CN103194626A - Separating and recycling method of rare earth elements - Google Patents
Separating and recycling method of rare earth elements Download PDFInfo
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- CN103194626A CN103194626A CN201310008678XA CN201310008678A CN103194626A CN 103194626 A CN103194626 A CN 103194626A CN 201310008678X A CN201310008678X A CN 201310008678XA CN 201310008678 A CN201310008678 A CN 201310008678A CN 103194626 A CN103194626 A CN 103194626A
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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 from the composition that contains multiple rare earth element.
Background technology
In recent years, recognize the importance of the environment of preserving our planet constantly, with concentrating one's energy exploitation can inferior limit ground use 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 efficient rotating machine (motor or generator), is extensive use of the magnet (that is rare earth element magnet) that contains rare earth element in this efficient rotating machine.For example, the rare earth element magnet that in the rotating machine of the CD-ROM drive motor of hybrid vehicle and the compressor of air conditioning machinery etc., uses, even in hot environment (for example require, about 200 ℃) in also have high coercive force, this class magnet is except containing neodymium, iron, boron, the heavy rare earth element (for example, dysprosium) that also contains high price in a large number.Rare earth element magnet has become indispensable material now, expects that demand also can enlarge from now on.
On the other hand, rare earth element becomes independent element owing to be 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 keep magnet can reduce consumption again.But, for making these technical applicationizations, also need the long period.Therefore, be important techniques from rejected material (for example, the rare earth element magnet in the discarded motor and the cutting powder (disintegrating slag) that in the production process of rare earth element magnet, produces etc.) middle Separation and Recovery rare earth element and with its recycle.
For example, patent documentation 1 discloses the separation method of rare earth element, it is characterized in that, to make a kind of containing be that the average valence mumber of the rare earth class ion more than 2 kinds is that the mishmetal class of 3 valencys of the divalent below 3 more than 2 is halid and be not with the aqueous solution or the mixture that exists with the state that is dissolved in the organic solvent by the rare earth element in the mixture that contains multiple rare earth element or its compound being carried out halogenation, then, utilize the different of divalent rare earth class halogenide and the halid character of 3 valency rare earth class, above-mentioned multiple rare earth element is separated at least 2 groups.According to patent documentation 1, can improve the separation factor between rare earth element by leaps and bounds, compare with method in the past, can be separated from each other effectively.And then, when from rare earth class concentrate such as phosphoric acid salt, separating, acid dissolving, filtration, the contamination precipitation that can be omitted in requisite concentrate in the wet method in the past removed, concentrates, neutralized, dry such operation, thereby can reduce separation costs significantly.
In addition, the recovery method of rare earth element is disclosed in the patent documentation 2, this method is to reclaim the method for rare earth element from the material that contains rare earth element and iron family element ting, it is characterized in that, has 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 the above-mentioned substance carry out chlorination reaction, come like this from above-mentioned substance, optionally to reclaim as muriatic rare earth element.According to patent documentation 2, can be from the chip of rare earth element magnet or disintegrating slag etc. contain the material of rare earth element and iron family element ting, particularly in the waste, only the rare earth class composition of extraction, separating high-purity can be established the method for rare earth element magnet recycle more cheaply thus.
The prior art document
Patent documentation
[patent documentation 1] spy opens the 2001-303149 communique
[patent documentation 2] spy opens the 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 enlarge.On the other hand, becoming rare earth element local ground such as the neodymium of rare earth element magnet raw material and dysprosium is present on the earth, consider that from the viewpoint of guaranteeing the stable supply of raw material and the viewpoint of efficent use of resources the technology of Separation and Recovery rare earth element and in addition recycle becomes even more important than in the past.
Therefore, the objective 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.
