CN103725880A - Extraction system, extraction method and reextraction method - Google Patents
Extraction system, extraction method and reextraction method Download PDFInfo
- Publication number
- CN103725880A CN103725880A CN201410010398.7A CN201410010398A CN103725880A CN 103725880 A CN103725880 A CN 103725880A CN 201410010398 A CN201410010398 A CN 201410010398A CN 103725880 A CN103725880 A CN 103725880A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- water
- extraction
- extraction system
- organic phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses an extraction system, an extraction method and a reextraction method. The extraction system disclosed in the invention comprises an organic phase and an aqueous phase, wherein the organic phase comprises a diluent and an extraction agent shown as a formula I; the aqueous phase comprises rare earth ions; the pH value in the aqueous phase is 2.5-4.5; M is hydrogen, alkali metal ions or positive ammonium ions. The extraction method disclosed in the invention comprises the following steps: oscillating and balancing the extraction system. The reextraction method disclosed in the invention comprises the following steps: (1) saponifying the organic phase of the extraction system, mixing with the aqueous phase containing the rare earth ions, and obtaining an organic phase loaded with the rare earth ions; and (2) mixing the organic phase loaded with the rare earth ions with an aqueous solution of acid. According to the extraction system, the rare earth ions can be efficiently separated under low acidity, the extraction system is high in saturation capacity and difficult in emulsification, realizes reextraction of the rare earth ions under low acidity and is suitable for actual production.
Description
Technical field
The present invention relates to a kind of extraction system, extracting process and reextraction method.
Background technology
The rare earth element magnetic abundant and unique because its unique 4f subgrade electronic structure has, the character such as optical, electrical, it is world developing high-tech and national defence sophisticated technology, the indispensable or alternative strategic materials of rebuilding traditional industry, and is described as " VITAMIN of modern industry " and " novel material treasure-house ".Along with rare earth is in the continuous expansion of high-tech sector range of application, rare earth material demand rapid growth.Rare earth resources consumes too fast, and production process is seriously polluted, and resource high-efficiency and sustainable use have become the Tough questions that must solve.
Currently used extraction agent is probably divided into following several: containing oxygen extraction agent, neutral organophosphorus extractant, acidic extractant, the extraction of amine type, chelating extractant.The extraction of rare earth with separation in often use phosphorous extraction system, Yuan Cheng industry in 1981 etc. have been reported with 2-ethylphosphonic acid single 2-ethyl polyhexamethylene (P507) extraction lanthanon, after this in Rare Earth Separation industry, P507 is able to widespread use, but its regenerability to heavy rare earths is poor.Along with the increase of the ordination number of rare earth element, the back extraction of its organic phase is more and more difficult, especially the back extraction to heavy rare earths thulium, ytterbium, lutetium, its extraction equilibrium time is long, and extraction equilibrium acidity is high, and it is clean that organic phase is difficult for regeneration, and the acid of back extraction consumption is many, causes seriously polluted.The second half in 20th century, U.S. Qing Te company (CYTEC) has produced two (2,4,4-tri-methyl-amyl) phospho acid (Caynex272) and has applied widely as Separation of nickel and cobalt extraction agent.United States Patent (USP) (US5622679) discloses the method for mixture extracting rare-earth element from acidic solution of phospho acid or its salt and another kind of phosphino-compound, centering, heavy rare earth element have good separation factor, back extraction acidity is also lower, but its saturated capacity is low, very easily there is emulsion simultaneously, cause phase-splitting difficulty, and cost is higher, has limited greatly the application of Caynex272 in rare-earth industry.
In addition, naphthenic acid under certain condition to the extracting power of yttrium lower than all other rare earth elements, it has special performance, therefore thinks that it can be used for separating yttrium from all other rare earth elements.But it is a kind of mixture of natural product, composition is extremely complicated, and changes along with place of production difference, and the solubleness in water is larger, easily run off, after life-time service, the component of organic phase can change, and affects the stability of technique, its acidity a little less than, need to be at higher pH(pH>5) under could extracting rare-earth, under this pH condition, many metal ions can be hydrolyzed, and easily occur emulsion, thereby cause phase-splitting difficulty.Therefore, be badly in need of the extraction system of a kind of high efficiency extraction rare earth of exploitation.
Summary of the invention
Technical problem to be solved by this invention be overcome the separation to heavy rare earths existing in the extraction of existing rare-earth separating poor, need to be under the acidity compared with high rare-earth separating, extraction agent purity is low, saturated capacity is low and the defect such as emulsification and a kind of extraction system, extracting process and reextraction method are provided very easily.Extraction system of the present invention can be under lower acidity (pH value is 2.5～4.5), rare-earth separating ion efficiently, simultaneously, the saturated capacity of this extraction system is high, be difficult for emulsification and can realize the reextraction of rare earth ion under low acidity, therefore, be more suitable for actual production.
