CN102352448A - 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 method of utilizing Prussian blue colloidal nanoparticles (PB-CNP) from earth solution, to reclaim rare earth as sorbent material.
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; 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 in the Rare Earth Production process, produces has obtained paying close attention to widely in recent years, especially studies 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.
In the recovery process of southern ion type rareearth resource, can produce a large amount of low concentration of rare earth leach liquor or waste water; Especially soak in the technology of ore deposit in the original place; The concentration of leach liquor can reach 2g/L even more than the 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.And the leaching tail washings that is lower than this concentration does not often directly reclaim but is used for circulation and soaks the ore deposit.Meanwhile; Since the original place soak the ore deposit to soak the amount that agent IR in ore deposit soaks than the pond big; It is residual in the ore body that to soak the ore deposit agent content also higher; In the ore deposit residual soak the ore deposit agent can be when moving with the ore deposit with leaching water in rare earth in residual rare earth or the 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 reclaim, rare earth and electrolyte content in the Environmental Water are increased, accelerate rare earth and run off influence ecological environment, or even drinking water safety.In a single day rare earth ion gets into environment, can not be by biological degradation, can hide for a long time in environment along with food chain gets into human body, and in human body, accumulate, cause various diseases and dysfunction, be detrimental to health.
Rare-earth enrichment recovery ionic method has much from low concentration of rare earth feed liquid or waste water.The most simply be the precipitator method, complicated any extraction process, reverse osmosis method and ion-exchange-resin process etc. are arranged.Reclaim in the rare earth scheme in the precipitator method, normally make solution be alkalescence with the lime neutralization, make rare earth separate out precipitation of hydroxide and with a large amount of water sepn.This method is simple, but because the water yield is big, 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.Although extraction process enrichment efficient is high, the enrichment multiple is big, compares too for a short time, and the extraction agent solution loss is big, cost high with also not thoroughly solution of problems such as secondary pollution is big.
Summary of the invention:
The objective of the invention is deficiency, a kind of short-cut method that can from low concentration of rare earth feed liquid or waste water, thoroughly remove rare earth ion and reclaim is provided to prior art.
The technical scheme that the present invention takes: utilize PB-CNP to the strong adsorpting characteristic of rare earth ion and dialysis membrane selection perviousness to rare earth ion; PB-CNP aaerosol solution and dialyzer are combined into the elementary cell that can from rare earth feed liquid or low concentration of rare earth waste water, adsorb rare earth; 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 by weighing corresponding raw material, be dissolved in respectively in the zero(ppm) water, at room temperature with FeCl according to the mol ratio of 1:1.05～1:1.2
3Drips of solution adds to K
4Fe (CN)
6In the solution, add small amount of acetone after stirring, leave standstill a moment, spinning, natural air drying obtains the PB-CNP solid;
[2] the synthetic PB-CNP of institute is distributed to the colloidal solution that can obtain high stability in the water; And pack into by in the made sack of dialyzer; Obtain directly being used to adsorb the elementary cell of 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, in pure water, lets the intact K of unreacted
4Fe (CN)
6Dialysis gets final product after coming out;
Contact in the dialysis tubing that [3] PB-CNP colloidal solution will be housed and the pending rare earth feed liquid, rare earth ion can be adsorbed by PB-CNP after getting into inner bag through fenestra.This dialysis tubing that PB-CNP suspension-s is housed can adsorb rare earth ion to come up from solution.The pH value of the earth solution that is processed be preferably between the 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+S-adsorption be respectively 216 μ g, 243 μ g, 254 μ g are about 160 μ g;
[4] handle the PB-CNP suspension-s that is adsorbed with rare earth ion with dilute acid soln, 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 use the general precipitator method to reclaim rare earth, also can directly be used to dispose rare earth feed liquid and advance the extracting and separating operation;
[5] meanwhile, also can adopt membrane module to realize the efficient absorption of rare earth ion, wherein PB-CNP colloidal solution and pending rare earth feed liquid place in the film respectively, the outer different passages of film go against the stream, and reach the efficiently concentrating effect.