Be used 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 this method wherein, has following operation for separating of reclaiming multiple rare earth element:
Add the operation (operation A) of the metal M of specified amount in the halid mixture that contains above-mentioned multiple rare earth element; The operation (process B) of the halid chemistry balance state by the mixture that has added above-mentioned metal M under atmospheric pressure being heated reach the divalence halogenide that generates above-mentioned multiple rare earth element and above-mentioned metal M; By to carrying out vacuum exhaust in the system that reaches 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 owing to disproportionation reaction generates of a kind of rare earth element in the 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 the system; Wherein, the metal that above-mentioned metal M can coexist for the halid three-phase of the oxide compound of metal M and metal M under the environment of above-mentioned chemistry balance state and metal M, afore mentioned rules amount are than the amount with respect to the halid chemical equivalent surplus of 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 this method wherein, has following operation for separating of reclaiming multiple rare earth element:
By using the compound chlorination that iron(ic) chloride will contain above-mentioned multiple rare earth element, iron, boron to generate the operation (operation E) that contains muriatic mixture; By distilling the operation (operation F) of from contain above-mentioned muriatic mixture, separating the muriatic mixture of above-mentioned multiple rare earth element to containing above-mentioned muriatic mixture; Add the operation (operation A ') of the metal M of specified amount in the muriatic mixture of above-mentioned multiple rare earth element; The mixture that has added above-mentioned metal M by heating under atmospheric pressure reaches the operation (process B ') of the muriatic chemistry balance state of the dichloride that generates above-mentioned multiple rare earth element and above-mentioned metal M; By making the dichloride of a kind of rare earth element in the above-mentioned multiple rare earth element because disproportionation reaction generates the operation (operation C ') of metal and the trichloride of above-mentioned a kind of rare earth element to carrying out vacuum exhaust in the system that reaches above-mentioned chemistry balance state; And by making said mixture be separated into the operation (step D ') of the distillation condensation product of trichloride and the residue of above-mentioned a kind of rare earth element to carrying out vacuum distilling in the system; Wherein, the metal that above-mentioned metal M can coexist for the muriatic three-phase of the oxide compound of metal M and metal M under the environment of above-mentioned chemistry balance state and metal M, afore mentioned rules amount are than the amount with respect to the muriatic chemical equivalent surplus of above-mentioned multiple rare earth element.
In addition, the present invention can resemble and be improved and change following in the separation and recovery method (I) of above-mentioned rare earth element, (II).
(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 than the halogen dividing potential drop height of other the a kind of rare earth element in the above-mentioned multiple rare earth element.
(v) above-mentioned metal M is at least a kind that is selected from thulium, terbium, erbium, holmium, the 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, the samarium.
(viii) above-mentioned halogen is chlorine.
The effect of invention
According to the present invention, can provide easier and can be with the method for high yield Separation and Recovery rare earth element than conventional art.Its result can regenerate the rare earth element of separating with low cost separation of rare earth elements (for example, neodymium, dysprosium etc.) accurately from the waste (for example, waste product, substandard products, disintegrating slag etc.) of rare earth element magnet as raw material.Can help efficent use of resources thus and guarantee the stable of rare earth class raw material.
Description of drawings
Fig. 1 is the schematic cross-section that is illustrated in the state of an example after being next to separation circuit of the water distilling apparatus that uses in the separation circuit of rare earth element and other elements.
Fig. 2 is the graphic representation that the quality of carrying out residue in the fractionation by distillation operation crucible afterwards among the embodiment 1 and the mass distribution that is attached to the condensation phase on the separate type inwall are shown.
Fig. 3 A is the graph that the compositional analysis result of the condensation phase of utilizing residue (except the Y fragment) in the crucible that XRF obtains and separate type inwall 8e～8g among the embodiment 1 is shown.
Fig. 3 B be the Dy that is calculated by formula (1) and formula (2) that Fig. 3 A is shown than and the graph of Nd ratio.
Fig. 4 is the XRD curve of the Powdered residue in the crucible among the embodiment 1.
Fig. 5 is for being attached to the XRD curve of the melts shape residue of crucible bottom among the embodiment 1.
Fig. 6 is the XRD curve of the condensation phase of separate type inwall 8g among the 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, the limit illustrates in greater detail embodiment of the present invention with reference to the accompanying drawing limit.Illustrated that the embodiment that the present invention is not limited to enumerate can be carried out appropriate combination or improvement herein in the scope that does not change main idea.
[the 1st embodiment of the present invention]
(basic step and principle thereof that rare earth element separates)
Basic step and principle thereof for the separation method of the rare earth element among 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 separating when mixture that uses Neodymium trichloride and Dysprosium trichloride is described, but the present invention is not limited to this.
