CN103194626B - Separating and recycling method of rare earth elements - Google Patents
Separating and recycling method of rare earth elements Download PDFInfo
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- CN103194626B CN103194626B CN201310008678.XA CN201310008678A CN103194626B CN 103194626 B CN103194626 B CN 103194626B CN 201310008678 A CN201310008678 A CN 201310008678A CN 103194626 B CN103194626 B CN 103194626B
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Abstract
The invention relates to a separating and recycling method of rare earth elements, and provides a method for separating and recycling rare earth elements with a high yield which is simpler and more convenient than the prior art. The method is characterized by comprising: a process of adding a specified amount of metal M to a halide mixture containing the abovementioned various rare earth elements; a process of achieving a chemical equilibrium state of a divalent halide generating the abovementioned various rare earth elements and a halide of the abovementioned metal M by heating under atmospheric pressure the mixture to which the abovementioned metal M is added; a process of generating a metal and a trivalent halide of a rare earth element due to disproportionation reaction of a divalent halide of a rear earth element among the abovementioned various rare earth elements by performing vacuum pumping on a system that achieves the abovementioned chemical equilibrium state; and a process of separating the abovementioned mixture into a distilled condensate of the trivalent halide of the abovementioned rare earth element and residues by performing vacuum distillation on the system.
Description
Technical field
The present invention relates to the technology of Separation and Recovery rare earth element, particularly relate to the method for Separation and Recovery rare earth element the composition from containing multiple rare earth element.
Background technology
In recent years, recognize the importance of the environment of preserving our planet constantly, concentrate one's energy to develop and can use to inferior limit the industrial system of fossil oil and traffic system etc.As system, the goods of this environment fitter type, for example can enumerate wind generator system, Railway System, hybrid vehicle, electromobile, energy-saving type air conditioner etc.
One of major equipment of these environment fitter type systems, goods is high-efficiency rotating motor (motor or generator), is widely used the magnet (that is, rare earth element magnet) that contains rare earth element in this high-efficiency rotating motor.For example, the rare earth element magnet using in the rotating machine of the CD-ROM drive motor of hybrid vehicle and the compressor of air conditioning machinery etc., for example, even if in hot environment (require, approximately 200 ℃) in also there is high coercive force, this class magnet is except containing neodymium, iron, boron, the heavy rare earth element (for example, dysprosium) that also contains in a large number high price.Rare earth element magnet has become indispensable material now, expects that demand also can expand from now on.
On the other hand, rare earth element becomes independent element owing to being difficult to separation and purification, is again expensive, and for this reason, people study intensively and developed technology and the equivalent material that the performance that can maintain magnet can reduce again consumption.But, for making these technical applications, also need the long period.Therefore, for example, from rejected material (, the rare earth element magnet in discarded motor and the cutting powder (disintegrating slag) producing in the production process of rare earth element magnet etc.) Separation and Recovery rare earth element be important technology by its recycle.
For example, patent documentation 1 discloses the separation method of rare earth element, it is characterized in that, by the rare earth element in the mixture that contains multiple rare earth element or its compound carry out halogenation manufacture a kind of contain be the average valence mumber of rare earth class ion of more than two kinds be more than 23 valencys of the divalent below 3 mishmetal Pseudohalides and be not with the aqueous solution or the mixture that exists with the state being dissolved in organic solvent, then, utilizing the different of divalent rare earth class halogenide and the halid character of 3 valency rare earth class, is at least 2 groups by above-mentioned multiple rare earths separation.According to patent documentation 1, can improve by leaps and bounds the separation factor between rare earth element, compare with method in the past, can effectively be separated from each other.And then, when carrying out separation from the rare earth class concentrate such as phosphoric acid salt, acid dissolving, filtration, the contamination precipitation that can be omitted in requisite concentrate in wet method in the past removed, concentrates, neutralizes, is dried such operation, thereby can reduce significantly separation costs.
In addition, the recovery method of rare earth element is disclosed in patent documentation 2, the method is the method for recovering rare earth element the material from containing rare earth element and iron family element ting, it is characterized in that, there is following operation: the material that the chip of rare earth element magnet or disintegrating slag etc. contain rare earth element and iron family element ting is contacted with the iron(ic) chloride of gas or molten state, under the condition of the metallic state of the iron family element ting in keeping above-mentioned substance, make the rare earth element in above-mentioned substance carry out chlorination reaction, come so optionally to reclaim as muriatic rare earth element from above-mentioned substance.According to patent documentation 2, the material that can contain rare earth element and iron family element ting from the chip of rare earth element magnet or disintegrating slag etc., particularly in waste, only the rare earth class composition of extraction, separating high-purity, can establish the method for rare earth element magnet recycle more cheaply thus.
Prior art document
Patent documentation
[patent documentation 1] JP 2001-303149 communique
[patent documentation 2] JP 2003-73754 communique
[summary of the invention]
Invent problem to be solved
As mentioned above, expect that rare earth element magnet demand from now on also can expand.On the other hand, becoming the rare earth element locals such as the neodymium of rare earth element magnet raw material and dysprosium is present on the earth, from guaranteeing that the viewpoint of the stable supply of raw material and the viewpoint of efficent use of resources consider, the technology of Separation and Recovery rare earth element in addition recycle becomes even more important than in the past.
Therefore, the object of the invention is to, provide a kind of easier and can be with the method for high yield Separation and Recovery rare earth element than conventional art.
