CN107699715A - The method of extracting and enriching recovering rare earth from low concentration of rare earth solution - Google Patents
The method of extracting and enriching recovering rare earth from low concentration of rare earth solution Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B59/00—Obtaining rare earth metals
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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Abstract
This application provides a kind of method of extracting and enriching recovering rare earth in solution from low concentration of rare earth.This method includes：Centrifugical extraction is carried out to low concentration of rare earth solution using non-saponified organic extractant, obtains supported rare earth organic phase and raffinate；Centrifugation back extraction is carried out to load organic phases using inorganic acid, obtains rare-earth enrichment liquid.Wherein low concentration of rare earth solution refers to count earth solution of the concentration as 0.05~8g/L using REO.According to the height of actual earth solution concentration, Centrifugical extraction is coupled once or twice, light rare earth and middle heavy rare earth can be enriched in supported rare earth organic phase by all rare earths or respectively, then centrifugation back extraction is carried out by inorganic acid, you can obtain including all rare earths or mainly the rare-earth enrichment liquid of light rare earth or middle heavy rare earth.The rare-earth enrichment method is simple to operate, green, and rare earth yield is high, and cost recovery is low.
Description
Technical field
The application is related to field of hydrometallurgy, and in particular to one kind, extracting and enriching returns from low concentration of rare earth solution
The method for receiving rare earth.
Background technology
Ion adsorption type rare earth ore (abbreviation ion type rareearth ore) is the rare precious resources rich in middle heavy rare earth in the world,
Contain lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium more than ten kinds of rare earth element (lanthanum, cerium, praseodymium, neodymium quilt
Referred to as " light rare earth ", samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium are referred to as " middle heavy rare earth "), wherein, middle heavy rare earth
Content be more than 40%.Rare earth element in ion adsorption type rare earth ore is mainly with the shape of hydrated ion or hydroxyl hydrated ion
Formula is adsorbed on clay mineral, and rare earth grade is (in terms of REO, similarly hereinafter) very low, and generally 0.03~0.1%, it can not use conventional
Beneficiation method is enriched with rare earth, at present mainly using ammonium sulfate leaching recovery in industrial production.
It is the low dense of 0.3~2g/L that ion type rareearth ore, which uses ammonium sulfate to leach to obtain rare earth concentration (in terms of REO, similarly hereinafter),
Earth solution is spent, after first removing impurity, the separation of solid and liquid such as aluminium, iron using ammonium hydrogen carbonate, leachate continues to use ammonium hydrogen carbonate or oxalic acid
Precipitating rare earth, obtained rare earth carbonate or oxalates by roasting, obtain content of rare earth (in terms of REO, similarly hereinafter) as 90% again
The mixed rare-earth oxide concentrate of left and right.Rare Earth Separation factory removal filtration, obtains above-mentioned rare earth oxide concentrate dissolving with hydrochloric acid
Multistep cascade extraction is carried out to high concentration mixed chlorinated rare earth solution, then using P507 or aphthenic acids, production purity 2N~
The single rare earth product of 5N levels.
Because rare earth leaching liquid middle rare earth concentration is low, ammonium hydrogen carbonate, oxalic acid unit consumption are high in removal of impurities, precipitation process, and can not
Produce the problems such as a large amount of ammonia nitrogen waste waters, oxalic acid and high salinity waste water discharge with avoiding, seriously pollute environment.It is additionally, since precipitation
Recovering rare earth technological process is complex, and interruption manual operations make it that rare earth loss late is high, and chemical materials consumption is high, causes to give birth to
It is high to produce cost.In addition, the rare earth oxide concentrate that precipitation recovering rare earth obtains contains 10% iron, aluminium, calcium, silicon and micro radiation
The impurity such as property nucleic, after dissolving with hydrochloric acid, above-mentioned impurity enriched causes acid dissolution slag specific radioactivity exceeded into slag, need to be by putting
Penetrating property waste residue disposal regulation builds storehouse stockpiling, potential safety hazard be present.
Therefore, low concentration of rare earth leachate and mine leaching ore deposit tail washings and mine tailing diafiltration in such as southern ion type rareearth ore
Low concentration of rare earth solution in liquid, above-mentioned similar process of enriching complexity all be present, rare earth yield is low, cost recovery is high asks
Topic.Therefore, it is badly in need of the green high-efficient low cost enriching and recovering technology of exploitation low concentration of rare earth solution, improves rare earth resources and utilize
Rate, and the problems such as being environmental pollution, is solved in rare earth resources removal process.
The content of the invention
The main purpose of the application is to provide a kind of method from low concentration of rare earth solution extracting and enriching recovering rare earth, with
Solve that recovery method of the prior art is complicated, rare earth yield is low, and the problem of cost is high.
To achieve these goals, according to the one side of the application, there is provided one kind extracts from low concentration of rare earth solution
The method for taking rare-earth enrichment recovery, low concentration of rare earth solution refer to count earth solution of the concentration as 0.05~8g/L, the party using REO
Method includes：First time Centrifugical extraction is carried out to low concentration of rare earth solution using non-saponified organic extractant, obtains the first load
Rare earth organic phase and the first raffinate；Centrifugation for the first time is carried out to the first supported rare earth organic phase using inorganic acid to be stripped, is obtained
First rare-earth enrichment liquid.
Further, REO concentration is more than or equal to 0.05g/L and is less than 1g/L in low concentration of rare earth solution.
Further, REO concentration is 1~8g/L in low concentration of rare earth solution, and method also includes carrying out the first raffinate
The step of the step of second of enrichment rare earth, preferably second of enrichment rare earth, includes：First raffinate is adjusted using alkaline matter
PH value between 2.5~5.0, preferably 3.0-4.5；Using non-saponified organic extractant to the first extraction after regulation pH value
Extraction raffinate carries out second of Centrifugical extraction, obtains the second supported rare earth organic phase and the second raffinate；It is negative to second using inorganic acid
Carry rare earth organic phase and carry out second of centrifugation back extraction, obtain the second rare-earth enrichment liquid.
Further, low concentration of rare earth solution is rare earth sulfate solution and/or re chloride.
Further, the pH value of low concentration of rare earth solution is 1.5~5, and preferably pH is 3~4.5.
Further, organic extractant is that P507 or P227, preferably P507 or P227 concentration are 0.5~1.5mol/L.
