CN102352448B - Method for recovering rare earth from low-concentration rare earth solution through prussian blue colloidal nanoparticles - Google Patents
Method for recovering rare earth from low-concentration rare earth solution through prussian blue colloidal nanoparticles Download PDFInfo
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Abstract
The invention relates to a method for recovering rare earth from low-concentration rare earth solution through prussian blue colloidal nanoparticles (PB-CNP). The method comprises the following steps: firstly synthesizing a stable PB-CNP colloidal solution, loading into a bag produced by a dialysis membrane, enabling a dialysis bag containing PB-CNP suspension to be in contact with rare earth material liquid (the pH value is 4-7), and enabling rare earth ions to pass through membrane holes to be in contact with the PB-CNP for being adsorbed. Dilute acid solution is used for desorbing the rare earth from the PB-CNP suspension which absorbs the rare earth ions, thereby achieving the purpose of recovering the rare earth. The PB-CNP suspension and the rare earth material liquid can also be arranged in different channels on the two sides of the membrane of a membrane component for flowing in a countercurrent way, thereby achieving the high-efficient enrichment effect. The method has the advantages of simple process, large rare earth loading amount, high rare earth recovery rate and the like, and can be widely used for the rare earth material liquid of rare earth mines and separation factories; and furthermore, by adopting the method, the rare earth ions in low-concentration rare earth wastewater can be completed removed and recovered, thereby having wide application prospects.
Description
Technical field:
The invention belongs to rare-earth wet method metallurgy and technical field of waste water processing, be specifically related to a kind of Prussian blue colloidal nanoparticles (PB-CNP) that utilizes as the method for sorbent material recovering rare earth from earth solution.
Background technology:
The application of Rare Earth Functional Materials in new high-tech industry and national defence, aeronautical and space technology is very extensive.But, along with the reinforcement of rare earth resources exploitation dynamics, the rare earth increase in demand, the higher-grade rare-earth mineral is reducing.Therefore; obtained paying close attention to widely in recent years for the rare earth recovery technology in the high efficiency rare-earth extractive technique of low-grade rare-earth mineral and the low concentration of rare earth waste water that produces in the Rare Earth Production process, especially studied the recovery technology of low concentration of rare earth feed liquid or waste water middle-weight rare earths from the angle of environment and conservation of resources.
Can produce a large amount of low concentration of rare earth leach liquor or waste water in the recovery process of southern ion type rareearth resource, especially soak in the technology of ore deposit in the original place, the concentration of leach liquor can reach 2g/L even more than 3g/L when the peak, but the concentration of most leach liquors is below 1g/L.Generally speaking, concentration all can be used precipitator method enriching and recovering rare earth wherein greater than the rare earth feed liquid of 0.3g/L.Soak the ore deposit and often directly do not reclaim but be used for circulation lower than the leaching tail washings of this concentration.Meanwhile, due to the original place soak the ore deposit to soak the amount that agent injection rate in ore deposit soaks than the pond large, it is residual in ore body that to soak the ore deposit agent content also higher, in the ore deposit residual soak the ore deposit agent can be with the ore deposit when moving with leaching water in rare earth in residual rare earth or downstream ore body bring stream stream into and run off, its content of rare earth is generally between 0.001～0.15g/L.If do not reclaimed, rare earth and electrolyte content in ambient water are increased, accelerate rare earth and run off, influence ecological environment, or even drinking water safety.In case the rare earth ion entered environment can not be biodegradable, can hide for a long time in environment along with food chain enters human body, accumulate in human body, cause various diseases and dysfunction, be detrimental to health.
The method of rare-earth enrichment recovery ion has much from low concentration of rare earth feed liquid or waste water.Be the most simply the precipitator method, complicated any extraction process, reverse osmosis method and ion-exchange-resin process etc. are arranged.In precipitator method recovering rare earth scheme, normally make solution be alkalescence with lime neutralization, make rare earth separate out precipitation of hydroxide and with a large amount of moisture from.This method is simple, but because the water yield is large, needs could discharge to neutral with the anti-pH of accent of acid.Resin adsorption method is also fairly simple, but charge capacity is little, and the resin cost is high, and the rare earth desorb is difficulty comparatively.The also not thoroughly solutions of problem such as although extraction process enrichment efficient is high, enrichment times is large, compares too littlely, and the extraction agent solution loss is large, and the high and secondary pollution of cost is large.