For solving the means of problem
(I) 1 scheme of the present invention is, in order to achieve the above object, provides the separation and recovery method of rare earth element, and the method, for separating of reclaiming multiple rare earth element, wherein, has following operation:
To the operation (operation A) of adding the metal M of specified amount in the halid mixture that contains above-mentioned multiple rare earth element; By under atmospheric pressure heating to reach to having added the mixture of above-mentioned metal M the operation (process B) that generates the divalence halogenide of above-mentioned multiple rare earth element and the halid chemistry balance state of above-mentioned metal M; By carrying out vacuum exhaust to reaching in the system of above-mentioned chemistry balance state, make metal and the halid operation of trivalent (operation C) of divalence halogenide above-mentioned a kind of rare earth element because disproportionation reaction generates of a kind of rare earth element in above-mentioned multiple rare earth element; And by making said mixture be separated into the halid distillation condensation product of trivalent of above-mentioned a kind of rare earth element and the operation (step D) of residue to carrying out vacuum distilling in system; Wherein, the metal that above-mentioned metal M can coexist for metal M and the oxide compound of metal M under the environment of above-mentioned chemistry balance state and the halid three-phase of metal M, afore mentioned rules amount is than the amount of the halid chemical equivalent surplus with respect to above-mentioned multiple rare earth element.
(II) another scheme of the present invention is, in order to achieve the above object, provides the separation and recovery method of rare earth element, and the method, for separating of reclaiming multiple rare earth element, wherein, has following operation:
By the compound chlorination that contains above-mentioned multiple rare earth element, iron, boron being generated with iron(ic) chloride to the operation (operation E) that contains muriatic mixture; By distill the operation (operation F) of the muriatic mixture of separated above-mentioned multiple rare earth element from contain above-mentioned muriatic mixture to containing above-mentioned muriatic mixture; To the operation (operation A ') of adding the metal M of specified amount in the muriatic mixture of above-mentioned multiple rare earth element; By the mixture that under atmospheric pressure above-mentioned metal M has been added in heating, reach the operation (process B ') that generates the dichloride of above-mentioned multiple rare earth element and the muriatic chemistry balance state of above-mentioned metal M; By to reach in the system of above-mentioned chemistry balance state, carry out dichloride that vacuum exhaust makes a kind of rare earth element in above-mentioned multiple rare earth element because disproportionation reaction generates the metal of above-mentioned a kind of rare earth element and the operation of trichloride (operation C '); And by making said mixture be separated into the distillation condensation product of trichloride of above-mentioned a kind of rare earth element and the operation of residue (step D ') to carrying out vacuum distilling in system; Wherein, the metal that above-mentioned metal M can coexist for metal M and the oxide compound of metal M under the environment of above-mentioned chemistry balance state and the muriatic three-phase of metal M, afore mentioned rules amount is than the amount of the muriatic chemical equivalent surplus with respect to above-mentioned multiple rare earth element.
In addition, the present invention, in the separation and recovery method (I) of above-mentioned rare earth element, (II), can resemble following and be improved and change.
(i) carry out above-mentioned operation C and above-mentioned step D simultaneously.
(ii) carry out above-mentioned operation C ' and above-mentioned step D ' simultaneously.
(iii) the oxygen gesture (Potential) of the oxidizing reaction of above-mentioned metal M is lower than the oxygen partial pressure of above-mentioned multiple rare earth element.
(iv) the halogen gesture of the above-mentioned a kind of rare earth element of halogen intrinsic standoff ratio of the halogenating reaction of above-mentioned metal M is low, and higher than the halogen dividing potential drop of other the a kind of rare earth element in above-mentioned multiple rare earth element.
(v) above-mentioned metal M is at least a kind that is selected from thulium, terbium, erbium, holmium, yttrium.
(vi) above-mentioned a kind of rare earth element is dysprosium.
(vii) above-mentioned multiple rare earth element also contains at least a kind that is selected from neodymium, gadolinium, samarium.
(viii) above-mentioned halogen is chlorine.
The effect of invention
According to the present invention, can provide easier than conventional art and can be with the method for high yield Separation and Recovery rare earth element.Its result, can for example, for example,, with low cost separation of rare earth elements (, neodymium, dysprosium etc.) accurately from the waste (, waste product, substandard products, disintegrating slag etc.) of rare earth element magnet, can regenerate the rare earth element of separating as raw material.Can contribute to thus efficent use of resources and guarantee the stable of rare earth class raw material.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section of the state of an example after being next to separation circuit that be illustrated in the water distilling apparatus using in the separation circuit of rare earth element and other elements.
Fig. 2 illustrates the quality and the graphic representation that is attached to the mass distribution of the condensation phase on separate type inwall of carrying out residue in fractionation by distillation operation crucible afterwards in embodiment 1.
Fig. 3 A is the graph that the compositional analysis result of the condensation phase of utilizing residue (except Y fragment) in the crucible that XRF obtains and separate type inwall 8e～8g in embodiment 1 is shown.
Fig. 3 B illustrates the Dy being calculated by formula (1) and formula (2) of Fig. 3 A than the graph with Nd ratio.
Fig. 4 is the XRD curve of the Powdered residue in crucible in embodiment 1.
Fig. 5 is the XRD curve that is attached to the melts shape residue of crucible bottom in embodiment 1.
Fig. 6 is the XRD curve of the condensation phase of separate type inwall 8g in embodiment 1.
Nomenclature
1 ... epimere well heater, 2 ... hypomere well heater, 3,3 ' ... thermopair, 4 ... stove core barrel, 5 ... venting port, 6 ... gas introduction port, 7 ... upper cap, 8 ... inwall, 8a～8m ... separate type inwall, 9 ... crucible, 10,11 ... condensation phase, 20 ... water distilling apparatus.
Embodiment
Below, limit illustrates in greater detail embodiment of the present invention with reference to accompanying drawing limit.Be explained, the embodiment that the present invention is not limited to enumerate herein can be carried out appropriately combined or improve in the scope that does not change main idea.
[the 1st embodiment of the present invention]
(basic step of rare earths separation and principle thereof)
Basic step and principle thereof for the separation method of the rare earth element in the present invention describe.Separation method of the present invention is characterised in that, will utilize the solid and gas separation of disproportionation reaction and consolidate discrete group altogether.Herein, as an example, the separated when mixture that uses Neodymium trichloride and Dysprosium trichloride is described, but the present invention is not limited to this.