At first, to neodymium trichloride (NdCl
3) and dysprosium trichloride (DyCl
3) mixture in add, mix the metallic yttrium (Y) as metal M.Shape for the metallic yttrium that adds does not have particular determination, has granular, bulk or the shred bigger than rare earth class muriate in order to separate easily in subsequent handling, to be preferably.
Secondly, this mixture under atmospheric pressure is heated to 700～900 ℃.So just make that the muriatic mixture of rare earth class that has added metallic yttrium reaches the chemistry balance state shown in following chemical formula (1), the 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)
Judge that according to chemical formula (1), (2) metallic yttrium works as reductive agent.In addition, by excessively adding metallic yttrium, chemical reaction is further carried out to the right.In other words, for the generation that makes the rare earth class dichloride is carried out, in the muriatic mixture to rare earth class, add, during the hybrid metal yttrium, preferably according to respect to the muriatic chemical equivalent of the rare earth class in the mixture be superfluous amount interpolation 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, and rotary pump reaches the medium vacuum degree as long as for example use.Under reduced pressure atmosphere, by the dichloride dysprosium (DyCl that generates in the chemical formula (2)
2) become unstable, cause the disproportionation reaction shown in the following chemical formula (3), resolve into metal dysprosium (Dy) and dysprosium trichloride (DyCl
3).Illustrated, for dichloride neodymium (NdCl
2), the degree of disproportionation reaction is very little.
[changing 3]
3DyCl
2=Dy+2DyCl
3Chemical formula (3)
Secondly, with above-mentioned system internal heating and remain on 1000～1100 ℃, carry out vacuum distilling.Herein, the NdCl that generates in the chemical formula (1)
2Steam force down the yttrium trichloride (YCl that generates in the chemical formula (1), (2)
3) and the middle DyCl that generates of chemical formula (3)
3The vapour pressure height, 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 that generates of chemical formula (3) of excess quantity.The above-mentioned operation that vacuum exhaust in the system is caused disproportionation reaction with vacuum distilling in the system can be carried out continuously with this operation that is separated into distillation condensation product and residue, also can carry out simultaneously.Consider from the viewpoint of simplifying step, preferably carry out two operations simultaneously.Illustrated that the implication of carrying out comprises heating (intensification) and vacuum exhaust are begun simultaneously simultaneously.
As mentioned above, because the Y metal adds with big granular or block or shred, therefore, can easily from residue, separate.Because the Dy metal that generates in the chemical formula (3) also becomes bulk, therefore also can easily separate.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 the rare earth class muriate is generally Powdered or solidifies is even the latter also can pulverize with simple impact.Therefore, they can easily carry out mechanical separation, can be from residue Separation and Recovery Y metal, Dy metal and NdCl
2In addition, can also from the distillation condensation product, reclaim DyCl
3And YCl
3DyCl is described
3And YCl
3Can adopt method (for example, solvent extration) in the past to separate.
(the selection policy of the metal M of interpolation)
Secondly, describe for the selection policy of adding the metal M in the muriatic mixture of rare earth class to.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.Oxygen partial pressure (pO in the table is described
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 the 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 the table, [s, l] refers to solid phase or liquid phase, and [g] refers to gas phase.
The metal M of adding preferably also has conduct for the effect of the reductor of the rare earth element generation oxidation that prevents from separating except the above-mentioned effect as reductive agent.In other words, a kind of metal that oxidation takes place under the condition of the oxygen gesture lower than the rare earth element that will separate preferably.If according to this viewpoint table 1, as the metal that oxidation takes place, can enumerate Tb (terbium), Tm (thulium), Ho (holmium), Ca (calcium), Er (erbium), Sc (scandium), Y (yttrium) under the condition of the oxygen gesture lower than Dy (dysprosium).By adding the metal than the easier oxidation of rare earth element that will separate, even residual in the system of separation of rare earth elements/sneak under the situation of oxygen composition, also can suppress the oxidation of the rare earth element that will separate.
On the other hand, when considering from chlorination reaction, the chlorine gesture of the chlorination reaction of the metal M of interpolation, preferably than the chlorination gesture height that is transformed into metal by the multiple rare earth element that will separate, and, lower by the gesture that trichloride is reduced to dichloride than multiple rare earth element.If see table 2 according to this viewpoint, as at the metal that chlorination all takes place than Nd, Dy 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.Illustrated that 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 goes for the mixture of mixture, samarium trichloride and the Dysprosium trichloride of Gadolinium trichloride and Dysprosium trichloride.In addition, above put down in writing 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 as the rare earth element magnet (compounds of rare earth element and other elements) of actual parent material the method for Separation and Recovery rare earth element describe.