Further, in first time Centrifugical extraction step, non-saponified organic extractant and low concentration of rare earth solution are controlled
Volume flow ratio be 1:2~1:80, preferably 1:10~1:50；Time of contact is 5~60s, preferably 8~15s；For the first time from
In heart stripping steps, it is 20 to control the volume flow ratio of the first supported rare earth organic phase and inorganic acid:1~80:1, preferably 20:
1~50:1, time of contact is 60~600s, preferably 100~200s.
Further, in second of Centrifugical extraction step, the body of non-saponified organic extractant and the first raffinate is controlled
Product flow-rate ratio is 1:3~1:80, preferably 1:10~1:50；Time of contact is 5~60s, preferably 8~15s；Second of centrifugation is anti-
Extract in step, it is 20 to control the volume flow ratio of the second supported rare earth organic phase and inorganic acid:1~80:1, preferably 20:1~
50:1, time of contact is 60~600s, preferably 100~200s；Preferably, inorganic acid is hydrochloric acid, nitric acid or sulfuric acid, more preferably
The organic phase obtained after back extraction for the first time and/or second of back extraction recycles as organic extractant.
Further, alkaline matter is at least one of carbonate, subcarbonate and hydroxide；Preferably carbon
Sour ammonium, ammonium hydroxide, ammonium hydrogen carbonate, the carbonate of alkali metal or alkaline-earth metal, alkali metal or alkaline-earth metal subcarbonate,
At least one of hydroxide of alkali metal or alkaline-earth metal；More preferably alkaline matter is the solid carbonic acid of calcic and/or magnesium
Salt, or the solid basic carbonate that alkaline matter is calcic and/or magnesium.
Further, after the second raffinate is obtained, method also includes carrying out oil removing to the second raffinate and reclaim to have
Machine thing, it is preferred to use carbonate and/or subcarbonate carry out oil removing to the second raffinate and reclaim organic matter；More preferably use
The carbonate of alkali metal and/or alkaline-earth metal, the subcarbonate of alkali metal and/or alkaline-earth metal, ammonium carbonate and bicarbonate
At least one of ammonium, further preferably the solid basic carbonic acid of the solid carbonate or calcic for calcic and/or magnesium and/or magnesium
Salt；Further preferably, the solid carbonate and/or solid basic carbonate source of calcic and/or magnesium in calcite, lime stone,
One or more in marble, magnesite, artinite and dolomite.
Further, the granularity of solid carbonate and/or subcarbonate is 50nm~350 μm, preferably 500nm~50
μm。
Further, in carrying out oil removing to the second raffinate and reclaiming organic matter step, the pH of the second raffinate is controlled
Value is between 3.0~7.0, and preferably 4.0~5.0.
Using the technical scheme of the application, by using non-saponified organic extractant, low concentration of rare earth solution is extracted
Take, according to the height of actual earth solution concentration, all rare earths or middle heavy rare earth can be enriched into the first supported rare earth has
In machine phase, then it is stripped by inorganic acid, you can obtain including all rare earths or the first rare earth of mainly middle heavy rare earth is rich
Liquid collecting (concentration is up to 200g/L~280g/L in terms of REO).The earth solution extraction and enrichment method is simple to operate, rare earth yield
High and cost recovery is low.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.In the accompanying drawings：
Fig. 1 shows that extracting and enriching reclaims from low concentration of rare earth solution in a kind of preferred embodiment according to the application
The method flow schematic diagram of rare earth；And
Fig. 2 shows that extracting and enriching returns from low concentration of rare earth solution in another preferred embodiment according to the application
Receive the method flow schematic diagram of rare earth.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.The application is described in detail below in conjunction with embodiment.
Solvent extraction has continuous easy to control, cost is low, easy the characteristics of realizing large-scale production and be widely used in gold
The separating-purifying of category.Wherein the rare earth extraction extractant that mainly uses of separation industrial production for：P507, P204, aphthenic acids etc..But
It is that, in order to improve production efficiency, reduce equipment investment, reduction organic phase loss, the extract and separate purification of rare earth is in REO
Carried out in the earth solution of more than 200g/L high concentration, the organic phase used in extraction process generally uses ammoniacal liquor or liquid caustic soda
It is higher to carry out the consumption such as saponifiable extraction, acid, alkali, salt, and produces a large amount of ammonia nitrogens or high-salt wastewater.
However, as mentioned by background technology, it is molten to 1 ton of rare earth of extraction and recovery, rare earth for low concentration of rare earth solution
Liquid (REO 1g/L or so) treating capacity is up to more than 1000 cubes.Rare earth concentration will be enriched to more than 200g/L from 0.5~2g/L,
Extraction, back extraction up to 30 times or so of ratio of stream.Extracting and enriching is carried out using the saponification organic phase of routine, largely organic fold will be caused
Band or solution loss, produce 1 ton of rare earth, and organic phase loss amount is up to 0.5~1 ton.
Therefore, it is a kind of typical real in the application in order to solve the problems, such as above-mentioned enriching and recovering complex process and cost is high
Apply in mode, there is provided a kind of method of extracting and enriching recovering rare earth in solution from low concentration of rare earth, the low concentration of rare earth solution
Refer to count earth solution of the concentration as 0.05~8g/L using REO, as shown in Fig. 2 this method includes：Using non-saponified organic extraction
Agent carries out first time Centrifugical extraction to low concentration of rare earth solution, obtains the first supported rare earth organic phase and the first raffinate；Using
Inorganic acid carries out centrifugation for the first time to the first load organic phases and is stripped, and obtains the first rare-earth enrichment liquid.
In the above-mentioned solution from low concentration of rare earth of the application in the method for rare-earth enrichment recovery, non-saponified organic extractant is not
Need to use the saponification such as ammoniacal liquor, liquid caustic soda, by using non-saponified organic extractant, low concentration of rare earth solution is extracted, according to
The height of actual earth solution concentration, all rare earths or middle heavy rare earth can be enriched in the first supported rare earth organic phase,
Then be stripped by inorganic acid, you can obtain comprising all rare earths or mainly in heavy rare earth the first rare-earth enrichment liquid (with
REO counts concentration up to 200g/L~280g/L).The earth solution extraction and enrichment method is simple to operate, and rare earth yield is high and returns
Harvest sheet is low.
