CN109161684A - A method of utilizing spirulina recovering rare earth - Google Patents
A method of utilizing spirulina recovering rare earth Download PDFInfo
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- CN109161684A CN109161684A CN201811340817.8A CN201811340817A CN109161684A CN 109161684 A CN109161684 A CN 109161684A CN 201811340817 A CN201811340817 A CN 201811340817A CN 109161684 A CN109161684 A CN 109161684A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention provides a kind of methods using spirulina recovering rare earth, comprising: S1, spirulina centrifugal treating, gathering screw algal biomass obtain spirulina adsorbent；S2, the spirulina adsorbent is mixed with earth solution, carries out oscillation absorption；S3, diluted acid are mixed with the spirulina adsorbent after the absorption rare earth ion, carry out desorption, recovering rare earth ion.Spirulina is adsorbed rare earth ion as a kind of new adsorbent by the method for above-mentioned spirulina recovering rare earth from low concentration of rare earth solution, and cultural method is simple, and condition limitation is few, has good adsorption effect to low concentration of rare earth solution.
Description
Technical field
The present invention relates to the separation and recovery technology fields of rare earth, and in particular to a kind of side using spirulina recovering rare earth
Method.
Background technique
Area is widely distributed (such as Ganzhou) with Rare Earth Mine existing for ion phase morphology in south China, often adopts at present
Realize that the exploitation of rare earth element is utilized with ammonium sulfate in_situ leaching method.But as rich ore is by preferential development, the Rare Earth Mine that leaves
Quality reduces increasingly, and leachate rare earth concentration is lower and lower, and subsequent Extraction of rare eart and separating difficulty increase.Further, since residual
Rare earth remaining in mine can be brought into the river on mine point periphery by the leaching mine agent stayed, even into lithic drainage, to cause water body
The loss of pollution and rare earth resources.Rare earth once enters human body, will cause various diseases, is detrimental to health.It can be seen that from low dense
Rare-earth enrichment recovery technology, which has become, in degree rare-earth liquid and waste water solves the important of current rare earth Domain resources and environmental problem
Approach and means.Currently, having " precipitation method " and " non precipitating method " from the technical method of Rare Earth Mine leachate Extraction of rare earth." precipitating
Method " includes oxalate precipitation method, ammonium bicarbonate precipitation method and precipitating-floatation, but the generally existing environmental pollution of these methods is asked
Topic, and when earth solution concentration is lower (1-100mg/L), traditional chemical precipitation method treatment effect is undesirable.It is " non-heavy
Shallow lake method " includes direx process, ion-exchange and microorganism adsorption method, and wherein microorganism adsorption method is because it is with raw material sources
Extensively, environmental-friendly, adsorption effect is good and has a good application prospect.
A kind of fungi A-Fu03 thallus is disclosed in Chinese patent literature CN105714114A from low concentration of rare earth leachate
The method of middle absorption enrichment rare earth ion obtains fungi suction by cultivating aspergillus oryzae Aspergillus oryzae sp.A-Fu03
Attached dose, adsorbent and the low concentration of rare earth solution of preparation carry out mixing oscillation absorption, recycle the dilute hydrochloric acid of 0.5-1mol/L into
Row desorption, thus rare-earth enrichment recovery ion.This method has at low cost, environment by fungi rare-earth enrichment recovery ion
Friendly advantage, but fungi absorption rare earth ion is active adsorption process in this method, dependent on living body fungi to rare earth ion
Active intake is carried out, thus is influenced by cell age, rare earth ion toxicity etc., to influence adsorption effect, and fungal culture connects
It repeatedly to be sterilized before kind, condition of culture is more harsh.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming in the prior art using living microorganism adsorbent, training
The condition of supporting is harsh, adsorption effect defect easily affected by various factors, thus provide a kind of culture simply, condition suffered by adsorbent
Limit a kind of few method using spirulina recovering rare earth.
For this purpose, the present invention provides a kind of methods using spirulina recovering rare earth, comprising:
S1, spirulina centrifugal treating, gathering screw algal biomass obtain spirulina adsorbent；
S2, the spirulina adsorbent is mixed with earth solution, carries out oscillation absorption；
S3, diluted acid with it is described absorption rare earth ion after spirulina adsorbent mix, progress desorption, recovering rare earth from
Son.