(separation circuits of rare earth element and other elements)
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 at first is described.Illustrated, often contain the praseodymium as another kind of element in the rare earth element in the actual rare earth element magnet disintegrating slag, but because physics, the chemical property of neodymium and praseodymium are closely similar, therefore, think that herein praseodymium is accompanied by neodymium and exists together.
The separation circuit of rare earth element and other elements (step), basic identical, specific as follows with patent documentation 2 disclosed operations.As being used for the rare earth element magnet that element separates, preferably use waste as described above (for example, waste product, substandard products, disintegrating slag etc.), consider from the viewpoint of Separation and Recovery efficient (chemical reaction efficiency), be preferably Powdered.Below describe with the example that is separated into from the disintegrating slag powder of rare earth element magnet.
Fig. 1 is the schematic cross-section that is illustrated in the state of an example after being next to separation circuit of the water distilling apparatus that uses 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 vertical electric furnaces of cylinder that periphery at vertical heater core barrel 4 has up and down 2 sections well heater (epimere well heater 1, hypomere well heater 2, thermopair 3,3 ').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.Illustrated that Fig. 1 shows the stove core barrel 4 at the end, but also can be the structure with the lower cover sealing.In addition, the place that arranges for venting port 5 and gas introduction port 6 does not have particular determination yet.
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 inboard of the hypomere (separate type inwall 8a) of inwall 8 in addition.
At first, with use drying machine etc. dry the fragmentation of disintegrating slag powder.Then, with breaked disintegrating slag powder, powdered graphite with than the iron protochloride (FeCl of the amount of chemical equivalent surplus
2) mix, be filled in the crucible 9.Crucible 9 is arranged on the inboard of the hypomere (separate type inwall 8a) of inwall 8, is assembled into water distilling apparatus 20.With the inner vacuum exhaust of stove core barrel 4, after rare gas element (for example, argon gas) displacement, Yi Bian feed rare gas element, Yi Bian under atmospheric pressure implement 700～900 ℃ heat treated.The result of this heat treated, the mixing material generation chemical reaction in the crucible 9 obtains the mixture (generation contains the operation of muriatic mixture) of rare earth class muriate, unreacted iron protochloride, iron or iron family element ting alloy in crucible 9.Illustrated that the oxygen composition that is fixed in the rare earth element magnet disintegrating slag powder is gasified by powdered graphite (carbon component), the gas of generation is discharged to outside the system by the rare gas element that flows.
Secondly, for the mixture of the rare earth class muriate that obtains, iron protochloride, iron or iron family element ting alloy, with decompressions such as rotary pumps, carry out fractionation by distillation Yi Bian be heated to 900～1100 ℃ by on one side.At this moment, preferably the temperature with epimere well heater 1 remains on 400～500 ℃, and the temperature of hypomere well heater 2 is remained on 700～1100 ℃.The result of this fractionation by distillation, inwall 8 in epimere well heater 1 zone (be the condensation phase 10 of formation iron protochloride of separate type inwall 8g～8h) among Fig. 1, (be the muriatic condensation phase 11 of formation rare earth class of separate type inwall 8d～8e) among Fig. 1, residual in crucible 9 have as the iron of residue and the alloy of iron family element ting (operation of separating the muriatic mixture of multiple rare earth element) inwall 8 in hypomere well heater 2 zone.If reclaim the condensation phase 11 of separate type inwall 8d～8e, then obtain the muriatic mixture of multiple rare earth class.Under the situation of this example, obtain the mixture of Neodymium trichloride and Dysprosium trichloride particularly.
(separation circuit of multiple rare earth element)
Secondly, the operation that is separated from each other rare earth element from the muriatic mixture of multiple rare earth class that reclaims is described.Also can use water distilling apparatus shown in Figure 1 20 in this operation.The muriatic mixture of multiple rare earth class that reclaims 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.At this moment, the rare earth class muriate is imbued with water absorbability, therefore, for fear of excessive moisture absorption, wishes weighing, mixes, is filled in the dry environment and carry out fast in (for example, kiln, glove box etc.).In addition, in order to remove excessive oxygen in the system that chemical reaction takes place as far as possible, also can add powdered graphite.