The method of extracting and enriching recovering rare earth in the above-mentioned solution from low concentration of rare earth, for concentration in 0.05~8g/L scopes
Interior rare-earth enrichment all has advantage simple to operate and low cost.For rare earth concentration below 1g/L earth solution richness
Collection, can be obtained comprising all rare earths including light rare earth and middle heavy rare earth by a step extraction-back extraction, not only reduced
Removal of impurities, precipitating rare earth, calcining, the acid tedious steps such as molten in the prior art, simplify recovery process, improve rare earth yield, reduce
Cost recovery；And reduce the discharge of ammonia nitrogen waste water, oxalic acid waste water, it is environmentally friendly.
The method of above-mentioned rare-earth enrichment recovery is equally applicable to the earth solution that concentration is 1~8g/L, relative to existing skill
For art, using the above-mentioned first time Centrifugical extraction of the application and the enriching and recovering method of centrifugation back extraction for the first time, it can simplify
The operating procedure of the first rare-earth enrichment liquid rich in middle heavy rare earth is obtained, reduces energy consumption, energy-saving and emission-reduction.Moreover, by follow-up right
The first raffinate containing light rare earth carries out second of Centrifugical extraction, by the efficient extraction and recovery of light rare earth of hardly possible extraction, passes through two
Centrifugical extraction coupling is walked, realizes the first separation of light, middle heavy rare earth, can equally simplify rare earth recovery step, improves rare earth recovery
Rate and reduction cost recovery.
In a kind of preferred embodiment of the application, REO concentration is 1~8g/L in low concentration of rare earth solution, such as Fig. 1 institutes
Show, the step of above method also includes carrying out the first raffinate second enrichment rare earth, preferably second of step for being enriched with rare earth
Suddenly include：Using the pH value of alkaline matter the first raffinate of regulation between 2.5~5, preferably 3.0~4.5；Had using non-saponified
Machine extractant carries out second of Centrifugical extraction to the first raffinate, obtains the second supported rare earth organic phase；Using inorganic acid to
Two supported rare earth organic phases carry out second of centrifugation back extraction, obtain the second rare-earth enrichment liquid.
It is by first time Centrifugical extraction in above preferred embodiment, in low concentration of rare earth solution more than 90% middle weight is dilute
Native ion extractuin is into the first load organic phases, then with inorganic acid the first load organic phases are carried out with centrifugation back extraction for the first time, obtains
To the first rare-earth enrichment liquid rich in middle heavy rare earth.Then the first raffinate that will be obtained using alkaline matter after the first Centrifugical extraction
The pH value of liquid is adjusted between 2.5~5, preferably 3~4.5, and follow-up non-saponifiable extraction agent can be ensured on this condition by residue
Light rare earth extraction it is complete, avoid the rare earth ion in solution to be deposited loss again, while dissolving or entrainment can also be reclaimed
Organic extractant.Finally pH value is carried out second in the first raffinate of above range using non-saponified organic extractant again
Centrifugical extraction and inorganic acid back extraction can obtain the second rare-earth enrichment liquid rich in light rare earth.The above method can be realized using same
A kind of extractant is to the efficient extracting and enriching of rare earth, and preliminary point of heavy rare earth and light rare earth in being realized while enrichment
From the acid and alkali consumption that can be saved in the extract and separate step of follow-up single rare earth, reducing cost.The above method also avoid use
Existing extractant cross pollution during a variety of extractants and be difficult to recycle the drawbacks of, realize the more efficient recovery of extractant
Recycle.
Low concentration of rare earth solution in the above method is preferably rare earth sulfate solution and/or re chloride.
In above-mentioned first time Centrifugical extraction step, when the pH value of low concentration of rare earth solution is 1.5~5, more preferably 3
When~4.5, using above-mentioned enriching and recovering method, can make rare earth extraction yield and rare earth the rate of recovery it is higher, concentration effect is more
It is good.
Preferably using P507, (ethylhexyl phosphoric acid list -2- ethylhexyls are also known as 2- second to organic extractant in the above method
Base hexyl phosphoric acid list -2- ethylhexyls) or P227 (double (2- ethylhexyls) phosphinic acids), P507 or P227 in use may be used
So that according to being actually needed, suitable concn is diluted to using diluent.Compared to other organic extractants, P507 or P227 are as extraction
Agent is taken, acid number is moderate (pka ＞ 4), can extract all rare earth ions under the non-saponifiable extraction process conditions of the application
Entirely, and can realizes the effect that the middle Heavy rare earth of its load is easily stripped, and acid and alkali consumption is low.Specific first time Centrifugical extraction
And the concentration of used extractant can rationally be adjusted according to the content of liquid middle rare earth to be extracted during second of Centrifugical extraction
It is whole.In a kind of preferred embodiment of the application, the concentration of above-mentioned organic extractant is 0.5~1.5mol/L.In the concentration model
In enclosing, organic extractant has of a relatively high mobility, be extracted that liquid contacts with each other relatively more fully, extraction efficiency is high
And Solvent quantity is saved, save production cost.
In the step of above-mentioned first time Centrifugical extraction, non-saponified organic extractant is molten with low concentration of rare earth as organic phase
The time of contact between volume flow ratio and two-phase between the aqueous phase of liquid, can be according to the dense of aqueous phase solution rare earth elements
The rare earth loaded amount of degree height and extractant carries out Reasonable adjustment.In the step of above-mentioned first centrifugation back extraction, the first supported rare earth
Organic phase concentration that can be according to obtained supported rare earth organic phase middle rare earth same with the volume flow ratio of inorganic acid, inorganic acid
Concentration and the concentration that reaches in advance of strip liquor Rare Earth Ion carry out Reasonable adjustment.In a kind of preferred embodiment of the application,
In first time Centrifugical extraction step, the volume flow ratio for controlling non-saponified organic extractant and low concentration of rare earth solution is 1:2
~1:80, preferably 1:10~1:50；Time of contact is 5~60s, preferably 8~15s；For the first time in centrifugation stripping steps, control
The volume flow ratio for making the first supported rare earth organic phase and inorganic acid is 20:1~80:1, preferably 20:1~50:1, during contact
Between be 60~600s, preferably 100~200s.