The method using spirulina recovering rare earth, spirulina algae is put into Zarrouk culture medium, cold light source
3000lx continuous illumination, revolving speed and temperature are set as 90rpm and 25 DEG C, carry out shaking table culture, obtain the spirulina.
The method using spirulina recovering rare earth, in S1 step, by the collected spiral algal biomass into
Row drying and grinding, and screened through 75-100 μm of sieve.
The method using spirulina recovering rare earth, in S2 step, the dosage of spirulina adsorbent is every liter
The earth solution at least 2g.
The method using spirulina recovering rare earth, in S2 step, the rare earth mixed with spirulina adsorbent is molten
Liquid intermediate ion concentration is not more than 100mg/L.
The method using spirulina recovering rare earth, in S2 step, the temperature for vibrating absorption is 25 DEG C, and pH value is
5。
The method using spirulina recovering rare earth, in S2 step, oscillation adsorption time is at least 60min.
The method using spirulina recovering rare earth, in the S3 step, the dilute acid soln are dilute hydrochloric acid, dilute nitre
One of acid, EDTA.
The method using spirulina recovering rare earth, the concentration of the dilute acid soln are 0.05-0.1mol/L.
The method using spirulina recovering rare earth, the rare earth ion being adsorbed are one of erbium, ytterbium, praseodymium
Or it is several.
The method using spirulina recovering rare earth, the earth solution is from southern area of China with ion shape
Rare Earth Mine existing for state.
Technical solution of the present invention has the advantages that
1. a kind of method using spirulina recovering rare earth provided by the invention, comprising: S1, spirulina centrifugal treating are received
Collect spiral algal biomass, obtains spirulina adsorbent；S2, the spirulina adsorbent is mixed with earth solution, is vibrated
Absorption；S3, diluted acid are mixed with the spirulina adsorbent after the absorption rare earth ion, carry out desorption, recovering rare earth ion.On
The method using spirulina recovering rare earth stated, for spirulina as adsorbent, cultural method is simple, and its absorption rare earth ion is
Chelatropic reaction is carried out using spirulina surface functional group abundant and rare earth ion, is passive adsorption, sorbent suspension is not active, dilute
The influence of native ion toxicity etc., adsorption effect is good and effect stability.
2. spirulina algae is put into Zarrouk training by a kind of method using spirulina recovering rare earth provided by the invention
It supports in base, cold light source 3000lx continuous illumination, revolving speed and temperature are set as 90rpm and 25 DEG C, carry out shaking table culture, obtain described
Spirulina.Under this condition, spirulina can preferably be grown, to obtain enough spiral algal biomass.
3. a kind of method using spirulina recovering rare earth provided by the invention, in S1 step, by the collected spiral shell
Grinding is dried in rotation algal biomass, and screens through 75-100 μm of sieve, can get the spirulina powder between 75-100 μm,
So that spirulina has biggish adsorption area in adsorption process, the rate of adsorption is improved, achievees the effect that quick adsorption.
4. a kind of method using spirulina recovering rare earth provided by the invention, in S2 step, spirulina adsorbent
Dosage is the every liter of earth solution at least 2g, by the way that enough spirulina adsorbents are added, can reach higher absorption effect
Rate.
5. a kind of method using spirulina recovering rare earth provided by the invention, in S2 step, with spirulina adsorbent
Mixed earth solution intermediate ion concentration is not more than 100mg/L, and spirulina adsorbent has low concentration of rare earth solution good
Adsorption effect, and by the ion concentration of control earth solution, it can reach higher adsorption efficiency.
6. a kind of method using spirulina recovering rare earth provided by the invention vibrates the temperature of absorption in S2 step
It is 25 DEG C, pH value 5 can reach higher adsorption efficiency and adsorbance by the temperature and pH value of control oscillation absorption.
7. a kind of method using spirulina recovering rare earth provided by the invention, in S2 step, oscillation adsorption time is
At least 60min can reach higher adsorption efficiency by oscillation absorption prolonged enough.