The crucible 9 of having filled is arranged on the inboard of the hypomere (separate type inwall 8a) of inwall 8, is assembled into water distilling apparatus 20.With the inner vacuum exhaust of stove core barrel 4, behind inert gas replacements such as argon gas, under atmospheric pressure implement 700～900 ℃, 6～24 hours heat treated while flow into rare gas element.The result of this heat treated, the mixing material generation chemical reaction in the crucible 9 reaches the chemistry balance state shown in chemical formula (1), (2) (making reaction reach the operation of chemistry balance state).Being illustrated, as mentioned above, is the metallic yttrium of excess quantity owing to mixed with respect to the muriatic chemical equivalent of rare earth class, therefore in fact obtains the dichloride neodymium (NdCl as resultant in crucible 9
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. with vacuum exhaust in the system.Its result in the disproportionation reaction that has caused in the dichloride dysprosium shown in chemical formula (3), decomposes generation metal dysprosium (Dy) and dysprosium trichloride (DyCl
3) (operation of disproportionation reaction takes place).
Then, while by continuing that fractionation by distillation is carried out in the further heating of vacuum exhaust in the system.At this moment, preferably the temperature with epimere well heater 1 remains on 400～500 ℃, and the temperature of hypomere well heater 2 is remained on 700～1100 ℃.By this vacuum distilling, make the high DyCl of vapour pressure
3And YCl
3Distillation, (for example, separate type inwall 8g～8h) goes up formation condensation phase 10 to the inwall 8 of (being low-temperature region in) in epimere well heater 1 zone.Simultaneously, because the DyCl in the crucible 9
3Reduce, the disproportionation reaction of chemical formula (3) is further carried out to the right.In crucible 9, the NdCl that generates in unreacted Y metal and the chemical formula (1)
2With the Dy metal that generates in the chemical formula (3) as residue and residual (carrying out the operation that solid and gas separates by vacuum distilling).
After the fractionation by distillation, water distilling apparatus 20 is cooled to room temperature.About the residue in the crucible 9, as mentioned above, because Y metal, Dy metal and NdCl
2Shape and vary in size, therefore, can be with they Separation and Recovery (utilizing shape or size to carry out solid operation of separating) mechanically.By the NdCl to separating
2In atmosphere, under the condition about 900 ℃, carry out roasting, can reclaim Neodymium trioxide.
On the other hand, at first the condensation of reclaiming 10 is put in the pure water and stirred mutually, prepare the aqueous solution of Dysprosium trichloride and Yttrium trichloride.After this aqueous solution carried out pH regulator, by adding precipitation agent (for example, volatile salt ((NH
4)
2CO
3), bicarbonate of ammonia (NH
4HCO
3), yellow soda ash (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 filtration, drying, by in atmosphere, under the condition about 900 ℃, carrying out roasting, can reclaim the mixture of dysprosium oxide and yttrium oxide.
In addition, omit detailed explanation, dysprosium oxide and yttrium oxide can adopt method (for example, solvent extration) in the past to separate after acidleach goes out.After the dysprosium salt and yttrium salt drying separated, by in atmosphere, under the condition about 900 ℃, carrying out roasting, can reclaim dysprosium oxide and yttrium oxide respectively.
(being reduced to the operation of rare earth metal)
By respectively Neodymium trioxide, dysprosium oxide and the yttrium oxide of above-mentioned recovery being used the fusion electrolysis of fluoride bath etc., it 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, be described more specifically the present invention based on embodiment, 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, about 5 * about 5 * about 2mm
3, purity 99.9%).Illustrated that because oxidized easily in the oxygen source of metallic yttrium in atmosphere, therefore, the metallic yttrium that preparation is preserved is removed the back with oil content and used when facing use in oil.