Summary of the invention:
The objective of the invention is for the deficiencies in the prior art, a kind of short-cut method that can thoroughly remove rare earth ion and reclaimed from low concentration of rare earth feed liquid or waste water is provided.
The technical scheme that the present invention takes: utilize PB-CNP to the strong adsorpting characteristic of rare earth ion and the dialysis membrane selection perviousness to rare earth ion, PB-CNP aaerosol solution and dialyzer are combined into adsorb the elementary cell of rare earth from rare earth feed liquid or low concentration of rare earth waste water, this rare earth ion that is adsorbed can get off with the dilute acid soln desorb easily, and then reaches the purpose of rare-earth enrichment recovery;
The present invention includes following steps:
[1] with FeCl
3 .6H
2O and K
4Fe (CN)
6Be raw material, accurately take corresponding raw material according to the mol ratio of 1:1.05～1:1.2, be dissolved in respectively in distilled water, at room temperature with FeCl
3Solution drops to K
4Fe (CN)
6In solution, add a small amount of acetone after stirring, standing a moment, centrifugation, natural air drying obtains the PB-CNP solid;
[2] PB-CNP that is synthesized is distributed to the colloidal solution that can obtain high stability in water, and pack into by in the made sack of dialyzer, obtain to be directly used in the elementary cell of absorption rare earth ion, this elementary cell of adsorbing rare earth ion by PB-CNP and dialysis tubing can be used for of forming also can be without separating out the PB-CNP solid but directly will be reacted the PB-CNP colloidal solution that the generates dialysis tubing of packing into, allows the complete K of unreacted in pure water
4Fe (CN)
6Dialysis out gets final product afterwards;
Contact in the dialysis tubing that [3] PB-CNP colloidal solution will be housed and pending rare earth feed liquid, rare earth ion can be adsorbed by PB-CNP after entering inner bag by fenestra.This dialysis tubing that PB-CNP suspension is housed can adsorb rare earth ion to come up from solution.The pH value of processed earth solution be preferably between 5-7, and rare earth concentration is not limit between 4-7.5; The every 1mg PB-CNP that measures is to La
3+, Gd
3+, Yb
3+, Y
3+Saturated extent of adsorption be respectively 216 μ g, 243 μ g, 254 μ g, 160 about μ g;
[4] process with dilute acid soln the PB-CNP suspension that absorption has rare earth ion, rare earth is desorbed, and then reach the purpose of rare-earth enrichment recovery; The pH value of desorb acid solution is less than 4, preferably less than 2; The rare earth stripping liquid of gained can with general precipitator method recovering rare earth, also can be directly used in the configuration rare earth feed liquid and advance the extracting and separating operation;
[5] meanwhile, also can adopt membrane module to realize the efficient adsorption of rare earth ion, wherein PB-CNP colloidal solution and pending rare earth feed liquid are placed in respectively in film, outside film, different passages are gone against the stream, and reach the efficiently concentrating effect.
The invention has the beneficial effects as follows: have advantages of that simple, the rare earth loaded amount of technique is large and rare earth yield is high, can be widely used in the rare earth feed liquid of Rare-earth Mine, separation plant, especially the removing fully and reclaim of low concentration of rare earth waste water Rare Earth Ion, be with a wide range of applications.
Description of drawings:
Fig. 1 is the particle size distribution figure of the PB nanoparticle of preparation in embodiment 1, can find out, the granularity of the PB-CNP that the present invention is prepared is that D50 is less than 100nm.
Fig. 2 is in embodiment 1, and the coagulation Performance Ratio that PB-CNP is dispersed in particle after the aqueous solution of different pH.As seen from the figure, in pH=3 ~ 7 scopes, synthetic PB-CNP is very stable, also not sedimentation under high speed centrifugation.But when under the condition of pH≤2 and pH 〉=8, this class PB-CNP can not stable existence, and the colloidal property of PB-CNP is destroyed and coagulation occurs under stronger acidic conditions, and at basic solution, decompose because the hydrolysis of iron produces FeOOH, especially pH 9 o'clock, decomposition faster.