First, to neodymium trichloride (NdCl
3) and dysprosium trichloride (DyCl
3) mixture in add, mix the metallic yttrium (Y) as metal M.Shape for added metallic yttrium is not particularly limited, and for easily separated in subsequent handling, be preferably and have than large granular, the bulk of rare earth class muriate or shred.
Secondly, this mixture is under atmospheric pressure heated to 700～900 ℃.So just make the muriatic mixture of rare earth class that has added metallic yttrium reach the chemistry balance state shown in following chemical formula (1), chemical formula (2).
[changing 1]
3NdCl
3+ Y=3NdCl
2+ YCl
3chemical formula (1)
[changing 2]
3DyCl
3+ Y=3DyCl
2+ YCl
3chemical formula (2)
According to chemical formula (1), (2) judgement, metallic yttrium works as reductive agent.In addition, by excessively adding metallic yttrium, can make chemical reaction further carry out to the right.In other words, for the generation of rare earth class dichloride is carried out, in the muriatic mixture to rare earth class, add, during hybrid metal yttrium, according to the muriatic chemical equivalent of the rare earth class with respect in mixture, be preferably that superfluous amount is added metallic yttrium.
Secondly, to carrying out vacuum exhaust in the above-mentioned system that reaches chemistry balance state.The method of vacuum exhaust and degree do not have special restriction, as long as use for example rotary pump to reach medium vacuum degree.Under reduced pressure atmosphere, the dichloride dysprosium (DyCl generating in chemical formula (2)
2) become unstable, cause the disproportionation reaction shown in following chemical formula (3), resolve into metal dysprosium (Dy) and dysprosium trichloride (DyCl
3).Be explained, for dichloride neodymium (NdCl
2), the degree of disproportionation reaction is very little.
[changing 3]
3DyCl
2=Dy+2DyCl
3chemical formula (3)
Secondly, by heating in above-mentioned system and remaining on 1000～1100 ℃, carry out vacuum distilling.Herein, the NdCl generating in chemical formula (1)
2steam force down, the yttrium trichloride (YCl generating in chemical formula (1), (2)
3) and the middle DyCl generating of chemical formula (3)
3vapour pressure high, therefore, YCl
3and DyCl
3be distilled out, and be condensed at low-temperature region.On the other hand, NdCl
2left behind as residue with Y metal and the middle Dy metal generating of chemical formula (3) of excess quantity.Vacuum exhaust in system caused to the above-mentioned operation of disproportionation reaction and vacuum distilling in system can be carried out continuously to be separated into this operation of distillation condensation product and residue, also can carry out simultaneously.From simplifying the viewpoint of step, consider, preferably carry out two operations simultaneously.Be explained, the implication of simultaneously carrying out comprises starts heating (intensification) and vacuum exhaust simultaneously.
As mentioned above, because Y metal adds with large granular or block or shred, therefore, can easily from residue, separate.Because the Dy metal generating in chemical formula (3) also becomes bulk, therefore also can easily carry out separation.In addition, when using iron (Fe) crucible as crucible, with crucible reaction, generate Fe-Y alloy or Fe-Dy alloy.On the other hand, the form that rare earth class muriate is generally Powdered or solidifies, even the latter, also can be simply to impact and to pulverize.Therefore, they can easily carry out mechanical separation, can be from residue Separation and Recovery Y metal, Dy metal and NdCl
2.In addition, can also from distillation condensation product, reclaim DyCl
3and YCl
3.Be explained DyCl
3and YCl
3can adopt method (for example, solvent extration) in the past to carry out separation.
(the selection policy of the metal M of interpolation)
Secondly, for the selection policy of adding the metal M in the muriatic mixture of rare earth class to, describe.The calculation result of the oxygen gesture of the oxidizing reaction of various metals is shown in table 1, and the calculation result of the chlorine gesture of the chlorination reaction of various metals is shown in table 2.Be explained the oxygen partial pressure (pO in table
2) and chlorine dividing potential drop (pCl
2) unit be respectively " atm ".
The oxygen gesture calculation result of the oxidizing reaction of the various metals of table 1
In table, [s, l] refers to solid phase or liquid phase, and [g] refers to gas phase.
The chlorine gesture calculation result of the chlorination reaction of the various metals of table 2
In table, [s, l] refers to solid phase or liquid phase, and [g] refers to gas phase.
The metal M of adding, except the above-mentioned effect as reductive agent, preferably also has the effect that the reductor of oxidation occurs as the rare earth element for preventing from separating.In other words, a kind of metal that oxidation occurs under the condition of the low oxygen gesture of the rare earth element than separating preferably.If according to this viewpoint table 1, as the metal of oxidation occurs under the condition of the oxygen gesture lower than Dy (dysprosium), can enumerate Tb (terbium), Tm (thulium), Ho (holmium), Ca (calcium), Er (erbium), Sc (scandium), Y (yttrium).By interpolation, compare the metal that the rare earth element that will separate is more easily oxidized, even in the situation that residual in the system of separation of rare earth elements/sneak into oxygen composition, also can suppress the oxidation of the rare earth element that will separate.
On the other hand, while considering from chlorination reaction, the chlorine gesture of the chlorination reaction of the metal M of interpolation, preferably than the multiple rare earth element by separating, be transformed into the chlorination gesture of metal high, and the gesture that is reduced to dichloride by trichloride than multiple rare earth element is low.If see table 2 according to this viewpoint, as than Nd, Dy, the metal of chlorination all occurring under the condition of high chlorine gesture, can enumerate Mg (magnesium), Tm, Tb, Er, Ho, Y, Gd (gadolinium).