First time Centrifugical extraction is that emphasis is by controlling non-saponified organic extractant under suitable organic extraction agent concentration
With the stream ratio of earth solution (aqueous phase), in earth solution more than 90% middle Heavy rare earth is extracted into organic phase, obtained
The first supported rare earth organic phase rich in middle heavy rare earth, centrifugation for the first time is then carried out using inorganic acid and is stripped, in being rich in
First rare-earth enrichment liquid of heavy rare earth.Wherein, the first raffinate obtained is rich in light rare earth.
In the step of above-mentioned second Centrifugical extraction and second of centrifugation back extraction, non-saponified organic extractant is as organic
The time of contact between volume flow ratio and two-phase between phase, and the aqueous phase of the first raffinate, can be according to aqueous phase solution
The concentration level of rare earth elements and the rare earth loaded amount of extractant carry out Reasonable adjustment.Second supported rare earth organic phase with it is inorganic
The volume flow ratio of acid, equally can be according to concentration, the concentration of inorganic acid of the supported rare earth organic phase middle rare earth actually obtained
And the concentration that strip liquor Rare Earth Ion reaches in advance carries out Reasonable adjustment.In a kind of preferred embodiment of the application, second
In secondary Centrifugical extraction step, it is 1 to control the volume flow ratio of non-saponified organic extractant and the first raffinate:3~1:80, preferably
For 1:10~1:50；Time of contact is 5~60s, preferably 8~15s.In second of centrifugation stripping steps, the load of control second
The volume flow ratio of rare earth organic phase and inorganic acid is 20:1~80:1, preferably 20:1~50:1, time of contact be 60~
600s, preferably 100~200s；Preferably, inorganic acid is hydrochloric acid, nitric acid or sulfuric acid.The back extraction of above-mentioned first time and/or second
The organic phase obtained after back extraction recycles as organic extractant.
It is organic according to aqueous phase middle rare earth concentration, control in above-mentioned Centrifugical extraction twice and the preferred embodiment of centrifugation back extraction
The total amount of phase extracting rare-earth adjusts the volume flow ratio of organic phase and aqueous phase so that extraction equilibrium acidity 0.001~
In the range of 0.10mol/L, relatively low equilibrium acidity tool can reach the effect for improving rare earth extraction rate.And during by the contact of two-phase
Between control in 5~60s, preferably 8~15s, the purpose for reducing impurity extraction rate is reached while ensureing that rare earth is extracted efficiently,
Increase substantially the disposal ability and Rare Earth Production efficiency of equipment.In addition, according to supported rare earth organic phase middle rare earth concentration not
Together, the volume flow ratio of the above-mentioned supported rare earth organic phase obtained twice and inorganic acid is controlled to control 20:1~80:1, can
Strip liquor middle rare earth concentration (REO) is set to reach 250g/L or so.And control supported rare earth organic phase and the volume flow of inorganic acid
Than 20:1~50:In the range of 1, rare earth back extraction ratio is higher, and the split-phase effect of water-oil phase is more preferable.
The specific species of above-mentioned inorganic acid can be hydrochloric acid, nitric acid or the sulfuric acid commonly used in production, and its specific concentration can be with
Reasonable selection is carried out according to the strip liquor rare earth concentration and back extraction ratio for being actually needed to obtain.In the application, preferably inorganic acid is dense
Degree is more than 4.5mol/L, preferably 5.0mol/L~7.0mol/L.
It is any to realize to the first raffinate in above-mentioned the step of adjusting pH value to the first raffinate using alkaline matter
The regulation of liquid pH value is so that subsequently equally the non-saponified organic extractant of use carries out the alkalescence of efficient extracting and enriching to light rare earth
Material is applied to the application.In a kind of preferred embodiment of the application, the preferred carbonate of alkaline matter, subcarbonate,
At least one of hydroxide；The preferably carbonate of alkali metal, the subcarbonate of alkali metal, the hydroxide of alkali metal
Thing, the carbonate of alkaline-earth metal, the subcarbonate of alkaline-earth metal, the hydroxide of alkaline-earth metal, ammonium carbonate, ammonium hydroxide with
And at least one of ammonium hydrogen carbonate；More preferably nature enriches the calcic of low cost and/or the solid carbonate of magnesium or contained
The solid basic carbonate of calcium and/or magnesium.
In the method for above-mentioned rare-earth enrichment recovery, the pH value of the first raffinate is adjusted using alkaline matter, is in order to by the
The pH value of one raffinate adjusts to the non-saponifiable extraction agent of the application the condition that can carry out Centrifugical extraction again, so as to by first
The light rare earth remained in raffinate directly extraction is complete, and the alkaline matter of mentioned kind can realize the effect above.In this situation
Under, the preferred carbonate of alkaline matter or the solid carbonate or solid basic of subcarbonate, especially calcic and/or magnesium
Carbonate, the pH value of the first raffinate can not only be adjusted, and the organic matter in the first raffinate can be reclaimed (such as
Fig. 1).In actual mechanical process, require different according to actual separation extraction process, select the carbonic acid of alkali metal or alkaline-earth metal
The subcarbonate of salt, alkali metal or alkaline-earth metal, the effect of pH value is not adjusted only, can also reach the effect of oil removing simultaneously.
Because during pH value regulation, carbonate and/or subcarbonate can produce two with the hydrogen ion reaction in the first raffinate
Carbonoxide, it will remain or be dissolved in the organic phases such as P507 in raffinate using carbon dioxide gas floating power and carry to aqueous phase table
Face, so as to by organic phase enriching and recovering.Moreover, when carbonate and/or subcarbonate are solid, it is a small amount of excessive unreacted
Solid matter adsorbs as adsorbent to organic matter in the first raffinate, obtains more efficient recovery.This causes so that
Load during single extraction is organic will not to enter second of extraction process with the first raffinate, therefore reduces and extracted
The middle heavy rare earth taken enters the link of light rare earth extraction (second of extraction), so as to reach separate middle heavy rare earth and light rare earth
More thorough purpose.