The invention has the beneficial effects as follows: have the advantage that simple, the rare earth loaded amount of technology is big and rare earth yield is high; Can be widely used in the rare earth feed liquid of rare earth mine, separation plant; Especially low concentration of rare earth waste water middle-weight rare earths ionic removes fully and reclaims, and is with a wide range of applications.
Description of drawings:
Fig. 1 is the particle size distribution figure of the PB nanoparticle of preparation among the embodiment 1, can find out that the granularity of the PB-CNP that the present invention is prepared is that D50 is less than 100nm.
Fig. 2 is among the embodiment 1, and the coagulation performance that PB-CNP is dispersed in particle behind the aqueous solution of different pH relatively.Can know that by 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 type PB-CNP can not stable existence, and the colloidal property of PB-CNP is destroyed and coagulation takes place under stronger acidic conditions; And at basic soln; Then decompose owing to the hydrolysis of iron produces FeOOH, especially pH 9 o'clock, decomposition faster.
Fig. 3 is among the embodiment 2, and under the room temperature, pH=3 ~ 7 o'clock contain the Gd of the aqueous solution of 1mg PB-CNP in the difference amount
3+There is the coagulation quantitative change curve of PB down in (10 ~ 300 μ g) because PB-CNP has the intensive adsorpting characteristic to rare earth, when the negative charge on PB-CNP surface by rare earth in after the coagulation of colloidal particle can take place.The Gd of X-coordinate for adding
3+Amount (0 ~ 300) μ g, ordinate zou are because Gd
3+The PB sinkability that causes of adding.Can know by 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 both 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 of pH value of solution and adding; In the acidity scope of pH=5 ~ 7, the gadolinium amount of the last 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 among the 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 adsorbed Gd of every mgPB
3+Amount, its initial consumption is 300 μ g.Reach in a basic balance by absorption after scheming to find out 30min.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 reached capacity, and its s-adsorption is about 240 ~ 250 μ g.The result can confirm according to diagram, and the optimal ph scope of PB-CNP absorption rare earth ion is 5-7.Can go up the desorb rare earth with pH from the saturated PB that is adsorbed with rare earth ion less than 4 solution, and pH is equal to or less than 2 solution and can gets off the rare earth ion desorb that is adsorbed on the PB.
Fig. 5 is among the 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 adsorbed Gd of every mg PB-CNP
3+Amount, its initial consumption is respectively 100 μ g, 200 μ g, 300 μ g, 400 μ g.Can find out that by last figure absorption can reach in a basic balance behind the 30min, and every mg PB-CNP is to Gd
3+S-adsorption be about 240 ~ 250 μ g.
Fig. 6 is that PB-CNP is to Gd among the embodiment 4
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 PB-CNP during for balance and goes up Gd
3+Concentration.
Fig. 7 is that PB-CNP is to Gd among the embodiment 4
3+The absorption relation curve of (0 ~ 500 μ g).Wherein X-coordinate is Gd
3+Starting point concentration, ordinate zou loads on PB-CNP during for balance and goes up Gd
3+Concentration.
Fig. 8 is that PB-CNP is to Gd among the embodiment 4
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 among the embodiment 5, pH=5 ~ 7 o'clock, and temperature change is to PB-CNP (1mg) absorption Gd
3+(200 μ g) influences relation curve.Visible by figure, between 30 ~ 80 ℃, along with the rising absorption of temperature 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.Explain that improving temperature can not only accelerate ion diffusion speed, reduces starting time, and can also improve equilibrium adsorption capacity.
Figure 10 is among the 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 that PB-CNP and this three kinds of rare earth ions can both adsorb, wherein, 1mg PB-CNP and La
3+S-adsorption be about 216 μ g, with Gd
3+S-adsorption be about 243 μ g, with Yb
3+S-adsorption be about 254 μ g, with Y
3+S-adsorption be about 160 μ g..