Therefore, as the metal M of adding, preferred above-mentioned Tm, Tb, Er, Ho, the Y that becomes common metallic element.In other words, the metal M of interpolation is under the environment of chemical formula (1)～(3), the metal that the muriatic three-phase of the oxide compound of metal M and metal M and metal M can coexist.Be explained, the state of the oxide compound of metal M and metal M and the muriatic three-phase coexistence of metal M also can be called " triple equilibrium state ".
In addition, as mentioned above, the present invention is not limited to the mixture of Neodymium trichloride and Dysprosium trichloride, for example, also go for the mixture of mixture, samarium trichloride and the Dysprosium trichloride of Gadolinium trichloride and Dysprosium trichloride.In addition, above recorded and used chlorine as the example of the system (muriate) of halogen, but same action effect is not limited to muriate, also goes for iodide, fluorochemical, bromide.
[the 2nd embodiment of the present invention]
(separation of rare earth elements from the compound that contains rare earth element)
Then, for adopt above-mentioned principle when the Separation and Recovery from the rare earth element magnet as actual parent material (compounds of rare earth element and other elements) method of Separation and Recovery rare earth element describe.
(separation circuits of rare earth element and other elements)
First the step that obtains the mixture of Neodymium trichloride and Dysprosium trichloride from contain neodymium, dysprosium, iron, the rare earth element magnet disintegrating slag of boron as principal constituent is described.Be explained, in actual rare earth element magnet disintegrating slag, often contain the praseodymium as another kind of element in rare earth element, but because physics, the chemical property of neodymium and praseodymium are closely similar, therefore, think that praseodymium is accompanied by neodymium and exists together herein.
The separation circuit of rare earth element and other elements (step), basic identical, specific as follows with the disclosed operation of patent documentation 2.As the rare earth element magnet for element separation, preferably use waste as described above (for example, waste product, substandard products, disintegrating slag etc.), from the viewpoint of Separation and Recovery efficiency (chemical reaction efficiency), consider, be preferably Powdered.With the example that is separated into the disintegrating slag powder from rare earth element magnet, describe below.
Fig. 1 is the schematic cross-section of the state of an example after being next to separation circuit that be illustrated in the water distilling apparatus using in the separation circuit of rare earth element and other elements.As shown in Figure 1, the basic structure of water distilling apparatus 20 is in the periphery of vertical heater core barrel 4, to have the vertical electric furnace of cylinder of the well heater (epimere well heater 1, hypomere well heater 2, thermopair 3,3 ') of upper and lower 2 sections.Stove core barrel 4 has venting port 5, gas introduction port 6, upper cap 7 can exhaust, gas displacement being carried out in inside.Venting port 5 is connected with (not shown) such as rotary pumps.Be explained, Fig. 1 shows the stove core barrel 4 at the end, but can be also the structure with lower cover sealing.In addition, the place that arranges for venting port 5 and gas introduction port 6 is also not particularly limited.
The inwall 8 of the internal configuration cylinder multi-stage type of stove core barrel 4 (separate type inwall 8a～8m).The crucible 9 of the material that has added separation to be distilled is set in the inner side of the hypomere (separate type inwall 8a) of inwall 8 in addition.
First, the disintegrating slag powder that uses drying machine etc. to be dried is broken.Then, by breaked disintegrating slag powder, powdered graphite with than the iron protochloride (FeCl of the amount of chemical equivalent surplus
2) mix, be filled in crucible 9.The inner side that crucible 9 is arranged on to the hypomere (separate type inwall 8a) of inwall 8, is assembled into water distilling apparatus 20.By the inner vacuum exhaust of stove core barrel 4, for example, with after rare gas element (, argon gas) displacement, Yi Bian pass into rare gas element, Yi Bian under atmospheric pressure implement the heat treated of 700～900 ℃.The result of this heat treated, the mixing material generation chemical reaction in crucible 9 obtains the mixture (operation that generation contains muriatic mixture) of rare earth class muriate, unreacted iron protochloride, iron or iron family element ting alloy in crucible 9.Be explained, the oxygen composition being fixed in rare earth element magnet disintegrating slag powder is gasified by powdered graphite (carbon component), and the gas of generation is discharged to outside system by mobile rare gas element.
Secondly, for the mixture of the rare earth class muriate obtaining, iron protochloride, iron or iron family element ting alloy, by one side, with decompressions such as rotary pumps, Yi Bian be heated to 900～1100 ℃, carry out fractionation by distillation.Now, preferably the temperature of epimere well heater 1 is remained on to 400～500 ℃, the temperature of hypomere well heater 2 is remained on to 700～1100 ℃.The result of this fractionation by distillation, the upper condensation phase 10 that forms iron protochloride of inwall 8 in epimere well heater 1 region (being separate type inwall 8g～8h in Fig. 1), the upper muriatic condensation phase 11 of rare earth class that forms of inwall 8 in hypomere well heater 2 regions (being separate type inwall 8d～8e in Fig. 1) remains as the iron of residue and the alloy of iron family element ting (operation of the muriatic mixture of separated multiple rare earth element) in crucible 9.If reclaim the condensation phase 11 of separate type inwall 8d～8e, obtain the muriatic mixture of multiple rare earth class.The in the situation that of this example, obtain particularly the mixture of Neodymium trichloride and Dysprosium trichloride.
(separation circuit of multiple rare earth element)
Secondly, to being separated from each other the operation of rare earth element the muriatic mixture of multiple rare earth class from reclaiming, describe.In this operation, also can use the water distilling apparatus 20 shown in Fig. 1.The muriatic mixture of multiple rare earth class reclaiming is mixed with the metallic yttrium that is excess quantity with respect to this rare earth class muriate chemical equivalent, be filled in the crucible 9 of molybdenum system.Now, rare earth class muriate is imbued with water absorbability, therefore, for fear of excessive moisture absorption, wishes weighing, mixes, is filled in dry environment and for example, carry out fast in (, kiln, glove box etc.).In addition, in order to remove excessive oxygen in the system that chemical reaction occurs as far as possible, also can add powdered graphite.
