added powdered graphite, so promoted the carrying out of technique by the interpolation of powdered graphite.
Claims (5)
1. a recovery method for rare earth element and transition metal, described method possesses following step:
Packing step into, is that RE-TM is that mixture packs in plumbago crucible by containing rare earth element with compound and/or the mixture of the transition metal that comprises Fe;
Separating step, to packed this RE-TM in inside, be that the plumbago crucible of mixture heats, making described RE-TM is that mixture separation is to using rare earth element as the oxide compound phase of main component and the metallographic phase that comprises transition metal, make described RE-TM is mixture melting simultaneously, and when making described RE-TM be mixture melting, the gas forming to the rare gas element importing in plumbago crucible by the oxygen that contains 1ppm～1%; And
Recycling step, is that mixture separation is to take the oxide compound that rare earth element is main component and the metal or alloy that comprises transition metal by described RE-TM, and reclaims respectively.
2. recovery method as claimed in claim 1, wherein,
In packing step into, the described RE-TM that is encased in plumbago crucible is that the median size of mixture is 10～20 μ m.
3. recovery method as claimed in claim 1, is characterized in that,
In separating step, making described RE-TM is mixture melting together with carbonaceous material, and described carbonaceous material does not comprise organism.
4. recovery method as claimed in claim 3, wherein,
In packing step into, be encased in the scope of the carbon content Wc in the described carbonaceous material of plumbago crucible suc as formula (i) with (ii), wherein the unit of Wc is g:
0<W
C≤W
Fe×M
C×N
C/(M
C×N
C+M
Fe×N
Fe) (i)
N
C≤10
12.728/T+0.7271×logT-3.049 (ii)
Herein, W
fe: be the amount of the Fe that packs in plumbago crucible, unit is g, T (K): be the temperature in the plumbago crucible in separating step, at the range that surpasses 1623K and not enough 1973K, M
fe: be the nucleidic mass 55.85 of Fe, unit is g, M
c: be the nucleidic mass 12 of C, unit is g, N
c: the saturation solubility converting for the mole fraction of carbon in Fe in Fe-C system, and N
fe=1-N
c.
5. recovery method as claimed in claim 4, wherein, in packing step into, the Fe amount being packed into the carbon amount that contains in described carbonaceous material and plumbago crucible meets the mode of following formula (iii), packs described carbonaceous material in plumbago crucible into
0.017W
Fe<W
C<0.048W
Fe (iii)。
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| Application Number | Priority Date | Filing Date | Title |
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| JP2009046495 | 2009-02-27 | ||
| JP2009-046495 | 2009-02-27 | ||
| PCT/JP2010/052947 WO2010098381A1 (en) | 2009-02-27 | 2010-02-25 | Method for recovering rare earth elements from re-tm-based mixture |
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| CN102325911B true CN102325911B (en) | 2014-04-09 |
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| WO2013018710A1 (en) | 2011-07-29 | 2013-02-07 | 日立金属株式会社 | Method for recovering rare earth element |
| JP5767993B2 (en) * | 2012-03-26 | 2015-08-26 | Jx日鉱日石金属株式会社 | Method for enriching rare earth elements from rare earth-containing materials |
| JP6299181B2 (en) * | 2012-11-28 | 2018-03-28 | 日立金属株式会社 | Recovery method of rare earth elements |
| CN104884649B (en) * | 2012-12-26 | 2018-05-29 | 日立金属株式会社 | The recovery method of rare earth element |
| US10233516B2 (en) | 2013-01-28 | 2019-03-19 | Hitachi Metals, Ltd. | Method for recovering heavy rare earth element |
| JP6060704B2 (en) * | 2013-01-28 | 2017-01-18 | 日立金属株式会社 | Recovery method of rare earth elements |
| US10023938B2 (en) | 2013-05-31 | 2018-07-17 | Hitachi Metals, Ltd. | Method for recovering rare earth element |
| CN104651612B (en) * | 2013-11-19 | 2017-06-20 | 荆门市格林美新材料有限公司 | The method of molten rare earth waste recovery rare earth |
| JP6187768B2 (en) * | 2014-03-26 | 2017-08-30 | 三菱マテリアル株式会社 | Recovery method of rare earth elements |
| JP6264195B2 (en) * | 2014-05-27 | 2018-01-24 | 日立金属株式会社 | Recovery method of rare earth elements |
| JP6413877B2 (en) * | 2014-03-28 | 2018-10-31 | 日立金属株式会社 | Recovery method of rare earth elements |
| EP3124629A4 (en) * | 2014-03-28 | 2017-11-22 | Hitachi Metals, Ltd. | Method for recovering rare earth element |
| JP5977385B2 (en) * | 2015-02-06 | 2016-08-24 | Ｊｘ金属株式会社 | Method for enriching rare earth elements from rare earth-containing materials |
| JP6641593B2 (en) | 2016-01-12 | 2020-02-05 | 三菱マテリアル株式会社 | Rare earth element and iron separation method |
| CA3092730C (en) * | 2018-03-01 | 2021-03-02 | Aurum Integra Inc. | Method for selectively oxidizing metals of an alloy |
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| JPWO2010098381A1 (en) | 2012-09-06 |
| JP5273241B2 (en) | 2013-08-28 |
| CN102325911A (en) | 2012-01-18 |
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