Fig. 3 is in embodiment 2, and under room temperature, pH=3 ~ 7 o'clock contain the aqueous solution of 1mg PB-CNP at the Gd of difference amount
3+There is the coagulation quantitative change curve of lower PB in (10 ~ 300 μ g), due to PB-CNP, rare earth had strong adsorpting characteristic, when the negative charge on PB-CNP surface by rare earth in and after the coagulation of colloidal particle can occur.X-coordinate is the Gd that adds
3+Amount (0 ~ 300) μ g, ordinate zou is due to Gd
3+Add the PB sinkability that causes.As seen from the figure: 1. pH=3 ~ 7 o'clock, Gd
3+: PB-CNP≤8/100, PB is sedimentation hardly; 2. pH=3 ~ 4 o'clock, Gd
3+: PB-CNP 〉=9/100 o'clock, PB almost can sedimentation; 3. pH=5 ~ 7 o'clock, Gd
3+: PB-CNP≤11/100 o'clock, PB is sedimentation hardly; Gd
3+: PB-CNP=12/100 ~ 13/100 o'clock, PB can a sedimentation part; Gd
3+: nearly all sedimentation of PB-CNP 〉=14/100 o'clock PB.The coagulation that PB is described is directly related with the rare earth content that adds with pH value of solution, in the Acidity Range of pH=5 ~ 7, the gadolinium amount of the upper load of PB-CNP can reach its weight 11% and coagulation not, along with the increase of gadolinium charge capacity, the coagulation amount of PB increases, when coagulation fully greater than 14% time.
Fig. 4 is in embodiment 3, and under constant temperature (T=30 ℃) constant volume (50mL) oscillating condition, 1mg PB-CNP is to 300 μ g Gd
3+Absorption relation curve about the pH change.X-coordinate is time T=0 ~ 60min, and ordinate zou is the Gd that every mgPB adsorbs
3+Amount, its initial consumption is 300 μ g.After 30min, absorption reaches in a basic balance as can be seen from Figure.When pH=2, PB is to Gd
3+Do not adsorb; PH=3 4 o'clock, can adsorb, but not reach capacity; PH=5 ~ 7 o'clock can be adsorbed, and be reached capacity, and its saturated extent of adsorption is 240 ~ 250 μ g left and right.Can determine according to the diagram result, the optimal ph scope of PB-CNP absorption rare earth ion is 5-7.Less than 4 solution, the upper desorb rare earth of PB of rare earth ion can be arranged from saturated adsorption with pH, and pH is equal to or less than 2 solution and can gets off the rare earth ion desorb that is adsorbed on PB.
Fig. 5 is in embodiment 4, and under constant temperature (T=30 ℃) constant volume (50mL) oscillating condition, 1mg PB-CNP is to 100 μ g, 200 μ g, 300 μ g, 400 μ g Gd
3+About time (0 ~ 60min) absorption relation curve.X-coordinate is time T=0 ~ 60min, and ordinate zou is the Gd that every mg PB-CNP adsorbs
3+Amount, its initial consumption is respectively 100 μ g, 200 μ g, 300 μ g, 400 μ g.After can finding out 30min by upper figure, absorption can reach in a basic balance, and every mg PB-CNP is to Gd
3+Saturated extent of adsorption be 240 ~ 250 about μ g.
Fig. 6 is that in embodiment 4, PB-CNP is to Gd
3+The adsorption isothermal line of (0 ~ 500 μ g).Gd in solution when wherein X-coordinate is balance
3+Concentration, ordinate zou loads on the upper Gd of PB-CNP when being balance
3+Concentration.
Fig. 7 is that in embodiment 4, PB-CNP is to Gd
3+The absorption relation curve of (0 ~ 500 μ g).Wherein X-coordinate is Gd
3+Starting point concentration, ordinate zou loads on the upper Gd of PB-CNP when being balance
3+Concentration.
Fig. 8 is that in embodiment 4, PB-CNP is to Gd
3+The absorption relation curve of (0 ~ 500 μ g).Wherein X-coordinate is Gd
3+Starting point concentration, Gd when ordinate zou is balance
3+Percent load.
Fig. 9 is in embodiment 5, pH=5 ~ 7 o'clock, temperature change is to PB-CNP(1mg) absorption Gd
3+(200 μ g) affects relation curve.As seen from the figure, between 30 ~ 80 ℃, along with the rising of temperature absorption can reach balance faster.In the time of 30 ~ 40 ℃, reaching adsorption equilibrium needs 30min; 50 ~ 60 ℃, reaching adsorption equilibrium needs 20min; 70 ~ 80 ℃, reaching adsorption equilibrium only needs 10min.And along with the rising of adsorption temp, the rare earth adsorptive capacity also has raising to a certain extent.Illustrate that improving temperature can not only accelerate the ion velocity of diffusion, reduces starting time, and can also improve equilibrium adsorption capacity.