The inner side that the crucible 9 of having filled is arranged on to the hypomere (separate type inwall 8a) of inwall 8, is assembled into water distilling apparatus 20.By the inner vacuum exhaust of stove core barrel 4, with after the inert gas replacements such as argon gas, while flow into rare gas element, under atmospheric pressure implement the heat treated of 700～900 ℃, 6～24 hours.The result of this heat treated, the mixing material generation chemical reaction in crucible 9, reaches the chemistry balance state shown in chemical formula (1), (2) (making reaction reach the operation of chemistry balance state).Be explained, as mentioned above, due to the metallic yttrium that to have mixed with respect to the muriatic chemical equivalent of rare earth class be excess quantity, therefore in crucible 9, in fact obtain the dichloride neodymium (NdCl as resultant
2), dichloride dysprosium (DyCl
2) and yttrium trichloride (YCl
3), and as the metallic yttrium (Y) of unreacted reactant.
Then, under the state of the temperature in maintenance system, with rotary pump etc. by vacuum exhaust in system.Its result has caused the disproportionation reaction as shown in chemical formula (3) in dichloride dysprosium, decomposes and generates metal dysprosium (Dy) and dysprosium trichloride (DyCl
3) (operation of disproportionation reaction occurs).
Then, while by continuing that the further heating of vacuum exhaust in system is carried out to fractionation by distillation.Now, preferably the temperature of epimere well heater 1 is remained on to 400～500 ℃, the temperature of hypomere well heater 2 is remained on to 700～1100 ℃.By this vacuum distilling, make the DyCl that vapour pressure is high
3and YCl
3distillation, the upper condensation phase 10 that forms of the inwall 8 of (being in low-temperature region) in epimere well heater 1 region (for example, separate type inwall 8g～8h).Meanwhile, due to the DyCl in crucible 9
3reduce, the disproportionation reaction of chemical formula (3) is further carried out to the right.In crucible 9, the NdCl generating in unreacted Y metal and chemical formula (1)
2with the Dy metal generating in chemical formula (3) as residue and residual (carrying out the separated operation of solid and gas by vacuum distilling).
After fractionation by distillation, water distilling apparatus 20 is cooled to room temperature.About the residue in crucible 9, as mentioned above, due to Y metal, Dy metal and NdCl
2shape and vary in size, therefore, can be by they Separation and Recovery (utilizing shape or size to carry out solid separated operation) mechanically.By to the NdCl separating
2in atmosphere, under the condition of 900 ℃ of left and right, carry out roasting, can reclaim Neodymium trioxide.
On the other hand, first the condensation of recovery 10 put in pure water and stirred mutually, preparing the aqueous solution of Dysprosium trichloride and Yttrium trichloride.This aqueous solution is carried out after pH regulator, for example, by adding precipitation agent (, volatile salt ((NH
4)
2cO
3), bicarbonate of ammonia (NH
4hCO
3), sodium carbonate (Na
2cO
3), sodium bicarbonate (NaHCO
3), oxalic acid ((COOH)
2), sodium oxalate ((COONa)
2), ammonium hydroxide (NH
4oH) etc.), generate the dysprosium salt of slightly water-soluble and the throw out of yttrium salt.After this throw out is filtered, is dried, by carry out roasting under the condition of 900 ℃ of left and right in atmosphere, can reclaim the mixture of dysprosium oxide and yttrium oxide.
In addition, omit detailed explanation, dysprosium oxide and yttrium oxide can, after Ore Leaching, adopt method (for example, solvent extration) in the past to carry out separation.After the dysprosium salt of separating and yttrium salt is dry, by carry out roasting under the condition of 900 ℃ of left and right in atmosphere, can reclaim respectively dysprosium oxide and yttrium oxide.
(being reduced to the operation of rare earth metal)
By respectively the Neodymium trioxide of above-mentioned recovery, dysprosium oxide and yttrium oxide being used the fusion electrolysis of fluoride bath etc., can be reduced to neodymium metal, metal dysprosium and metallic yttrium.These rare earth metals can be used as the raw material recycling of rare earth element magnet.
[embodiment]
Below, based on embodiment, be described more specifically the present invention, but the present invention is not limited to these embodiment.
[embodiment 1]
The Separation and Recovery of experimental verification from the muriatic mixture of rare earth class.As the muriatic starting raw material of rare earth class, use anhydrous neodymium trichloride (NdCl
3) powder and anhydrous dysprosium trichloride (DyCl
3) powder.As the powder reagent of starting raw material, all use the 3N level reagent of (strain) high-purity chemical institute system.As the metal M of adding, use the fragment of metallic yttrium (Y) (with the pure pharmaceutical worker's industry of light (strain) system, approximately 5 * approximately 5 * about 2mm
3, purity 99.9%).Be explained, due to easily oxidized in the oxygen source of metallic yttrium in atmosphere, therefore, the metallic yttrium that preparation is preserved in oil, is used after when facing use, oil content being removed.
In kiln, weigh the NdCl of 2.5g
3the DyCl of powder, 2.5g
3the Y fragment of powder and 1.16g, puts in molybdenum (Mo) crucible 9 processed and mixes.Use the water distilling apparatus 20 shown in Fig. 1, in the inner side of the hypomere (separate type inwall 8a) of inwall 8, the crucible 9 that has added mixing material is set, assembling inwall 8.Inwall 8 is cylinder multi-stage type, has the structure that is separated into separate type inwall 8a～8m (graphite-made, separately internal diameter 50mm * high 50mm).Thus, reclaim distillation condensation and become mutually easily, in addition, can investigate the distribution of distillation condensation phase.Be explained, Mo crucible 9 processed and graphite-made separate type inwall 8a～8m are implemented to the roasting of 3 hours in advance in a vacuum at 800 ℃, then carry out quality determination.