A small amount of organic extractant is dissolved in second raffinate entrainment obtained above, not only causes the organic extractant of costliness
Loss, and environment is seriously polluted, it is necessary to carry out oil removal treatment and reclaim organic matter.It is less than 1g/L rare earth for rare earth concentration
Solution, rare earth ion extracting and enriching all in solution can be reclaimed by a Centrifugical extraction, obtained raffinate emphasis is
Want oil removing and reclaim organic phase (such as Fig. 2), avoid the organic extractant loss of costliness and pollution is produced to environment, now oil removing
Method can be identical with the second raffinate deoiling method.Preferably, the second raffinate is entered using carbonate and/or subcarbonate
Row oil removing simultaneously reclaims organic matter.The preferably carbonate of alkali metal, subcarbonate, carbonate, the basic carbonate of alkaline-earth metal
Salt, preferably at least one of ammonium carbonate and ammonium hydrogen carbonate, nature enrich the calcic of low cost and/or the solid carbon of magnesium
At least one of solid basic carbonate of hydrochlorate or calcic and/or magnesium；Further preferably, the calcic and/or magnesium
Solid carbonate and/or solid basic carbonate source in calcite, lime stone, marble, magnesite, artinite and
One or more in dolomite.
, can also be by entrained oil by standing clarification point when there is the situation that oil is carried secretly in the second raffinate obtained above
Xiang Hou, it is preliminary to collect recovery upper strata oil slick or organic matter, the step of then carrying out above-mentioned oil removal treatment again and reclaim organic matter, with
Improve organic matter organic efficiency.
For the second raffinate, it is preferred to use carbonate and/or subcarbonate produce with the hydrogen ion reaction in raffinate
Raw carbon dioxide, the organic phase for being remained the organic extractant for remaining or being dissolved in raffinate using carbon dioxide gas floating power
Carrier band is to aqueous phase surface, so as to by organic phase enriching and recovering.
When carbonate and/or subcarbonate are solid, except can be removed using the air supporting effect of carbon dioxide
Outside organic matter, excessive unreacted solid carbonate and/or subcarbonate are by CO2Air supporting carries out the suction of microparticle organic matter
It is attached to get off.In addition, the foreign ion such as the aluminium that may contain in raffinate, iron can form hydroxide, carbonate or alkali formula carbon
Hydrochlorate precipitates, also can be by CO2The microparticle organic matter adsorption and sedimentation that air supporting carries out gets off, and improves the removal effect of organic matter
Fruit.The carbonate and/or subcarbonate of mentioned kind is cheap and wide material sources, advantageously reduces enriching and recovering cost.
In above-mentioned the step of oil removing is carried out to the second raffinate and reclaims organic matter, in order to improve deoiling effect, in this Shen
In a kind of preferred embodiment, the pH value of second degreasing fluid please be controlled between 3.0~7.0, preferably between 4.0~5.0.pH
Value has the higher effect of deoiling effect within the range.
In the application another kind preferred embodiment, the carbonate source of above-mentioned calcic and/or magnesium is in calcite, lime
One or more in stone, marble, magnesite, artinite and dolomite.Using these natural crystals as calcic
And/or the carbonate of magnesium is applied in the deoiling step of raffinate, can reduce processing cost.Above-mentioned tune pH value step or organic
Treatment temperature and time in thing recycling step can be according to being actually needed carry out Reasonable adjustment.In a kind of preferable implementation of the application
In example, at a temperature of 0 DEG C~50 DEG C, typically carry out at normal temperatures, avoid heating increase energy consumption as far as possible.Processing time be 20~
600min, preferably 40~180min.Raffinate is handled within above-mentioned time and temperature range, had real in a short time
Existing pH value regulation and/or the effect of high efficiente callback organic matter, reduce the enriching and recovering time, shorten the production cycle.Second raffinate
After organic matter reclaims, organophosphor and COD contents reach national rare-earth industry pollutant emission standard.
In a kind of preferred embodiment of the application, in organic matter recycling step, when the carbonate and/or alkali formula of addition
Carbonate facics to it is excessive when, in addition to entered to unnecessary in aqueous phase with carbonate existing for precipitation form and/or subcarbonate
Row clarification split-phase or filtering, the step of obtaining aqueous phase and solid slag；Then carbon dioxide air supporting is carried to aqueous phase surface has
Machine is mutually directly separated recovery, you can the second raffinate being recycled after organic phase and purification.According to needs of production, may be used also
To be handled using diluted acid solid slag, so as to reclaim the organic phase in solid slag；It is preferred that it is 1% that diluted acid, which is selected from mass concentration,
One or more in~30% hydrochloric acid, sulfuric acid or nitric acid, preferred acid mass concentration are 3%~15%；The organic phase of recovery
Composition is mainly P507 or P227 extractants and/or organic diluent.
In organic matter removal process, when addition diluted acid dissolves to solid slag, lysate terminal is preferably controlled
PH is 0.8~2.Recovery is directly separated to the upper organic phase in above-mentioned aqueous phase, the second raffinate after being purified.
In another preferred embodiment of the application, when there is no solid generation after raffinate processing, then organic matter
Aqueous top layer is floated over, directly organic matter is separated and recovered.Due to being liquid or non-mistake when carbonate and/or subcarbonate
Therefore amount, is directly separated more simple and convenient in use, be solution to the mixture after wastewater treatment.
In order to further improve the elimination effect to organic extractant in raffinate, in another preferable implementation of the application
In example, the granularity of carbonate and/or subcarbonate solid is 50nm~350 μm, preferably 500nm~50 μm.By above-mentioned carbon
The solid powder of hydrochlorate and/or subcarbonate is milled to less than 350 μm, preferably 500nm~50 μm, is favorably improved the work of powder
Property and adsorptivity, so as to improve reaction speed, reduce dosage.Granularity has adsorption capacity strong within the range, and it is molten to be easy to part
Solution produces the advantages that carbon dioxide.
In above-mentioned organic matter recycling step (including it is organic in the step of first time raffinate pH regulations and the second raffinate
The step of thing reclaims), according to the species of specifically used alkaline matter, carbonate and/or subcarbonate and raffinate
The difference of acidity, its mass ratio (kg with raffinate:Kg) also have differences, can rationally be adjusted according to endpoint pH accordingly
It is whole.In a kind of preferred embodiment, using alkaline matter adjust the first raffinate pH value the step of in, alkaline matter with
The mass ratio of first raffinate is 1:5000~1:100, preferably 1:2000~1:500.In another preferred embodiment,
In the step of organic matter in the second raffinate reclaims, carbonate and/or subcarbonate and the second raffinate
Mass ratio is 1:5000~1:100, preferably 1:2000~1:500.