8. a kind of method using spirulina recovering rare earth provided by the invention, in the S3 step, the dilute acid soln is
One of dilute hydrochloric acid, dust technology, EDTA will can preferably be adsorbed on spiral using one of these types of dilute acid soln
Rare earth ion on algae desorbs.
9. a kind of method using spirulina recovering rare earth provided by the invention, the concentration of the dilute acid soln is 0.05-
The rare earth ion of absorption can sufficiently be desorbed in the concentration range, reach higher desorption efficiency by 0.1mol/L.
10. a kind of method using spirulina recovering rare earth provided by the invention, the rare earth ion being adsorbed be erbium,
One or more of ytterbium, praseodymium use spirulina for adsorbent these types of rare earth ion, can achieve good absorption
Effect.
Detailed description of the invention
In order to illustrate more clearly of the technical solution in the specific embodiment of the invention, specific embodiment will be retouched below
Attached drawing needed in stating is briefly described, it should be apparent that, the accompanying drawings in the following description is some realities of the invention
Mode is applied, it for those of ordinary skill in the art, without creative efforts, can also be attached according to these
Figure obtains other attached drawings.
Fig. 1 is the method flow diagram provided by the invention using spirulina recovering rare earth.
Fig. 2 is the adsorption efficiency relational graph of the absorption of spirulina under different ph values rare earth ion of the invention.
Fig. 3 is the adsorbance graph of relation that spirulina under different ph values of the invention adsorbs rare earth ion.
Fig. 4 is influence relational graph of the dosage of different adsorbents in the present invention to adsorption efficiency.
Fig. 5 is influence relational graph of the initial rare earth ion concentration to adsorption efficiency in the present invention.
Fig. 6 is the graph of relation of different adsorption times and adsorption efficiency in the present invention.
Fig. 7 is in the present invention while to adsorb the relational graph for interfering adsorption efficiency when a variety of rare earth ions between each ion.
Fig. 8 is the desorption efficiency relational graph of present invention strippant each under various concentration.
Specific embodiment
Spirulina involved in following embodiments is blunt top spirulina, and algae is commercial product, purchased from algae in Jiangxi
Biotech inc, Zarrouk culture medium are voluntarily prepared by laboratory, are formed as follows:
Table 1Zarrouk culture medium composition
| Component | Dosage (g/L) |
| NaHCO3 | 16.80 |
| K2HPO4 | 0.50 |
| NaNO3 | 2.50 |
| K2SO4 | 1.00 |
| MgSO4·7H2O | 0.20 |
| CaCl2 | 0.04 |
| FeSO4·7H2O | 0.01 |
| EDTA | 0.08 |
| H3BO3 | 2.86 |
| MnCl2·4H2O | 1.81 |
| ZnSO4 | 0.22 |
| CuSO4 | 0.02 |
| MoO3 | 0.01 |
The preparation method of Zarrouk culture medium is as follows: take 1L deionized water in beaker, according to dosage listed by table 1 according to
The secondary each component that weighs is added in beaker, sufficiently dissolves, it should be noted that the sequence according to table 1 is successively added, if wrong order can
It can cause to precipitate, a kind of in the case where adding again after former component is completely dissolved, after finally addition is completed, culture medium is transparent
Clear solution, component are that analysis is pure.
Embodiment 1
Present embodiments provide a kind of method using spirulina recovering rare earth, comprising:
S1, culture spirulina, spirulina algae are put into Zarrouk culture medium, cold light source 3000lx continuous illumination, are turned
Speed and temperature are set as 90rpm and 25 DEG C, shaking table culture 14 days, obtain spirulina；The spirulina that culture is completed is through centrifuge
8min is centrifuged under 8000rmp, obtained spiral algal biomass is put into baking oven in 70 DEG C of dryings by gathering screw algal biomass
For 24 hours, it and is ground, is screened through 75-100 μm of sieve, obtain spirulina adsorbent, stored spare；
S2, the spirulina adsorbent for taking 2g/L and 50ml 100mg/L erbium ion (Er3+) solution mixing, carry out oscillation suction
Attached, temperature is 25 DEG C, and pH value is set to 2,3,4,5,6, and oscillation adsorption time is 60min.