Assemble after inwall 8, by 4 use upper caps 7 sealings of stove core barrel, by venting port 5 use rotary pumps by the interior decompression of stove core barrel 4.Then, 300 ℃ of heating, more than 12 hours, will in mixing material and stove core barrel 4, carry out after vacuum-drying, from gas introduction port 6, import argon gas, make to become in system normal atmosphere.In order to remove residual oxygen composition in stove core barrel 4 and gas introduction port 6 etc. as far as possible, repeat 5 gas exhausts and import the operation of gas.
Then, Yi Bian flow into argon gas, Yi Bian make the temperature of the low-temp. portion epimere well heater 1 of epimere, be 400 ℃, the temperature that makes hypomere well heater 2 is 800 ℃, implements the heat treated of 6 hours, makes to reach the chemistry balance state shown in chemical formula (1), (2).Then,, under the state of the temperature in maintenance system, with rotary pump, by vacuum exhaust in system, make to occur the disproportionation reaction shown in chemical formula (3).
Then, continue system in vacuum exhaust on one side, making the temperature of the low-temp. portion epimere well heater 1 of epimere is on one side 500 ℃, the temperature that makes hypomere well heater 2 is 1000 ℃, carries out the fractionation by distillation of 3 hours.By this vacuum distilling, on the inwall 8 in low-temperature region, form condensation phase 10.After distillation, under the state of vacuum exhaust, be cooled to room temperature.
After cooling, the sample of vacuum distilling (residue in condensation phase 10 and crucible 9) is carried out to various evaluations.First, in order to investigate the distribution of condensation phase 10, by weighing the quality of separate type inwall 8a～8m in the difference of experiment front and back, measure the quality together with the condensation phase 10 of separate type inwall.Also measure the quality of crucible 9 interior residues.In addition, to the residue in crucible 9 and condensation 10 samplings mutually that are attached on separate type inwall, utilize x-ray fluorescence analysis (XRF:X-ray fluorescence analysis) to carry out compositional analysis, utilize X-ray diffraction (XRD:X-ray diffraction) to carry out the evaluation of precipitated phase.
From the composition of the residue obtained with XRF and aggegation phase, calculate separation rate and the yield of Nd and Dy.The Dy concentration of obtaining with XRF and the Dy scale that goes out according to the Mass Calculation of residue or aggegation phase are shown to [Dy], equally the Nd concentration of obtaining with XRF and the Nd scale that goes out according to the Mass Calculation of residue or aggegation phase are shown to [Nd], from following formula (1), formula (2), obtain Dy than (R respectively
dy) and Nd than (R
nd).
[several 1]
[several 2]
In addition, about Dy yield (yield
dy) and Nd yield (yield
nd), Dy amount and Nd amount during by mixing are expressed as [Dy]
0[Nd]
0, by following formula (3), formula (4), obtained.
[several 3]
formula (3)
[several 4]
Fig. 2 illustrates the quality and the graphic representation that is attached to the mass distribution of the condensation phase on separate type inwall of carrying out residue in fractionation by distillation operation crucible afterwards in embodiment 1.As shown in Figure 2, confirm approximately to have in crucible 9 residue of 3.5g, confirm that the quality on separate type inwall 8e～8g has remarkable increase (approximately 0.7～0.9g).
In more detail, as the residue of Mo crucible 9 processed, be confirmed to be melts shape residue and Powdered residue.In addition we know, the Y fragment of input is sneaked in residue under the state that retains this chip shape.Residual Y fragment, can easily take out.Weighing this residual Y fragment, is about 0.7g.That is, can think, add in the Y composition mixing, about 0.7g is as Y metal residual, and about 0.4g is chlorinated and is present in system.
Fig. 3 A is for to illustrate the condensation phase for residue in crucible in embodiment 1 (removing Y fragment) and separate type inwall 8e～8g, utilizes the graph of the compositional analysis result that XRF obtains.Fig. 3 B is for illustrating according to Fig. 3 A and the Dy ratio calculating according to formula (1) and formula (2) and the graph of Nd ratio.
As shown in Figure 3A, the residue in crucible 9 (removing Y fragment) mainly consists of Cl, Nd, Dy, detects in addition some Y.Specifically, Cl is that 24.3%, Nd is that 41.2%, Dy is 30.4%.Be explained, Dy metal and Nd muriate due to its shape, vary in size, therefore mechanical separation easily.
On the other hand, in the condensation mutually of separate type inwall 8e～8g, significantly detect Cl, Y, Dy, and the containing ratio of Nd is few.Specifically, on separate type inwall 8e, Cl is that 24.3%, Y is that 19.7%, Dy is that 29.1%, Nd is 9.5%.On separate type inwall 8f, Cl is that 41.1%, Y is that 20.6%, Dy is that 28.2%, Nd is 10.0%.In addition, on separate type inwall 8g, Cl is that 49.2%, Y is that 25.6%, Dy is that 22.4%, Nd is 2.8%.
As shown in Figure 3 B, about the Dy ratio in condensation mutually, on separate type inwall 8e, be 75.5%, on separate type inwall 8f, be 73.9%, on separate type inwall 8g, be 89.0%, obtain high value.Dy during due to making mixing material is 50.0% than (initial stage Dy ratio), therefore can judge, according to separating technology of the present invention, can carry out good separation.In addition, during the yield of the mean value calculation Dy of the Dy ratio from the condensation mutually of separate type inwall 8e～8g, be " yield
dy=59.5% ".