Figure 10 is in embodiment 6, T=30 ℃, and pH=5 ~ 7 o'clock, PB-CNP and La
3+, Gd
3+, Yb
3+, Y
3+The absorption relation curve.Can find out, PB-CNP and this three kinds of rare earth ions can both adsorb, wherein, and 1mg PB-CNP and La
3+Saturated extent of adsorption be 216 about μ g, with Gd
3+Saturated extent of adsorption be 243 about μ g, with Yb
3+Saturated extent of adsorption be 254 about μ g, with Y
3+Saturated extent of adsorption be 160 about μ g..
Figure 11 is in embodiment 7, T=30 ℃, and during pH=2, during V=50mL, the desorption graph of a relation of adsorbent.As seen from the figure: contain La
3+The desorption rate of adsorbent Rare Earth Ion be 199 μ g, contain Gd
3+The desorption rate of adsorbent Rare Earth Ion be 187 μ g, contain Yb
3+The desorption rate of adsorbent Rare Earth Ion be 198 μ g, contain Y
3+The desorption rate of adsorbent Rare Earth Ion be 146 μ g.Its desorption rate gets final product complete desorb in 90% left and right through 2-3 desorb, reaches the purpose of recovering rare earth.Also can be designed to the adverse current desorption mode rare earth desorption efficiency is further improved, obtain the stripping liquid of higher concentration, be beneficial to post precipitation or extraction recovery.
Figure 12 is in embodiment 7, reclaims the graph of a relation of absorption again of PB-CNP.As seen from the figure: the PB-CNP of recovery still has adsorptive power, compares to some extent when just the adsorptive capacity of rare earth ion being followed first the use to descend.Wherein, to La
3+Adsorptive capacity be 125 about μ g, to Gd
3+Adsorptive capacity be 131 about μ g, to Yb
3+Adsorptive capacity be 78 about μ g, to Y
3+Adsorptive capacity be 108 about μ g, still the adsorptive capacity than general sorbent material is high.
Specific embodiments:
Embodiment 1: with FeCl
3 .6H
2O and K
4Fe (CN)
6Be raw material, according to 1:1.2(K
4Fe (CN)
6Slightly excessive in to guarantee to obtain gluey PB) mol ratio accurately take corresponding raw material, under room temperature, after being dissolved in respectively in distilled water, with FeCl
3Solution slowly dropwise adds K
4Fe (CN)
6In solution, after stirring 15min, add a small amount of acetone, standing, centrifugal, namely get solid-state PB after natural air drying.Its particle size distribution figure is seen Fig. 1.Synthetic PB-CNP is distributed to respectively the pH=1 of 20mL, 2,3,4,5, in 6,7,8,9 the aqueous solution, its PB-CNP concentration is 0.1mg/mL.Centrifugal with the rotating speed of 6000 rev/mins on supercentrifuge after standing 3h, get supernatant liquor and survey absorbancy, calculate the not amount of sedimentation PB-CNP according to the typical curve of PB-CNP, thereby extrapolate the amount of the PB of sedimentation.Its relation curve is seen Fig. 2.
Embodiment 2: under room temperature, respectively at the pH=3 that contains 1mg PB-CNP, add the Gd of different amounts in 4,5,6,7 the aqueous solution
3+(10 ~ 300 μ g), standing adsorption is high speed centrifugation after 3 hours, with remaining PB-CNP amount in the colorimetric method for determining supernatant liquor, investigates the PB-CNP coagulation property that the absorption due to rare earth ion causes.Take the condition of pH=3 as example, get 12 parts of colloid aqueous solutions that contain 1mg PB in beaker, add respectively 10 μ g/mLGd
3+Solution 5,8,9,10,11,12,13,14,15,20,25,30mL, standing adsorption 3h after stirring, high speed centrifugation is got supernatant liquor and is surveyed absorbancy, calculates the not amount of sedimentation PB-CNP according to the typical curve of PB, thereby extrapolates the amount of the PB of sedimentation.PH=4 ~ 7 relation curves are also made with same method.Its adsorption curve is seen Fig. 3.