The NdCl of weighing 2.5g in kiln
3The DyCl of powder, 2.5g
3The Y fragment of powder and 1.16g is put in molybdenum (Mo) crucible 9 processed and is mixed.Use water distilling apparatus 20 shown in Figure 1, the crucible 9 that has added mixing material is set, assembling inwall 8 in the inboard of the hypomere (separate type inwall 8a) of inwall 8.Inwall 8 is the cylinder multi-stage type, has the structure that is separated into separate type inwall 8a～8m (graphite system, internal diameter 50mm * high 50mm) separately.Thus, reclaim the distillation condensation and become mutually easily, in addition, can investigate the distribution of distillation condensation phase.Illustrated, Mo crucible 9 processed and graphite separate type inwall processed 8a～8m are implemented 3 hours roastings in advance in a vacuum under 800 ℃, carried out quality determination then.
After assembling inwall 8, with 7 sealings of stove core barrel 4 usefulness upper caps, will reduce pressure in the stove core barrel 4 by venting port 5 usefulness rotary pumps.Then, more than 12 hours, after carrying out vacuum-drying in mixing material and the stove core barrel 4, import argon gas from gas introduction port 6 300 ℃ of heating, making becomes normal atmosphere in the system.In order to remove residual oxygen composition in stove core barrel 4 and the 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, be 400 ℃ Yi Bian make the temperature of the low-temp. portion epimere well heater 1 of epimere, the temperature that makes hypomere well heater 2 is 800 ℃, implements 6 hours heat treated, makes to reach the chemistry balance state shown in chemical formula (1), (2).Then, under the state of the temperature in maintenance system,, make the disproportionation reaction shown in the chemical formula (3) takes place vacuum exhaust in the system with rotary pump.
Then, continue system in vacuum exhaust on one side, making the temperature of the low-temp. portion epimere well heater 1 of epimere on one side is 500 ℃, the temperature that makes hypomere well heater 2 is 1000 ℃, carries out 3 hours fractionation by distillation.By this vacuum distilling, the inwall 8 in low-temperature region forms condensation phase 10.After the distillation, under the state of vacuum exhaust, be cooled to room temperature.
After the cooling, to the sample of vacuum distilling (condensation mutually 10 and crucible 9 in residue) carry out various evaluations.At first, in order to investigate condensation 10 distribution mutually, by the difference of quality before and after experiment of weighing separate type inwall 8a～8m, measure the quality together with the condensation phase 10 of separate type inwall.Also measure the quality of residue in the crucible 9.In addition, residue in the crucible 9 10 is taken a sample mutually with the condensation on being attached to the 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.
Calculate separation rate and the yield of Nd and Dy from the residue obtained with XRF and aggegation composition mutually.The Dy concentration that to obtain with XRF and be shown [Dy] according to the Dy scale that the Mass Calculation of residue or aggegation phase goes out, the Nd concentration that to obtain with XRF and be shown [Nd] according to the Nd scale that the Mass Calculation of residue or aggegation phase goes out is obtained Dy than (R from following formula (1), formula (2) respectively equally
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 with mixing are expressed as [Dy] respectively
0[Nd]
0, obtained by following formula (3), formula (4).
[several 3]
[several 4]
Fig. 2 be quality that residue in the crucible that carries out among the embodiment 1 after the fractionation by distillation operation is shown be attached to the separate type inwall on the graphic representation of condensation mass distribution mutually.As shown in Figure 2, confirm to have approximately in the crucible 9 residue of 3.5g, confirm that the quality on separate type inwall 8e～8g has remarkable increase (about 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 keeps this chip shape.Residual Y fragment can easily take out.This residual Y fragment of weighing is about 0.7g.That is, can think that add in the Y composition that mixes, about 0.7g is as the Y metal residual, about 0.4g is chlorinated and is present in the system.
Fig. 3 A is for illustrating condensation phase for residue in the crucible among the embodiment 1 (removing the Y fragment) and separate type inwall 8e～8g, utilizes the compositional analysis result's that XRF obtains graph.Fig. 3 B is for illustrating the Dy that calculates according to Fig. 3 A with according to formula (1) and formula (2) and compare and the graph of Nd ratio.
As shown in Figure 3A, the residue (removing the Y fragment) in the crucible 9 mainly is made of Cl, Nd, Dy, detects some Y in addition.Specifically, Cl is that 24.3%, Nd is that 41.2%, Dy is 30.4%.Illustrated that Dy metal and Nd muriate be owing 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%.