Fig. 4 is the XRD curve of the Powdered residue in crucible in embodiment 1.As shown in Figure 4, the Powdered residue in crucible 9, mainly detects NdCl
2peak, detect in addition YOCl, Y
3o
4cl (Y
2o
3yOCl), the peak of DyOCl.Can think, oxychlorination thing is because residual in the system/oxygen composition of sneaking into generates.
Fig. 5 is the XRD curve that is attached to the melts shape residue of crucible bottom in embodiment 1.As shown in Figure 5, the melts shape residue for being attached to the bottom of Mo crucible 9 processed, except detecting the Mo metal being caused by crucible, also detects Dy metal and YOCl.
Fig. 6 is the XRD curve of the condensation phase of separate type inwall 8g in embodiment 1.As shown in Figure 6, mainly detect DyCl
3and YCl
3, also detect some NdCl
3.
From above mensuration and analytical results, can say in chemical reaction and the sepn process shown in the 1st embodiment of the present invention and be confirmed.
[embodiment 2]
Rare earth element magnet (the RE of research from containing neodymium, dysprosium, praseodymium, iron, boron
2fe
14b, RE: separated, recovering rare earth element in waste material rare earth element).The quality group of the rare earth element magnet using becomes 61.2%Fe-23.1%Nd-3.5%Dy-2.0%Pr-1.0%B.In this useless magnet Shi manufacturing process, implement after nickel plating, owing to there are crackle or defect etc., become substandard products.
First, by use electric furnace in nitrogen atmosphere in 800 ℃ of heating, the coarse reduction of the magnet that gives up.As mentioned above, although this useless magnet has been implemented nickel plating, plated nickel film can utilize hydrogen pulverizing process to peel off, and that plated film after peeling off can adopt sieve method was separated with ferromagnetic powder.
Using the ferromagnetic powder obtaining with as the FeCl in chlorine source
2powder mixes, and then joins in iron crucible 9, is configured in the water distilling apparatus 20 shown in Fig. 1.To chromium ferronickel heat-resistant and etching-resistant alloy stove core barrel 4 processed is interior, with after rotary pump exhaust, use argon replaces, making the temperature of hypomere well heater 2 is 800 ℃, and the temperature that makes epimere well heater 1 is 400 ℃, keeps 10～15 hours, carries out the chlorination reaction of ferromagnetic powder.Then, the temperature of hypomere well heater 2 is warming up to 1000 ℃, the temperature of epimere well heater 1 is warming up to 500 ℃, Yi Bian use rotary pump exhaust, Yi Bian carry out vacuum distilling in 3 hours.After vacuum distilling, in making stove core barrel 4, remain under the state of vacuum stove is cooling.
Stove is cooled to after room temperature, when observing the condensation phase attachment of inwall 8 (separate type inwall 8a～8m), region at 500～800 ℃, lilac is Powdered, the material generation condensation of shallow green powder shape, white powder, in the temperature province lower than 500 ℃, the material generation condensation of orange powder shape.When these condensed materials are during in general indoor placement, observe the situation of moisture absorption at short notice.On the other hand, when these condensed materials of quick recovery and while carrying out semi-quantitative analysis with XRF device, confirmed that the condensed material in 500～800 ℃ of regions mainly comprises the muriate of rare earth element (neodymium, praseodymium, dysprosium), its containing ratio is 98%.
For the muriatic mixture of rare earth class of above-mentioned recovery, if carry out the separation circuit same with above-described embodiment 1, neodymium, praseodymium, dysprosium can be separated from each other.
Claims (11)
1. the separation and recovery method of rare earth element, the method, for separating of reclaiming multiple rare earth element, is characterized in that,
The method has following operation:
Operation A: to the operation of adding the metal M of specified amount in the halid mixture that contains above-mentioned multiple rare earth element;
Process B: by under atmospheric pressure heating to reach to having added the mixture of above-mentioned metal M the operation that generates the divalence halogenide of above-mentioned multiple rare earth element and the halid chemistry balance state of above-mentioned metal M;
Operation C: by carrying out vacuum exhaust to reaching in the system of above-mentioned chemistry balance state, make metal and the halid operation of trivalent of divalence halogenide above-mentioned a kind of rare earth element because disproportionation reaction generates of a kind of rare earth element in above-mentioned multiple rare earth element; And
Step D: by making said mixture be separated into the halid distillation condensation product of trivalent of above-mentioned a kind of rare earth element and the operation of residue to carrying out vacuum distilling in system;
The metal that above-mentioned metal M can coexist for metal M and the oxide compound of metal M under the environment of above-mentioned chemistry balance state and the halid three-phase of metal M,
Afore mentioned rules amount is than the amount of the halid chemical equivalent surplus with respect to above-mentioned multiple rare earth element,
Above-mentioned multiple rare earth element is dysprosium and neodymium, and above-mentioned a kind of rare earth element is dysprosium.
2. the separation and recovery method of rare earth element claimed in claim 1, is characterized in that, carries out above-mentioned operation C and above-mentioned step D simultaneously.
3. the separation and recovery method of the rare earth element described in claim 1 or 2, is characterized in that, the oxygen gesture of the oxidizing reaction of above-mentioned metal M is lower than the oxygen gesture of above-mentioned multiple rare earth element.
4. the separation and recovery method of the rare earth element described in claim 1 or 2, is characterized in that, the halogen gesture of the halogenating reaction of above-mentioned metal M is lower than the halogen gesture of above-mentioned a kind of rare earth element, and higher than the halogen gesture of other the a kind of rare earth element in above-mentioned multiple rare earth element.
5. the separation and recovery method of the rare earth element described in claim 1 or 2, is characterized in that, above-mentioned metal M is at least a kind that is selected from thulium, terbium, erbium, holmium, yttrium.
6. the separation and recovery method of the rare earth element described in claim 1 or 2, is characterized in that, above-mentioned halogenide is muriate.