Embodiment 3: under constant temperature (T=30 ℃) constant volume (50mL) oscillating condition, measure 1mg PB-CNP to 300 μ g Gd
3+Adsorptive capacity change curve under different pH and balance time conditions.Concrete experimental technique is: as example, six dialysis tubings that 10mL 0.2mg/mL PB is housed are put into respectively Erlenmeyer flask under the pH=2 condition, add respectively 60mL 10 μ g/mL Gd
3+After 10mL distilled water, regulator solution arrives the pH that sets, and the constant temperature oscillation different time (10 ~ 60min), get supernatant liquor, (survey absorbancy, according to Gd with residual gadolinium concentration in azo arsenic III determination of color solution
3+Typical curve calculate the Gd that is not adsorbed
3+Amount), calculate the Gd that has been adsorbed by PB with minusing
3+Amount.With the gadolinium adsorptive capacity, the time is mapped, the adsorption curve that obtains under condition of different pH is seen Fig. 4.
Embodiment 4: at T=30 ℃, pH=5 ~ 7 during V=50mL, in water bath with thermostatic control vibration groove, are used the colloidal solution that contains 1mg PB-CNP and contain 100 μ g, 200 μ g, 300 μ g, 400 μ g Gd
3+Solution Contact-sorption different time (0 ~ 60min), measure gadolinium concentration to the relation that affects of adsorptive capacity and time of equilibrium adsorption.With 1mg PB-CNP to 100 μ g Gd
3+Be adsorbed as example, six dialysis tubings that 10mL 0.1mg/mL PB-CNP is housed are put into respectively Erlenmeyer flask, add respectively 10mL 10 μ g/mL Gd
3+After 30mL distilled water, and the constant temperature oscillation different time (10 ~ 60min), get supernatant liquor, by gadolinium concentration residual in the azo arsenic III determination of color solution in embodiment 3 and calculate the Gd that is adsorbed by PB
3+Amount.Measure equally, respectively Gd
3+Adsorpting data during=200 μ g ~ 400 μ g.With the gadolinium adsorptive capacity, the time is mapped, the adsorption curve that obtains under different gadolinium concentrations conditions is seen Fig. 5.Result shows: PB-CNP is to Gd
3+Time of equilibrium adsorption in about 30min.
In fixedly adsorption time and temperature, and pH value of solution is worth measuring respectively PB-CNP to 250 μ g, 280 μ g, 500 μ g Gd under condition (setting T=30 ℃, t=30min, pH=5 ~ 7)
3+Absorption.The data obtained is mapped as Fig. 6 to the gadolinium concentration in the solution of equilibrium water with adsorptive capacity together with the above results, is PB-CNP to Gd
3+Adsorption isothermal line.Simultaneously, also map to such an extent that its relation curve is seen Fig. 7 with adsorptive capacity to the initial gadolinium concentration in the aqueous solution, the percentage ratio that is adsorbed with gadolinium ion in solution is to the initial concentration Fig. 8 that maps to get.
Embodiment 5:pH=5 ~ 7 are during V=50mL, PB-CNP(1mg) and Gd
3+(200 μ g) is about the relation curve of temperature change.Take T=30 ℃ as example, six dialysis tubings that 10mL 0.2mg/mL PB-CNP is housed are put into respectively Erlenmeyer flask, add respectively 40mL 10 μ g/mL Gd
3+After, constant temperature oscillation 10 ~ 60min gets supernatant liquor, by gadolinium concentration residual in the azo arsenic III determination of color solution in embodiment 3 and calculate the Gd that is adsorbed by PB
3+Amount.Relation curve during T=40 ~ 80 ℃ is also made with same method.Its adsorption curve is seen Fig. 9.
Embodiment 6:T=30 ℃, pH=5 ~ 7 o'clock, V=50mL, 1mg PB-CNP and 300 μ g La
3+, Gd
3+, Yb
3+, Y
3+The absorption relation curve.With 1mg PB-CNP to 300 μ g Gd
3+Be adsorbed as example, six dialysis tubings that 10mL 0.2mg/mL PB-CNP is housed are put into respectively Erlenmeyer flask, add respectively 30mL 10 μ g/mL Gd
3+After 10mL distilled water, and the constant temperature oscillation different time (10 ~ 60min), get supernatant liquor, by gadolinium concentration residual in the azo arsenic III determination of color solution in embodiment 3 and calculate the Gd that is adsorbed by PB-CNP
3+Amount.Similarly, La
3+, Yb
3+, Y
3+The absorption relation curve also make with same method.Its adsorption curve is seen Figure 10.