Shown in Fig. 3 B, about the ratio of the Dy in the condensation mutually, be 75.5% at separate type inwall 8e, be 73.9% at separate type inwall 8f, 8g is 89.0% at the separate type inwall, obtains high value.Because the Dy when making mixing material is 50.0% than (initial stage Dy ratio), therefore can judge, can carry out good separation according to separating technology of the present invention.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 the crucible among the embodiment 1.As shown in Figure 4, the Powdered residue in the crucible 9 mainly detects NdCl
2The peak, detect YOCl, Y in addition
3O
4Cl (Y
2O
3YOCl), the peak of DyOCl.Can think that the oxychlorination thing is owing to residual in the system/oxygen composition of sneaking into generates.
Fig. 5 is for being attached to the XRD curve of the melts shape residue of crucible bottom among the embodiment 1.As shown in Figure 5, the melts shape residue for the bottom that is attached to Mo crucible 9 processed except detecting the Mo metal that is caused by crucible, also detects Dy metal and YOCl.
Fig. 6 is the XRD curve of the condensation phase of separate type inwall 8g among the embodiment 1.As shown in Figure 6, mainly detect DyCl
3And YCl
3, also detect some NdCl
3
From above mensuration and analytical results, we can say in chemical reaction and the sepn process shown in the 1st embodiment of the present invention to be confirmed.
[embodiment 2]
Research is from containing the rare earth element magnet (RE of neodymium, dysprosium, praseodymium, iron, boron
2Fe
14B, RE: separate, reclaim rare earth element in waste material rare earth element).The quality group of the rare earth element magnet that uses becomes 61.2%Fe-23.1%Nd-3.5%Dy-2.0%Pr-1.0%B.Should useless magnet be after in manufacturing process, implementing nickel plating, become substandard products owing to crackle or defective etc. take place.
At first, by use electric furnace in nitrogen atmosphere in 800 ℃ of heating, the coarse reduction of the magnet that gives up.As mentioned above, though this useless magnet has been implemented nickel plating, plated nickel film can utilize the hydrogen pulverizing process to peel off, and the plated film after peeling off can adopt sieve method to separate with ferromagnetic powder.
With the ferromagnetic powder that obtains and FeCl as the chlorine source
2Powder mixes joins in the iron crucible 9 then, is configured in the water distilling apparatus shown in Figure 1 20.After using the rotary pump exhaust in the chromium ferronickel heat-resistant and etching-resistant alloy stove core barrel 4 processed, use argon replaces, making the temperature of hypomere well heater 2 is 800 ℃, 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 the rotary pump exhaust, Yi Bian carry out vacuum distilling in 3 hours.After the vacuum distilling, in making stove core barrel 4, remain under the state of vacuum stove is cooled off.
After stove is cooled to room temperature, when observing inwall 8 (when the condensation of separate type inwall 8a～8m) is adhered to situation mutually, zone at 500～800 ℃, lilac is Powdered, the material generation condensation of shallow green powder shape, white powder, in the temperature province that is lower than 500 ℃, the material generation condensation of orange powder shape.When these condensed materials during in general indoor placement, observe the situation of moisture absorption at short notice.On the other hand, when carrying out semi-quantitative analysis when these condensed materials of quick recovery and with the XRF device, confirmed that the condensed material in 500～800 ℃ of zones mainly comprises the muriate of rare earth element (neodymium, praseodymium, dysprosium), its containing ratio is 98%.
For the muriatic mixture of the 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 (15)
1. the separation and recovery method of rare earth element, this method is characterized in that for separating of reclaiming multiple rare earth element,
This method has following operation:
Add the operation (operation A) of the metal M of specified amount in the halid mixture that contains above-mentioned multiple rare earth element;
The operation (process B) of the halid chemistry balance state by the mixture that has added above-mentioned metal M under atmospheric pressure being heated reach the divalence halogenide that generates above-mentioned multiple rare earth element and above-mentioned metal M;
By to carrying out vacuum exhaust in the system that reaches 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 owing to disproportionation reaction generates of a kind of rare earth element in the 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 the system;
The metal that above-mentioned metal M can coexist for the halid three-phase of the oxide compound of metal M and metal M under the environment of above-mentioned chemistry balance state and metal M,
The afore mentioned rules amount is than the amount with respect to the halid chemical equivalent surplus of above-mentioned multiple rare earth element.