In above-mentioned two preferred embodiment, mass ratio is 1:5000~1:The effect except organic matter is respectively provided with the range of 100
Fruit.As mass ratio increases, organic removal rate gradually rises, therefore the dosage for improving carbonate and/or subcarbonate has
Beneficial to raising organic removal rate.But adding multi-carbonate will cause subsequent treatment cost to increase.Therefore carbonic acid is considered
Utilization rate, cost of material and the follow-up processing cost of salt, preferably solid-to-liquid ratio is 1:2000~1:In the range of 500.
In order to improve the back extraction ratio of the extraction yield of rare earth and load organic phases middle rare earth, in the application, another is preferable real
To apply in example, Centrifugical extraction and centrifugation back extraction series are respectively 2~8 grades, and series increase, rare earth extraction rate and back extraction ratio can improve,
But investment increase, preferably 3~5 grades.In order to further speed up the speed for removing organic matter, in another preferred embodiment of the application
In, in the step of being reclaimed to organic matter, raffinate is reclaimed using air stirring and/or churned mechanically mode
Processing.Handled by agitating mode, be advantageous to improve the adsorption efficiency of carbonate and/or subcarbonate to organic matter,
And be advantageous to carbon dioxide and be uniformly distributed in waste water, so as to realize the efficient carrier band to organic matter, and cost it is low,
Invest small, easy to control.
Further illustrate the beneficial effect of the application below in conjunction with specific embodiments.
It should be noted that extractant used in following examples is non-saponifiable extraction agent.Embodiment 1-25 is 3
Level Centrifugical extraction and 3 grades of centrifugation back extraction.
Embodiment 1
Use concentration for 1.5mol/L P507 to low concentration re chloride (REO count concentration be 0.99g/L, pH=
4.0) first time Centrifugical extraction is carried out, the volume flow ratio for controlling P507 and low concentration of rare earth solution is 1:3, two-phase time of contact
For 10s, the first supported rare earth organic phase and the first raffinate that rare earth concentration is 2.95g/L are obtained.Wherein, rare earth extraction rate is
99.3%.First extract can carry out recovery organic phase by adding the pH of dolomite to the first raffinate for 5.
Centrifugation back extraction is carried out to the first supported rare earth organic phase using hydrochloric acid, and controls the first supported rare earth organic phase and salt
The volume flow ratio of acid is 80:1, two-phase time of contact is 300s, (wherein, obtained rare earth concentration is calculated as 232.1g/L with REO
Theoretical REO concentration is 235.9g/L) the first rare-earth enrichment liquid (containing middle heavy rare earth and light rare earth).Rare earth yield is
98.8%.
Embodiment 2-6
The step of embodiment 2 to 6 is with embodiment 1 is identical, using the process conditions shown in table 1, to low concentration of rare earth solution
In rare earth be enriched with, enrichment the results are shown in Table 2.
Table 1：
Table 2：
Embodiment 7
The P507 that concentration is 1.5mol/L is used to low-concentration sulfuric acid earth solution (REO meter concentration is 8g/L, pH=4.5)
First time Centrifugical extraction is carried out, the volume flow ratio for controlling P507 and low concentration of rare earth solution is 1:2, two-phase time of contact is
15s, obtain the first supported rare earth organic phase and the first raffinate.(wherein, the first supported rare earth organic phase middle rare earth concentration is
10.72g/L, rare earth extraction rate are 67%, 0.8%) impurity extraction rate is.
Centrifugation for the first time is carried out to the first supported rare earth organic phase using hydrochloric acid to be stripped, controls the first load organic phases and salt
The volume flow ratio of acid is 23:1, two-phase time of contact is 200s, obtains the first rare-earth enrichment liquid rich in middle heavy rare earth.Its
In, the concentration of rare earth is 244.1g/L (theoretical concentration 245.6g/L), and the back extraction ratio of rare earth is 99.0%.
The pH value of the first raffinate is adjusted to 4.5 using calcium hydroxide, the after then being adjusted using P507 to pH value
One raffinate carries out second of Centrifugical extraction.It is 1 to control the volume flow ratio of P507 and the first raffinate:3, two-phase time of contact
For 10s, the second supported rare earth organic phase and the second raffinate are obtained.Wherein, the extraction yield of second of Centrifugical extraction is
98.60%, impurity extraction rate is 1.5%, and the second supported rare earth organic phase middle rare earth concentration is 7.81g/L.
Carry out second of centrifugation to the second supported rare earth organic phase respectively using hydrochloric acid to be stripped, and control the second supported rare earth
The volume flow ratio of organic phase and hydrochloric acid is 33:1, two-phase time of contact is 200s, obtains 253.8g/L the second rare-earth enrichment
Liquid (lree enrichment liquid) (theoretical rare earth concentration is 257.7g/L).The rare earth back extraction rate of recovery is 98.5%.
Embodiment 8 is to embodiment 25
Embodiment 8 is handled low concentration of rare earth solution to embodiment 25 using step same as Example 7, low dense
Degree earth solution and extractant raw material condition are shown in Table 3, and the Parameter Conditions in concrete processing procedure are shown in Table 4, first time rare earth it is rich and
The result of second of rare-earth enrichment is shown in Table 5 and table 6 respectively.
Table 3：
Table 4：
Table 5：
Table 6：
Embodiment 26-28
In embodiment 26-28,4 grades, 5 grades and 6 grades extractions are respectively adopted except first time extraction extracts with second, first
Secondary be stripped is respectively adopted outside 4 grades, 5 grades and 6 grades back extraction with second of back extraction, and remaining enrichment condition is same as Example 7.It is rich
The difference of collection result and embodiment 7 is shown in Table 7 and table 8.
Table 7：
Table 8：
The organic phase remained in above-described embodiment 7-28 in second of raffinate can be by adding alkaline matter to be reclaimed.
Embodiment 29
The second raffinate in embodiment 7, volume 1000L, phosphorus concentration 32mg/L, first separates and recovers upper strata
Organic phase,.Then with the solid dolomite that 1000g granularities are 5 μm to being handled containing organic wastewater, reaction end pH value is
4.Liquid phase and solid slag are directly filtrated to get to the mixed serum after stirring.It is 1.9mg/L that phosphorus concentration is remained in liquid phase, organic matter
Clearance reaches 94.0%.