Embodiment 7:T=30 ℃, pH=2, during V=50mL, constant temperature oscillation 2h, PB-CNP and La in water bath with thermostatic control vibration groove
3+, Gd
3+, Yb
3+, Y
3+Adsorbent desorption can occur, and its desorption rate is larger.Its relation curve is seen Figure 11.
Embodiment 8:T=30 ℃, during pH=4, V=50mL, constant temperature oscillation 40min in water bath with thermostatic control vibration groove sees the dialysis bag that contains 1mgPB and La after desorption
3+, Gd
3+, Yb
3+, Y
3+The absorption situation.With it to 300 μ g Gd
3+Be adsorbed as example, the dialysis bag that contains PB after desorption is constantly rinsed with the clear water vibration, until its pH=5 left and right, add the follow-up persistent oscillation of micro-citric acid, after PB disperses homogeneous, constantly rinse with the clear water vibration, until about its pH=5, discard clear water, add 30mL 10 μ g/mL Gd
3+After 10mL distilled water, constant temperature oscillation 10 ~ 60min gets supernatant liquor, by gadolinium concentration residual in the azo arsenic III determination of color solution in embodiment 3 and calculate the Gd that is adsorbed by PB
3+Amount.Itself and La
3+, Yb
3+, Y
3+Relation curve also make with same method.Its relation curve is seen Figure 12.
Claims (2)
1. one kind is utilized Prussian blue colloidal nanoparticles PB-CNP as the method for sorbent material recovering rare earth from earth solution, it is characterized in that: utilize PB-CNP to the strong adsorpting characteristic of rare earth ion and the dialysis membrane selection perviousness to rare earth ion, PB-CNP aaerosol solution and dialyzer are combined into adsorb the elementary cell of rare earth from rare earth feed liquid, this rare earth ion that is adsorbed can get off with the dilute acid soln desorb easily, and then reaches the purpose of rare-earth enrichment recovery;
Said method comprising the steps of:
(1) with FeCl
3 .6H
2O and K
4Fe (CN)
6Be raw material, accurately take corresponding raw material according to the mol ratio of 1:1.05～1:1.2, be dissolved in respectively in distilled water, at room temperature with FeCl
3Solution drops to K
4Fe (CN)
6In solution, add proper amount of acetone after stirring, standing a moment, centrifugation, natural air drying obtains the PB-CNP solid;
(2) PB-CNP that is synthesized is distributed to the colloidal solution that can obtain high stability in water, and packs into by in the made sack of dialyzer, obtain to be directly used in the elementary cell of absorption rare earth ion; This elementary cell of adsorbing rare earth ion by PB-CNP and dialysis tubing can be used for of forming also can be without separating out the PB-CNP solid, but directly will react the PB-CNP colloidal solution that the generates dialysis tubing of packing into, allows the complete K of unreacted in pure water
4Fe (CN)
6Dialysis out gets final product afterwards;
The dialysis tubing that (3) PB-CNP colloidal solution will be housed contacts with pending rare earth feed liquid, and rare earth ion sees through fenestra and adsorbed by PB-CNP; The pH value of processed earth solution is between 4-7.5, and rare earth concentration is not limit;
(4) process with dilute acid soln the PB-CNP suspension that absorption has rare earth ion, rare earth is desorbed, and then reach the purpose of rare-earth enrichment recovery; The pH value of desorb acid solution is less than 4, and the rare earth stripping liquid of gained can with general precipitator method recovering rare earth, also can be directly used in the configuration rare earth feed liquid and advance the extracting and separating operation;
(5) also can adopt membrane module to realize the efficient adsorption of rare earth ion, wherein PB-CNP colloidal solution and the pending rare earth feed liquid different passages that are placed in respectively film both sides are gone against the stream, and reach the efficiently concentrating effect.
2. the method for the Prussian blue colloidal nanoparticles of a kind of use described according to right 1 recovering rare earth from earth solution: it is characterized in that: film used is to allow water, metal ion, small molecules negatively charged ion and neutral molecule to pass through, and particle diameter is greater than the intransitable symmetric membrane of the particle of 10nm or asymmetric membrane.
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