Pass through adsorption efficiency (%)=(C0-Ce)/C0× 100% measures adsorption efficiency, wherein C0It (mg/L) is initial dilute
Native ion concentration, Ce(mg/L) be adsorption equilibrium when solution rare earth ion concentration.Rare earth ion in solution is according to Chinese state
" GB/T 18115.11-2006 single-channel scanning inductively coupled plasma atomic emission (ICP-AES) method " in family's standards system
It is measured.
As seen from Figure 2, as pH=5, adsorption efficiency highest reaches 92%, it can thus be appreciated that reach highest absorption
Efficiency should keep pH value of solution=5.
Embodiment 2
According to the same manner as in Example 1 utilize spirulina recovering rare earth, be a difference in that earth solution type be ytterbium from
Son (Yb3+) solution.
As seen from Figure 2, as pH=5, adsorption efficiency highest reaches 87.62%, it can thus be appreciated that reach highest suction
Attached efficiency should keep pH value of solution=5.
Embodiment 3
According to the same manner as in Example 1 utilize spirulina recovering rare earth, be a difference in that earth solution type be praseodymium from
Son (Pr3+) solution.
As seen from Figure 2, as pH=5, adsorption efficiency highest reaches 86.15%, it can thus be appreciated that reach highest suction
Attached efficiency should keep pH value of solution=5.
Embodiment 4
Present embodiments provide a kind of method using spirulina recovering rare earth, comprising:
S1, culture spirulina, spirulina algae are put into Zarrouk culture medium, cold light source 3000lx continuous illumination, are turned
Speed and temperature are set as 90rpm and 25 DEG C, shaking table culture 14 days, obtain spirulina；The spirulina that culture is completed is through centrifuge
8min is centrifuged under 8000rmp, obtained spiral algal biomass is put into baking oven in 70 DEG C of dryings by gathering screw algal biomass
For 24 hours, it and is ground, is screened through 75-100 μm of sieve, obtain spirulina adsorbent, stored spare；
S2, the spirulina adsorbent for taking 2g/L and 50ml 100mg/L erbium ion (Er3+) solution mixing, carry out oscillation suction
Attached, temperature is 25 DEG C, and pH value is set to 2,3,4,5,6, and oscillation adsorption time is 60min.
Pass through adsorbance=(C0-Ce) V/M measures adsorbance, wherein C0It (mg/L) is initial rare earth ion concentration, CeFor
Rare earth ion concentration when adsorption equilibrium in solution, V (L) are liquor capacity, and M (g) is adsorbent dosage.Rare earth in solution
Ion is according to " the GB/T18115.11-2006 single-channel scanning inductively coupled plasma body transmitting light in chinese national standard system
Spectrum (ICP-AES) method " it is measured.
As seen from Figure 3, as pH=5, adsorbance is maximum, is 46mg/g, it can thus be appreciated that reach maximal absorptive capacity,
It should keep pH value of solution=5.
Embodiment 5
According to the same manner as in Example 4 utilize spirulina recovering rare earth, be a difference in that earth solution type be ytterbium from
Son (Yb3+) solution.
As seen from Figure 3, as pH=5, adsorbance is maximum, is 43.81mg/g, it can thus be appreciated that reach maximum adsorption
Amount, should keep pH value of solution=5.
Embodiment 6
According to the same manner as in Example 4 utilize spirulina recovering rare earth, be a difference in that earth solution type be praseodymium from
Son (Pr3+) solution.
As seen from Figure 3, as pH=5, adsorbance is maximum, is 43.075mg/g, it can thus be appreciated that reach maximum suction
Attached amount should keep pH value of solution=5.
Embodiment 7
Present embodiments provide a kind of method using spirulina recovering rare earth, comprising:
S1, culture spirulina, spirulina algae are put into Zarrouk culture medium, cold light source 3000lx continuous illumination, are turned
Speed and temperature are set as 90rpm and 25 DEG C, shaking table culture 14 days, obtain spirulina；The spirulina that culture is completed is through centrifuge
8min is centrifuged under 8000rmp, obtained spiral algal biomass is put into baking oven in 70 DEG C of dryings by gathering screw algal biomass
For 24 hours, it and is ground, is screened through 75-100 μm of sieve, obtain spirulina adsorbent, stored spare；
S2, the spirulina adsorbent and 50ml 100mg/L for taking 0.4g/L, 1g/L, 2g/L, 4g/L, 6g/L, 8g/L respectively
Erbium ion (Er3+) solution mixing, oscillation absorption is carried out, temperature is 25 DEG C, and pH value 5, oscillation adsorption time is 60min.