Figure 11 is among the embodiment 7, T=30 ℃, and during pH=2, during V=50mL, the desorption graph of a relation of adsorbent.Can know by figure: contain La
3+Adsorbent middle-weight rare earths ionic desorption rate be 199 μ g, contain Gd
3+Adsorbent middle-weight rare earths ionic desorption rate be 187 μ g, contain Yb
3+Adsorbent middle-weight rare earths ionic desorption rate be 198 μ g, contain Y
3+Adsorbent middle-weight rare earths ionic desorption rate be 146 μ g.Its desorption rate gets final product complete desorb through 2-3 desorb about 90%, reach the purpose that reclaims 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 among the embodiment 7, reclaims the graph of a relation of absorption again of PB-CNP.Can be known by 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 about 125 μ g, to Gd
3+Adsorptive capacity be about 131 μ g, to Yb
3+Adsorptive capacity be about 78 μ g, to Y
3+Adsorptive capacity be about 108 μ g, still high than the adsorptive capacity of general sorbent material.
Specific embodiments:
Embodiment 1: with FeCl
3 .6H
2O and K
4Fe (CN)
6Be raw material, according to 1:1.2 (K
4Fe (CN)
6Excessive in slightly to guarantee to obtain gluey PB) mol ratio accurately take by weighing corresponding raw material, under the room temperature, be dissolved in the zero(ppm) water respectively after, with FeCl
3Solution slowly dropwise adds K
4Fe (CN)
6In the solution, behind the stirring 15min, add small amount of acetone, leave standstill, centrifugal, promptly get solid-state PB behind the natural air drying.Its particle size distribution figure is seen Fig. 1.Synthetic PB-CNP is distributed to the pH=1 of 20mL respectively, 2,3,4,5, in 6,7,8,9 the aqueous solution, its PB-CNP concentration is 0.1mg/mL.Leave standstill behind the 3h centrifugally with 6000 rev/mins rotating speed on supercentrifuge, get supernatant and survey absorbancy, calculate the not amount of sedimentation PB-CNP according to the typical curve of PB-CNP, thereby extrapolate the amount of settled PB.Its relation curve is seen Fig. 2.
Embodiment 2: under the room temperature,, add the Gd of different amounts in 4,5,6,7 the aqueous solution respectively at the pH=3 that contains 1mg PB-CNP
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, investigates because the PB-CNP coagulation characteristic that absorption caused of rare earth ion.Condition with pH=3 is an example, gets 12 parts of colloid aqueous solutions that contain 1mg PB in beaker, adds 10 μ g/mLGd respectively
3+ Solution 5,8,9,10,11,12,13,14,15,20,25,30mL stirs back standing adsorption 3h, and high speed centrifugation is got supernatant and is surveyed absorbancy, calculates the not amount of sedimentation PB-CNP according to the typical curve of PB, thereby extrapolates the amount of settled PB.PH=4 ~ 7 relation curves are also used with quadrat method and are made.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: to be example under the pH=2 condition, six dialysis tubings that 10mL 0.2mg/mL PB is housed are put into Erlenmeyer flask respectively, add 60mL 10 μ g/mL Gd respectively
3+Behind 10mL zero(ppm) water, regulator solution arrives the pH that sets, and the constant-temperature shaking different time (10 ~ 60min), get supernatant, (survey absorbancy, with gadolinium concentration residual in the azo arsenic III determination of color solution according to Gd
3+Typical curve calculate the Gd that is not adsorbed
3+Amount), calculate by the Gd of PB absorption with minusing
3+Amount.With the gadolinium adsorptive capacity time is mapped, the adsorption curve that obtains under the 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 are contained 100 μ g, 200 μ g, 300 μ g, 400 μ g Gd
3+Solution contact absorption different time (0 ~ 60min), measure gadolinium concentration adsorptive capacity and the influence of adsorption equilibrium time concerned.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 Erlenmeyer flask respectively, add 10mL 10 μ g/mL Gd respectively
3+Behind 30mL zero(ppm) water, and the constant-temperature shaking different time (10 ~ 60min), get supernatant, by gadolinium concentration residual in the azo arsenic III determination of color solution among the embodiment 3 and calculate by the Gd of PB absorption
3+Amount.Measure Gd equally, respectively
3+Adsorpting data during=200 μ g ~ 400 μ g.With the gadolinium adsorptive capacity time is mapped, the adsorption curve that obtains under the different gadolinium concentrations conditions is seen Fig. 5.The result shows: PB-CNP is to Gd
3+The adsorption equilibrium time about 30min.