2. the separation and recovery method of the described rare earth element of 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 claim 1 or the described rare earth element of claim 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 each described rare earth element of claim 1～claim 3, it 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 than the halogen gesture height of other the a kind of rare earth element in the above-mentioned multiple rare earth element.
5. the separation and recovery method of each described rare earth element of claim 1～claim 4 is characterized in that, above-mentioned metal M is at least a kind that is selected from thulium, terbium, erbium, holmium, the yttrium.
6. the separation and recovery method of each described rare earth element of claim 1～claim 5 is characterized in that, above-mentioned halogen is chlorine.
7. the separation and recovery method of each described rare earth element of claim 1～claim 6 is characterized in that, above-mentioned a kind of rare earth element is dysprosium.
8. the separation and recovery method of the described rare earth element of claim 7 is characterized in that, above-mentioned multiple rare earth element also contains at least a kind that is selected from neodymium, gadolinium, the samarium.
9. the separation and recovery method of rare earth element, this method is characterized in that for separating of reclaiming multiple rare earth element this method has following operation:
By using the compound chlorination that iron(ic) chloride will contain above-mentioned multiple rare earth element, iron, boron to generate the operation (operation E) that contains muriatic mixture;
By distilling the operation (operation F) of from contain above-mentioned muriatic mixture, separating the muriatic mixture of above-mentioned multiple rare earth element to containing above-mentioned muriatic mixture;
Add the operation (operation A ') of the metal M of specified amount in the muriatic mixture of above-mentioned multiple rare earth element;
The mixture that has added above-mentioned metal M by heating under atmospheric pressure reaches the operation (process B ') of the muriatic chemistry balance state of the dichloride that generates above-mentioned multiple rare earth element and above-mentioned metal M;
By making the dichloride of a kind of rare earth element in the above-mentioned multiple rare earth element because disproportionation reaction generates the operation (operation C ') of metal and the trichloride of above-mentioned a kind of rare earth element to carrying out vacuum exhaust in the system that reaches above-mentioned chemistry balance state;
By making said mixture be separated into the operation (step D ') of the distillation condensation product of trichloride and the residue of above-mentioned a kind of rare earth element to carrying out vacuum distilling in the system;
The metal that above-mentioned metal M can coexist for the muriatic three-phase of the oxide compound of metal M and metal M under the environment of above-mentioned chemistry balance state and metal M,
The afore mentioned rules amount is than the amount with respect to the muriatic chemical equivalent surplus of above-mentioned multiple rare earth element.
10. the separation and recovery method of the described rare earth element of claim 9 is characterized in that, carries out above-mentioned operation C ' and above-mentioned step D simultaneously '.
11. the separation and recovery method of claim 9 or the described rare earth element of claim 10 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.
12. the separation and recovery method of each described rare earth element of claim 9～claim 11, it 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 than the chlorine gesture height of other the a kind of rare earth element in the above-mentioned multiple rare earth element.
13. the separation and recovery method of each described rare earth element of claim 9～claim 12 is characterized in that, above-mentioned metal M is at least a kind that is selected from thulium, terbium, erbium, holmium, the yttrium.
14. the separation and recovery method of each described rare earth element of claim 9～claim 13 is characterized in that, above-mentioned a kind of rare earth element is dysprosium.
15. the separation and recovery method of the described rare earth element of claim 14 is characterized in that, above-mentioned multiple rare earth element also contains at least a kind that is selected from neodymium, gadolinium, the samarium.
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| CN109112317A (en) * | 2018-10-16 | 2019-01-01 | 内蒙古科技大学 | The method of redox rare-earth separating mixture La2O3-Re2O3 |
| 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 |
| 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 |
| 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 |
| 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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| WO2013103099A1 (en) | 2012-01-06 | 2013-07-11 | 日立金属株式会社 | Method for separating and recovering rare-earth element |
| 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 |
| 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 |
| CN114752788A (en) * | 2022-04-24 | 2022-07-15 | 华卫国 | Roasting method of rare earth ore concentrate added with active agent |
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| 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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|---|---|
| JP2013139617A (en) | 2013-07-18 |
| JP5792079B2 (en) | 2015-10-07 |
| CN103194626B (en) | 2014-11-26 |
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