Pass through adsorption efficiency (%)=(C0-Ce)/C0× 100% measures adsorption efficiency, wherein C0It (mg/L) is initial dilute
Native ion concentration, Ce(mg/L) be adsorption equilibrium when solution rare earth ion concentration.Rare earth ion in solution is according to Chinese state
" GB/T 18115.11-2006 single-channel scanning inductively coupled plasma atomic emission (ICP-AES) method " in family's standards system
It is measured.
As seen from Figure 4, when spirulina dosage is 2g/L, adsorption efficiency reaches balance, continues to add spirulina,
Adsorption efficiency variation is no longer obvious, it can thus be appreciated that dosage should be at least 2g/L.
Embodiment 8
According to the same manner as in Example 7 utilize spirulina recovering rare earth, be a difference in that earth solution type be ytterbium from
Son (Yb3+) solution.
As seen from Figure 4, when spirulina dosage is 2g/L, adsorption efficiency reaches balance, continues to add spirulina,
Adsorption efficiency variation is no longer obvious, it can thus be appreciated that dosage should be at least 2g/L.
Embodiment 9
According to the same manner as in Example 7 utilize spirulina recovering rare earth, be a difference in that earth solution type be praseodymium from
Son (Pr3+) solution.
As seen from Figure 4, when spirulina dosage is 2g/L, adsorption efficiency reaches balance, continues to add spirulina,
Adsorption efficiency variation is no longer obvious, it can thus be appreciated that dosage should be at least 2g/L.
Embodiment 10
Present embodiments provide a kind of method using spirulina recovering rare earth, comprising:
S1, culture spirulina, spirulina algae are put into Zarrouk culture medium, cold light source 3000lx continuous illumination, are turned
Speed and temperature are set as 90rpm and 25 DEG C, shaking table culture 14 days, obtain spirulina；The spirulina that culture is completed is through centrifuge
8min is centrifuged under 8000rmp, obtained spiral algal biomass is put into baking oven in 70 DEG C of dryings by gathering screw algal biomass
For 24 hours, it and is ground, is screened through 75-100 μm of sieve, obtain spirulina adsorbent, stored spare；
S2, take the spirulina adsorbent of 2g/L and 50ml concentration be respectively 20mg/L, 50mg/L, 100mg/L, 200mg/L,
Erbium ion (the Er of 300mg/L, 500mg/L3+) solution mixing, oscillation absorption is carried out, temperature is 25 DEG C, pH value 5, oscillation absorption
Time is 60min.
Pass through adsorption efficiency (%)=(C0-Ce)/C0× 100% measures adsorption efficiency, wherein C0It (mg/L) is initial dilute
Native ion concentration, Ce(mg/L) be adsorption equilibrium when solution rare earth ion concentration.Rare earth ion in solution is according to Chinese state
" GB/T 18115.11-2006 single-channel scanning inductively coupled plasma atomic emission (ICP-AES) method " in family's standards system
It is measured.
As seen from Figure 5, spirulina behaves oneself best to the adsorption effect of 100mg/L erbium ion solution.
Embodiment 11
According to the same manner as in Example 10 utilize spirulina recovering rare earth, be a difference in that earth solution type be ytterbium from
Son (Yb3+) solution.
As seen from Figure 5, spirulina behaves oneself best to the adsorption effect of 100mg/L ytterbium ion solution.
Embodiment 12
According to the same manner as in Example 10 utilize spirulina recovering rare earth, be a difference in that earth solution type be praseodymium from
Son (Pr3+) solution.
As seen from Figure 5, spirulina behaves oneself best to the adsorption effect of 100mg/L praseodymium ion solution.