7. the separation and recovery method of rare earth element, the method, for separating of reclaiming multiple rare earth element, is characterized in that, the method has following operation:
Operation E: by the compound chlorination that contains above-mentioned multiple rare earth element, iron, boron being generated to the operation that contains muriatic mixture with iron(ic) chloride;
Operation F: by distill the operation of the muriatic mixture of separated above-mentioned multiple rare earth element from contain above-mentioned muriatic mixture to containing above-mentioned muriatic mixture;
Operation A ': to the operation of adding the metal M of specified amount in the muriatic mixture of above-mentioned multiple rare earth element;
Process B ' by the mixture that under atmospheric pressure above-mentioned metal M has been added in heating, reach the operation that generates the dichloride of above-mentioned multiple rare earth element and the muriatic chemistry balance state of above-mentioned metal M;
Operation C ': by reach in the system of above-mentioned chemistry balance state, carry out dichloride that vacuum exhaust makes a kind of rare earth element in above-mentioned multiple rare earth element because disproportionation reaction generates the metal of above-mentioned a kind of rare earth element and the operation of trichloride;
Step D ': by making said mixture be separated into the distillation condensation product of trichloride of above-mentioned a kind of rare earth element and the operation of residue to carrying out vacuum distilling in system;
The metal that above-mentioned metal M can coexist for metal M and the oxide compound of metal M under the environment of above-mentioned chemistry balance state and the muriatic three-phase of metal M,
Afore mentioned rules amount is than the amount of the muriatic chemical equivalent surplus with respect to above-mentioned multiple rare earth element,
Above-mentioned multiple rare earth element is dysprosium and neodymium, and above-mentioned a kind of rare earth element is dysprosium.
8. the separation and recovery method of rare earth element claimed in claim 7, is characterized in that, carries out above-mentioned operation C ' and above-mentioned step D simultaneously '.
9. the separation and recovery method of the rare earth element described in claim 7 or 8, is characterized in that, the oxygen gesture of the oxidizing reaction of above-mentioned metal M is lower than the oxygen gesture of above-mentioned multiple rare earth element.
10. the separation and recovery method of the rare earth element described in claim 7 or 8, is characterized in that, the chlorine gesture of the chlorination reaction of above-mentioned metal M is lower than the chlorine gesture of above-mentioned a kind of rare earth element, and higher than the chlorine gesture of other the a kind of rare earth element in above-mentioned multiple rare earth element.
The separation and recovery method of the rare earth element described in 11. claims 7 or 8, is characterized in that, above-mentioned metal M is at least a kind that is selected from thulium, terbium, erbium, holmium, yttrium.
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| US9376736B2 (en) | 2012-01-06 | 2016-06-28 | Hitachi Metals, Ltd. | Method for separating and recovering rare-earth elements |
| JP6179699B1 (en) * | 2016-03-28 | 2017-08-16 | 日立金属株式会社 | Method for separating both from an alloy containing Dy and Tb |
| CN109154034A (en) * | 2016-03-28 | 2019-01-04 | 日立金属株式会社 | The method for separating the two from the alloy containing Dy and Tb |
| CN109112317B (en) * | 2018-10-16 | 2020-02-18 | 内蒙古科技大学 | Reduction-oxidation separation of rare earth mixture La2O3-RE2O3Method (2) |
| CN110538478A (en) * | 2018-10-29 | 2019-12-06 | 天津包钢稀土研究院有限责任公司 | High-quality anhydrous rare earth halide purification device |
| CN111218559A (en) * | 2018-11-26 | 2020-06-02 | 广东先导稀材股份有限公司 | Melt evaporation device and method |
| CN111321296A (en) * | 2018-12-13 | 2020-06-23 | 有研工程技术研究院有限公司 | Method for recovering vanadium and nickel from waste petroleum catalyst |
| CN114752788A (en) * | 2022-04-24 | 2022-07-15 | 华卫国 | Roasting method of rare earth ore concentrate added with active agent |
| CN115627372B (en) * | 2022-09-30 | 2023-12-19 | 中稀(广西)金源稀土新材料有限公司 | Rare earth precipitation method |
| CN115821075A (en) * | 2022-11-23 | 2023-03-21 | 昆明理工大学 | Method for recovering rare earth metal in samarium cobalt permanent magnet waste |
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| CN1004427B (en) * | 1984-10-05 | 1989-06-07 | 通用汽车公司 | Metallothermic reduction of rare earth oxides |
| JPS63176440A (en) * | 1987-01-16 | 1988-07-20 | Mitsubishi Kasei Corp | Heating furnace |
| JPS63282218A (en) * | 1987-05-15 | 1988-11-18 | Nippon Mining Co Ltd | Manufacture of high-purity rare-earth metal |
| JPH04176887A (en) * | 1990-11-13 | 1992-06-24 | Nikko Kyodo Co Ltd | Apparatus for producing high-purity y |
| JPH0551208A (en) * | 1991-08-22 | 1993-03-02 | Kinya Adachi | Individual separation of rare-earth elements utilizing formation of gaseous complex |
| US5728355A (en) * | 1995-09-27 | 1998-03-17 | Santoku Metal Industry Co., Ltd. | Method for recovering reusable rare earth compounds |
| JP2001303149A (en) * | 2000-04-24 | 2001-10-31 | Tetsuya Uda | Method for separating rare earth element and composition for separating rare earth element |
| JP2003073754A (en) * | 2001-08-30 | 2003-03-12 | Tetsuya Uda | Method for recovering rare-earth element |
| CN101307384A (en) * | 2007-05-14 | 2008-11-19 | 北京有色金属研究总院 | Process for preparing high pure rare earth metals by layered distillation method and device |
| WO2009119720A1 (en) * | 2008-03-26 | 2009-10-01 | 財団法人生産技術研究奨励会 | Method and apparatus for collection of rare earth element |
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