Embodiment 30 is to embodiment 47
Embodiment 30 has to the step same or like with embodiment 29 of embodiment 47 to what is remained in second of raffinate
Machine is mutually handled, and specific recovery condition and recovery the results are shown in Table 9.
Table 9：Oil removing condition and recovery result
As can be seen from the above description, the application the above embodiments realize following technique effect：
1) simplification of flowsheet, rare earth yield is improved, reduces pollutant emission, reduces cost.
By directly to low concentration of rare earth solution flow greatly carried out than under the conditions of non-saponified Centrifugical extraction and centrifugation be stripped, can
The efficiently concentrating (mixed rare earth solution that REO contents are higher than 200g/L can be obtained) of rare earth is realized, concentration ratio is up to more than 200.
(low concentration of rare earth solution is enriched with through impurity and purification, ammonium bicarbonate precipitation, and generation crystal formation is good with ammonium bicarbonate precipitation beneficiation technologies
Carbonated rare earth precipitation, ion type rareearth concentrate is obtained by high temperature sintering, then sour molten obtain high concentration rare earth solution) compare,
The technological process of the application greatly simplifies, and rare earth loss can reduce by 10% or so, do not consume ammonium hydrogencarbonate, oxalic acid, avoid to ring
The pollution in border, production cost are greatly reduced.And in can realizing heavy rare earth and light rare earth initial gross separation, be follow-up rare earth
Extract and separate provides more convenient condition.
2) good impurity removing effect.
In the prior art, be first using ammonium hydrogen carbonate to low concentration of rare earth solution before enriching and recovering is carried out to rare earth
Neutralization removal of impurities is carried out, to remove the impurity such as iron removaling and/or aluminium.And the application is by effectively controlling two-phase mixtures time of contact, i.e.,
The fast rare earth of mass transfer velocity substantially achieves the dynamics and thermodynamic equilibrium state of mass transport process, so as to efficiently be extracted into organic
The foreign ion such as phase, the slow iron of mass transfer velocity, aluminium then dynamics and thermodynamic equilibrium state away from mass transport process, substantially not
(iron, aluminium extraction yield are less than 5%) is extracted, remains in aqueous phase, it is achieved thereby that the impurity such as rare earth and iron and/or aluminium effectively divides
From the step of not only saving neutralization removal of impurities, and ammonium hydrogen carbonate not being consumed, so as to reduce production cost and dirt to environment
Dye.
3) loss of organic phase is lacked.
By reasonably optimizing Centrifugical extraction, stripping process two-phase mixtures and centrifugation split-phase time and mixing intensity, ensureing
While rare earth extraction rate, two-phase laminated flow effect is improved, reduces the loss of organic phase.In addition, using alkali metal, alkaline-earth metal
Carbonate or subcarbonate carry out oil removal treatment to raffinate, obtain entrainment or the organic extractant being dissolved in raffinate
Effective recycling, organic phase recovery utilization rate reach more than 98%, and organic phosphorous content is less than 1mg/ in the raffinate after oil removing
L, reach national environmental standard requirement.
43) extracting and enriching efficiency high.
P507, P227 are acidic phosphorus extractant, extract a rare earth ion, 3 hydrogen ions are replaced, with aqueous phase
Acidity raises, and rare earth extraction rate declines, i.e., the extraction yield of rare earth is inversely proportional with aqueous phase acidity.For rare earth concentration higher than 1g/L's
Earth solution, heavy rare earth in first being extracted with P507, then by adjusting raffinate aqueous phase acidity, it is further light dilute with P507 extractions again
Soil, so as to reach the effect for improving rare earth extraction rate (＞ 99), and rare earth concentration is enriched with 500 times or so.
5) compared with traditional extracting process, the investment of equipment and raw material is reduced.
The process that trace rare-earth extracts in low concentration of rare earth solution, the volume of aqueous phase are big, it is necessary to flow ratio and format high throughput greatly
Extraction equipment.During using mixed settler extractor or tower extraction equipment, equipment volume is big, floor space is big, and required has
Machine input amount is more, and uses centrifugal extraction equipment small volume, organic input amount small, only the 1/30~1/ of slot type extraction equipment
10。
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (12)
1. a kind of method of extracting and enriching recovering rare earth in solution from low concentration of rare earth, it is characterised in that the low concentration of rare earth
Solution refers to count earth solution of the concentration as 0.05~8g/L using REO, and methods described includes：
First time Centrifugical extraction is carried out to the low concentration of rare earth solution using non-saponified organic extractant, obtains the first load
Rare earth organic phase and the first raffinate；
Centrifugation for the first time is carried out to the first supported rare earth organic phase using inorganic acid to be stripped, obtains the first rare-earth enrichment liquid.
2. according to the method for claim 1, it is characterised in that REO concentration is more than or equal in the low concentration of rare earth solution
0.05g/L and it is less than 1g/L.
3. according to the method for claim 1, it is characterised in that REO concentration is 1~8g/ in the low concentration of rare earth solution
L, the step of methods described also includes carrying out first raffinate second enrichment rare earth, preferably it is described be enriched with for the second time it is dilute
The step of soil includes：
Using the pH value of alkaline matter regulation first raffinate between 2.5~5.0, preferably 3.0~4.5；
Second of centrifugation is carried out using the non-saponified organic extractant to first raffinate after regulation pH value to extract
Take, obtain the second supported rare earth organic phase and the second raffinate；
Second of centrifugation is carried out to the second supported rare earth organic phase using inorganic acid to be stripped, obtains the second rare-earth enrichment liquid.
4. according to the method in any one of claims 1 to 3, it is characterised in that the low concentration of rare earth solution is sulfuric acid
Earth solution and/or re chloride.
5. according to the method for claim 1, it is characterised in that the pH value of the low concentration of rare earth solution is 1.5~5, excellent
PH is elected as 3~4.5.
6. according to the method in any one of claims 1 to 3, it is characterised in that the organic extractant be P507 or
P227, preferably described P507 or P227 concentration are 0.5~1.5mol/L.