Embodiment 13
Present embodiments provide a kind of method using spirulina recovering rare earth, comprising:
S1, culture spirulina, spirulina algae are put into Zarrouk culture medium, cold light source 3000lx continuous illumination, are turned
Speed and temperature are set as 90rpm and 25 DEG C, shaking table culture 14 days, obtain spirulina；The spirulina that culture is completed is through centrifuge
8min is centrifuged under 8000rmp, obtained spiral algal biomass is put into baking oven in 70 DEG C of dryings by gathering screw algal biomass
For 24 hours, it and is ground, is screened through 75-100 μm of sieve, obtain spirulina adsorbent, stored spare；
S2, the spirulina adsorbent for taking 2g/L and 50ml concentration are the erbium ion (Er of 100mg/L3+) solution mixing, it carries out
Oscillation absorption, temperature are 25 DEG C, pH value 5, and the time for vibrating absorption is 0-150min.
Pass through adsorption efficiency (%)=(C0-Ct)/C0× 100% measures the adsorption efficiencies of various time points, wherein C0
It (mg/L) is initial rare earth ion concentration, CtIt (mg/L) is the rare earth ion concentration of various time points solution.Rare earth in solution
Ion is according to " the GB/T 18115.11-2006 single-channel scanning inductively coupled plasma body transmitting light in chinese national standard system
Spectrum (ICP-AES) method " it is measured.
From fig. 6 it can be seen that adsorption efficiency is maximum when absorption proceeds to 60min, hereafter with the progress of time, inhale
Attached efficiency is almost unchanged.
Embodiment 14
By method identical with embodiment 13 utilize spirulina recovering rare earth, be a difference in that earth solution type be ytterbium from
Son (Yb3+) solution.
From fig. 6 it can be seen that adsorption efficiency is maximum when absorption proceeds to 60min, hereafter with the progress of time, inhale
Attached efficiency is almost unchanged.
Embodiment 15
By method identical with embodiment 13 utilize spirulina recovering rare earth, be a difference in that earth solution type be praseodymium from
Son (Pr3+) solution.
From fig. 6 it can be seen that adsorption efficiency is maximum when absorption proceeds to 60min, hereafter with the progress of time, inhale
Attached efficiency is almost unchanged.
Embodiment 16
Present embodiments provide a kind of method using spirulina recovering rare earth, comprising:
S1, culture spirulina, spirulina algae are put into Zarrouk culture medium, cold light source 3000lx continuous illumination, are turned
Speed and temperature are set as 90rpm and 25 DEG C, shaking table culture 14 days, obtain spirulina；The spirulina that culture is completed is through centrifuge
8min is centrifuged under 8000rmp, obtained spiral algal biomass is put into baking oven in 70 DEG C of dryings by gathering screw algal biomass
For 24 hours, it and is ground, is screened through 75-100 μm of sieve, obtain spirulina adsorbent, stored spare；
S2, the spirulina adsorbent for taking 2g/L are added separately to the erbium (Er that 50ml concentration is 100mg/L3+), ytterbium (Yb3 +), praseodymium (Pr3+) in solion, oscillation absorption is carried out, temperature is 25 DEG C, pH value 5, and the time for vibrating absorption is 60min.
Pass through adsorbance=(C0-Ce) V/M measures the adsorbance of each ion, wherein C0It (mg/L) is initial rare earth ion
Concentration, Ce(mg/L) when being adsorption equilibrium solution rare earth ion concentration, V (L) is liquor capacity, and M (g) adds for adsorbent
Amount.Rare earth ion in solution is according to " the GB/T 18115.11-2006 single-channel scanning inductance coupling in chinese national standard system
Plasma emission spectroscopy (ICP-AES) method of conjunction " it is measured.