In fixedly adsorption time and temperature, and pH value of solution is worth measuring PB-CNP respectively to 250 μ g, 280 μ g, 500 μ g Gd under the condition (setting T=30 ℃, t=30min, pH=5 ~ 7)
3+Absorption.The gained data are mapped like Fig. 6 to the gadolinium concentration in the solution of equilibrium water with adsorptive capacity with The above results, are PB-CNP to Gd
3+Adsorption isothermal line.Simultaneously, also map to such an extent that its relation curve is seen Fig. 7 to the initial gadolinium concentration in the aqueous solution with adsorptive capacity, the percentage ratio that is adsorbed with gadolinium ion in the solution to initial concentration map Fig. 8.
Embodiment 5:pH=5 ~ 7, during V=50mL, PB-CNP (1mg) and Gd
3+(200 μ g) is about the relation curve of temperature change.With T=30 ℃ be example, six dialysis tubings that 10mL 0.2mg/mL PB-CNP is housed are put into Erlenmeyer flask respectively, add 40mL 10 μ g/mL Gd respectively
3+After, constant-temperature shaking 10 ~ 60min gets supernatant, by gadolinium concentration residual in the azo arsenic III determination of color solution among the embodiment 3 and calculate by the Gd of PB absorption
3+Amount.Relation curve during T=40 ~ 80 ℃ is also used with quadrat method and is made.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 Erlenmeyer flask respectively, add 30mL 10 μ g/mL Gd respectively
3+Behind 10mL zero(ppm) water, and the constant-temperature shaking different time (10 ~ 60min), get supernatant, by gadolinium concentration residual in the azo arsenic III determination of color solution among the embodiment 3 and calculate by the Gd of PB-CNP absorption
3+Amount.Similarly, La
3+, Yb
3+, Y
3+The absorption relation curve also use and make with quadrat method.Its adsorption curve is seen Figure 10.
Embodiment 7:T=30 ℃, pH=2, during V=50mL, constant-temperature shaking 2h, PB-CNP and La in water bath with thermostatic control vibration groove
3+, Gd
3+, Yb
3+, Y
3+Adsorbent desorption can take place, and its desorption rate is bigger.Its relation curve is seen Figure 11.
Embodiment 8:T=30 ℃, during pH=4, V=50mL, constant-temperature shaking 40min in water bath with thermostatic control vibration groove sees dialysis bag that contains 1mgPB and La behind the desorption
3+, Gd
3+, Yb
3+, Y
3+The absorption situation.With it to 300 μ g Gd
3+Be adsorbed as example, with the dialysis bag that contains PB behind the desorption constantly with clear water vibration flushing, until about its pH=5; Add micro-Hydrocerol A continued vibration, after PB disperses homogeneous, constantly with clear water vibration flushing; Until about its pH=5, discard clear water, add 30mL 10 μ g/mL Gd
3+Behind 10mL zero(ppm) water, constant-temperature shaking 10 ~ 60min gets supernatant, by gadolinium concentration residual in the azo arsenic III determination of color solution among the embodiment 3 and calculate by the Gd of PB absorption
3+Amount.Itself and La
3+, Yb
3+, Y
3+Relation curve also use and make with quadrat method.Its relation curve is seen Figure 12.