7. according to the method in any one of claims 1 to 3, it is characterised in that
In the first time Centrifugical extraction step, the non-saponified organic extractant and the low concentration of rare earth solution are controlled
Volume flow ratio is 1:2~1:80, preferably 1:10~1:50；Time of contact is 5~60s, preferably 8~15s；
In the first time centrifugation stripping steps, the first supported rare earth organic phase and the volume flow of the inorganic acid are controlled
Than for 20:1~80:1, preferably 20:1~50:1, time of contact is 60~600s, preferably 100~200s.
8. according to the method for claim 3, it is characterised in that
In second of Centrifugical extraction step, the volume of the non-saponified organic extractant and first raffinate is controlled
Flow-rate ratio is 1:3~1:80, preferably 1:10~1:50；Time of contact is 5~60s, preferably 8~15s；
In second of centrifugation stripping steps, the second supported rare earth organic phase and the volume flow of the inorganic acid are controlled
Than for 20:1~80:1, preferably 20:1~50:1, time of contact is 60~600s, preferably 100~200s；
Preferably, the inorganic acid is hydrochloric acid, nitric acid or sulfuric acid, more preferably described first time back extraction and/or it is described second it is anti-
The organic phase obtained after extraction recycles as the organic extractant.
9. according to the method for claim 3, it is characterised in that the alkaline matter be carbonate, subcarbonate and
At least one of hydroxide；Preferably the carbonate of ammonium carbonate, ammonium hydroxide, ammonium hydrogen carbonate, alkali metal or alkaline-earth metal,
At least one of hydroxide of the subcarbonate of alkali metal or alkaline-earth metal, alkali metal or alkaline-earth metal；More preferably institute
Alkaline matter is stated as calcic and/or the solid carbonate of magnesium, or the solid basic carbon that the alkaline matter is calcic and/or magnesium
Hydrochlorate.
10. according to the method for claim 3, it is characterised in that after second raffinate is obtained, methods described is also
Including carrying out oil removing to second raffinate and reclaiming organic matter, it is preferred to use carbonate and/or subcarbonate are to described
Second raffinate carries out oil removing and reclaims organic matter；More preferably using alkali metal and/or carbonate, the alkali metal of alkaline-earth metal
And/or at least one of subcarbonate, ammonium carbonate and ammonium hydrogen carbonate of alkaline-earth metal, it is further preferably calcic and/or magnesium
Solid carbonate or the solid basic carbonate of calcic and/or magnesium；Further preferably, the solid of the calcic and/or magnesium
Carbonate and/or solid basic carbonate source are in calcite, lime stone, marble, magnesite, artinite and white clouds
One or more in stone.
11. the method according to claim 9 or 10, it is characterised in that the solid carbonate and/or the basic carbonate
The granularity of salt is 50nm~350 μm, preferably 500nm~50 μm.
12. according to the method for claim 10, it is characterised in that carrying out oil removing to second raffinate and reclaiming to have
In machine thing step, the pH value of second raffinate is controlled between 3.0~7.0, preferably 4.0~5.0.
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| CN201610644810.XA CN107699715B (en) | 2016-08-08 | 2016-08-08 | The method of extracting and enriching recovering rare earth from low concentration of rare earth solution |
| PCT/CN2017/096222 WO2018028543A1 (en) | 2016-08-08 | 2017-08-07 | Method for extraction, enrichment and recovery of rare earths from low-concentration rare earth solution |
| MYPI2019000184A MY189673A (en) | 2016-08-08 | 2017-08-07 | Method for extraction, enrichment and recovery of rare earths from low-concentration rare earth solution |
| BR112019002095-0A BR112019002095B1 (en) | 2016-08-08 | 2017-08-07 | METHOD FOR EXTRACTION, ENRICHMENT AND RECOVERY OF RARE-EARTHS FROM LOW CONCENTRATION OF RARE-EARTH SOLUTIONS |
| CL2019000171A CL2019000171A1 (en) | 2016-08-08 | 2019-01-22 | Rare earth extraction and recovery method from a rare earth dissolution of low concentration. |
| ZA201900637A ZA201900637B (en) | 2016-08-08 | 2019-01-30 | Method for extraction, enrichment and recovery of rare earths from low-concentration rare earth solution |
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| CN109912093A (en) * | 2019-02-19 | 2019-06-21 | 北京中科康仑环境科技研究院有限公司 | A kind of zero-discharge production process based on praseodymium, neodymium anti-stripping agent |
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| CN108707753B (en) * | 2018-07-06 | 2020-07-14 | 赣州富尔特电子股份有限公司 | Process for recovering rare earth-containing waste material by solvent extraction |
| CN109266873A (en) * | 2018-11-13 | 2019-01-25 | 中国北方稀土（集团）高科技股份有限公司 | The device and method of oil slick in earth solution is removed in Rare-Earth Extraction Process |
| CN111977883A (en) * | 2020-09-21 | 2020-11-24 | 鑫联环保科技股份有限公司 | Method and equipment for extracting high-purity cesium sulfate from high-salinity wastewater |
| CN115679130A (en) * | 2021-07-21 | 2023-02-03 | 中国科学院长春应用化学研究所 | Ionic rare earth ore erbium and thulium grouping method |
| CN114011112A (en) * | 2021-11-17 | 2022-02-08 | 朱辰宇 | Efficient extraction equipment and extraction method for rare earth oxide |
| CN114524540A (en) * | 2022-02-16 | 2022-05-24 | 信丰华锐钨钼新材料有限公司 | Reutilization method of N263 alkaline extraction raffinate |
| CN115354157B (en) * | 2022-08-01 | 2023-11-24 | 江西群鑫强磁新材料股份有限公司 | Neodymium iron boron waste material extraction edulcoration device |
| CN115448505A (en) * | 2022-09-09 | 2022-12-09 | 江西理工大学 | Method for advanced treatment of raffinate wastewater in rare earth industry by multiple coupling reinforcement electro-Fenton |
| CN115554981B (en) * | 2022-10-18 | 2024-01-26 | 江西理工大学 | Method for adsorbing and enriching low-concentration rare earth ions by using excess sludge carbonized product |
| CN116002745A (en) * | 2023-01-09 | 2023-04-25 | 江西离子型稀土工程技术研究有限公司 | Method for preparing mixed rare earth oxide from rare earth film enriched liquid |
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| CL2019000171A1 (en) | 2019-04-26 |
| CN107699715B (en) | 2019-10-01 |
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