As shown in Figure 7, spirulina is to erbium (Er3+) ytterbium (Yb3+) praseodymium (Pr3+) this 3 kinds of ions have good absorption, and praseodymium
(Pr3+) adsorption effect it is best, erbium (Er3+) secondly, ytterbium (Yb3+) third.Saturated extent of adsorption be respectively 22.965mg/g,
19.75mg/g、18.27mg/g。
Embodiment 17
Present embodiments provide a kind of method using spirulina recovering rare earth, comprising:
S1, culture spirulina, spirulina algae are put into Zarrouk culture medium, cold light source 3000lx continuous illumination, are turned
Speed and temperature are set as 90rpm and 25 DEG C, shaking table culture 14 days, obtain spirulina；The spirulina that culture is completed is through centrifuge
8min is centrifuged under 8000rmp, obtained spiral algal biomass is put into baking oven in 70 DEG C of dryings by gathering screw algal biomass
For 24 hours, it and is ground, is screened through 75-100 μm of sieve, obtain spirulina adsorbent, stored spare；
S2, the spirulina adsorbent for taking 2g/L are added separately to the erbium (Er that 50ml concentration is 100mg/L3+), ytterbium (Yb3 +), praseodymium (Pr3+) in solion, oscillation absorption is carried out, temperature is 25 DEG C, pH value 5, and the time for vibrating absorption is 60min.
S3, dilute hydrochloric acid (0.05mol/L, 0.1mol/L), dust technology (0.05mol/L, 0.1mol/L), EDTA are taken
(0.05mol/L, 0.1mol/L) 3 kinds of strippants, be added separately to absorption rare earth ion after spirulina in, by rare earth ion solution
It sucks out.
Pass through desorption efficiency (%)=(rare earth ion concentration in strippant/rare earth ion concentration being adsorbed) ×
100% calculates the desorption efficiency of each ion, and the rare earth ion in solution is according to " the GB/T in chinese national standard system
Single-channel scanning inductively coupled plasma atomic emission 18115.11-2006 (ICP-AES) method " it is measured.
As it can be observed in the picture that erbium (Er contained in solution after ion parsing3+) ytterbium (Yb3+) praseodymium (Pr3+) ion concentration is respectively
97.12%, 91.71%, 92.29%, it can thus be appreciated that these three strippants are to erbium (Er3+) ytterbium (Yb3+) praseodymium (Pr3+) this 3 kinds of ions
There is good desorption, and desorption efficiency reaches 90% or more.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of method using spirulina recovering rare earth characterized by comprising
S1, spirulina centrifugal treating, gathering screw algal biomass obtain spirulina adsorbent；
S2, the spirulina adsorbent is mixed with earth solution, carries out oscillation absorption；
S3, diluted acid are mixed with the spirulina adsorbent after the absorption rare earth ion, carry out desorption, recovering rare earth ion.
2. the method according to claim 1 using spirulina recovering rare earth, which is characterized in that spirulina algae to be put into
In Zarrouk culture medium, cold light source 3000lx continuous illumination, revolving speed and temperature are set as 90rpm and 25 DEG C, carry out shaking table training
It supports, obtains the spirulina.
3. the method according to claim 1 or 2 using spirulina recovering rare earth, which is characterized in that, will in S1 step
Grinding is dried in the collected spiral algal biomass, and screens through 75-100 μm of sieve.
4. the method according to claim 1 to 3 using spirulina recovering rare earth, which is characterized in that in S2 step
In, the dosage of spirulina adsorbent is the every liter of earth solution at least 2g.
5. the method according to claim 1 to 4 using spirulina recovering rare earth, which is characterized in that in S2 step
In, the earth solution intermediate ion concentration mixed with spirulina adsorbent is no more than 100mg/L.
6. -5 any method using spirulina recovering rare earth according to claim 1, which is characterized in that in S2 step
In, the temperature for vibrating absorption is 25 DEG C, pH value 5.
7. -6 any method using spirulina recovering rare earth according to claim 1, which is characterized in that in S2 step
In, oscillation adsorption time is at least 60min.
8. -7 any method using spirulina recovering rare earth according to claim 1, which is characterized in that in S3 step
In, the dilute acid soln is one of dilute hydrochloric acid, dust technology, EDTA.
9. the method according to claim 8 using spirulina recovering rare earth, which is characterized in that the dilute acid soln it is dense
Degree is 0.05-0.1mol/L.
10. -9 any method using spirulina recovering rare earth according to claim 1, which is characterized in that described to be inhaled
Attached rare earth ion is one or more of erbium, ytterbium, praseodymium.
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| CN117025985B (en) * | 2023-08-15 | 2024-04-05 | 中国科学院大学 | Method for recycling rare earth elements from red mud by utilizing acidophilic thermophilic red algae and application |
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