Claims (4)
1. method of utilizing Prussian blue colloidal nanoparticles (PB-CNP) from earth solution, to reclaim rare earth as sorbent material; It is characterized in that: utilize PB-CNP the strong adsorpting characteristic of rare earth ion and dialysis membrane selection perviousness to rare earth ion; PB-CNP aaerosol solution and dialyzer are combined into the elementary cell that can from rare earth feed liquid or low concentration of rare earth waste water, adsorb rare earth; 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 by weighing corresponding raw material, be dissolved in respectively in the zero(ppm) water, at room temperature with FeCl according to the mol ratio of 1:1.05～1:1.2
3Drips of solution adds to K
4Fe (CN)
6In the solution, add proper amount of acetone after stirring, leave standstill a moment, spinning, natural air drying obtains the PB-CNP solid;
(2) the synthetic PB-CNP of institute is distributed to the colloidal solution that can obtain high stability in the water, and packs by in the made sack of dialyzer the elementary cell that obtains directly being used to adsorb rare earth ion into;
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, in pure water, lets the intact K of unreacted
4Fe (CN)
6Dialysis gets final product after coming out;
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 the earth solution that is processed be preferably between the 5-7, and rare earth concentration is not limit between 4-7.5;
(4) handle the PB-CNP suspension-s that is adsorbed with rare earth ion with dilute acid soln, 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 use the general precipitator method to reclaim rare earth, also can directly be used to dispose rare earth feed liquid and advance the extracting and separating operation;
(5) also can adopt membrane module to realize the efficient absorption of rare earth ion, wherein PB-CNP colloidal solution places the different passages of film both sides to go against the stream respectively with pending rare earth feed liquid, reaches the efficiently concentrating effect.
2. from low concentration of rare earth solution, reclaim the method for rare earth according to the Prussian blue colloidal nanoparticles of right 1 described a kind of usefulness: it is characterized in that: used film is to allow water, metals ion, small molecules negatively charged ion and neutral molecule to pass through, and particle diameter is greater than intransitable symmetric membrane of the particle of 10nm or asymmetric membrane.
3. from low concentration of rare earth solution, reclaim the method for rare earth according to the Prussian blue colloidal nanoparticles of right 1 described a kind of usefulness: it is characterized in that: the pH value of the earth solution that is processed is preferably between the 5-7, and rare earth concentration is not limit.
4. from low concentration of rare earth solution, reclaim the method for rare earth according to the Prussian blue colloidal nanoparticles of right 1 described a kind of usefulness: it is characterized in that: the pH value of desorb acid solution is best less than 2.
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| CN103418166A (en) * | 2013-08-05 | 2013-12-04 | 南昌大学 | Method for adsorbing and separating low-concentration rare earth ions with oxidized graphene colloid |
| CN105714114A (en) * | 2016-04-22 | 2016-06-29 | 江西省科学院应用化学研究所 | Method for adsorbing enriched rare earth ions from low-concentration rare earth lixivium through fungus A-Fu03 thalli |
| CN111239347A (en) * | 2020-03-27 | 2020-06-05 | 暨南大学 | Method for detecting desorption rate of organic matters in solid waste |
| WO2024051095A1 (en) * | 2022-09-05 | 2024-03-14 | 广东邦普循环科技有限公司 | Recycling method for waste prussian sodium battery positive electrode material, and use |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418166A (en) * | 2013-08-05 | 2013-12-04 | 南昌大学 | Method for adsorbing and separating low-concentration rare earth ions with oxidized graphene colloid |
| CN105714114A (en) * | 2016-04-22 | 2016-06-29 | 江西省科学院应用化学研究所 | Method for adsorbing enriched rare earth ions from low-concentration rare earth lixivium through fungus A-Fu03 thalli |
| CN111239347A (en) * | 2020-03-27 | 2020-06-05 | 暨南大学 | Method for detecting desorption rate of organic matters in solid waste |
| WO2024051095A1 (en) * | 2022-09-05 | 2024-03-14 | 广东邦普循环科技有限公司 | Recycling method for waste prussian sodium battery positive electrode material, and use |
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| Publication number | Publication date |
|---|---|
| CN102352448B (en) | 2013-06-19 |
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