In the present invention, described extraction agent exists with dimeric form in polar solvent.Formula 1 represents extraction process.In extraction process, the rare earth ion of water enters in organic phase, with the H in extraction agent
+exchange H
+enter water.When other influences factor is fixing, known according to balance moving principle, H
+enter after water, can suppress balance and move right, the amount of the rare earth being extracted can reduce relatively.Meanwhile, the partition ratio D in water and separation factor β are also affected.Visible, H in extraction process
+concentration can limit and affect the generation of extraction process, and therefore pH value is very important influence factor in extraction process.Kex in formula 2 represents that the equilibrium constant extracts and closes constant, and its value is: water H while entering rare earth ion concentration in organic phase and balance
+the product of concentration 3 powers, with the ratio of water rare earth ion concentration 3 powers with free organic phase 3 power products.Wherein, RE represents rare earth ion, and aq represents water, and org represents organic phase, and HL represents extraction agent monomer, because the extraction agent in the present invention is that dimerization form exists in polar solvent, therefore be written as (HL) 2.In formula 3, D is partition ratio, and its value is the rare earth ion of organic phase coordination and the ratio of raffinate water Rare Earth Ion, and raffinate water is the water after extraction equilibrium.In formula 4, β is separation factor, and its value is the ratio of the equilibrium constant of two kinds of metals.
β=Kex
2/Kex
1 （4）
The present invention is mainly achieved through the following technical solutions.
The invention provides a kind of extraction system, it comprises organic phase and water, and described organic phase comprises thinner and suc as formula the extraction agent shown in I; Described water comprises rare earth ion, and the pH value in described water is 2.5～4.5;
Wherein, M is hydrogen, alkalimetal ion or ammonium positive ion.
PH value in described water is preferably 2.5～3.5, is more preferably 2.8～3.5.
Described alkalimetal ion can be the alkalimetal ion of this area routine, is preferably sodium ion or potassium ion.Described ammonium positive ion can be the ammonium positive ion of this area routine, is preferably NH
4 +.
Described suc as formula in the extraction agent shown in I, M is preferably hydrogen.Now, suc as formula the compound shown in I referred to as P227.
Described thinner can be the conventional thinner using of ability, is preferably one or more in sulfonated kerosene, aero oil, kerosene, benzene, toluene, heptane and n-dodecane.
The volumetric molar concentration of described extraction agent in thinner can be the volumetric molar concentration of this area routine, be preferably 0.2mol/L～2.5mol/L, be more preferably 0.2mol/L～1.5mol/L, be 0.8mol/L～1.5mol/L best, wherein, described volumetric molar concentration refers to that the amount of substance of extraction agent accounts for the ratio of the volume of the thinner that contains extraction agent.
Described rare earth ion is the rare earth ion of this area routine, and described rare earth ion is preferably La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+and Y
3+in one or more, more preferably for comprising above-mentioned 15 kinds of rare earth ions.
The preparation method who contains the water of rare earth ion can prepare according to the method for this area routine, and in the present invention, the preparation method of the described water containing rare earth ion, preferably comprises the following step: rare earth oxide is reacted with acid.Described rare earth oxide refers to that rare earth element and oxygen element are in conjunction with the compound forming.The method of described reaction and condition are method and the condition of this area routine.
The organic phase of described extraction system can be comparing of ability routine compared with water, is preferably 10:1～1:10, is more preferably 5:1～1:5, and wherein, described comparing refers to the volume ratio of organic phase and water.The volumetric molar concentration of the rare earth ion in described water can be volumetric molar concentration conventional in the water of this area, be preferably 0.01mol/L～3.5mol/L, wherein, described volumetric molar concentration refers to that the amount of substance of rare earth ion accounts for the ratio of the volume of the water that contains rare earth ion.
In described extraction system, preferably also can comprise salting-out agent.Described salting-out agent can be salting-out agent conventional in the extraction system of this area, are preferably sodium-chlor and/or sodium perchlorate.The consumption of described salting-out agent can be the consumption of this area routine, and preferably, the volumetric molar concentration of described salting-out agent in water is 0.1mol/L～4mol/L, and described volumetric molar concentration refers to that the amount of substance of salting-out agent accounts for the ratio of salting-out agent aqueous solution volume.
Described extraction system refers to the system before vibration balance.
The present invention also provides a kind of extracting process, and it comprises the following steps: foregoing extraction system vibration balance.The method of described vibration balance and condition can be this area routine method and condition, the time of described vibration balance is preferably 5min～30min.
The present invention also provides a kind of reextraction method, and it comprises the following steps:
(1) by the organic phase of described extraction system after saponification, and mixes containing the water of rare earth ion, the balance of vibrating, obtains the organic phase of supported rare earth ion; Wherein, the pH value of the described water containing rare earth ion is 2.5～4.5;
(2) organic phase of described supported rare earth ion is mixed with aqueous acid.
In step (1), the pH value of the described water containing rare earth ion is preferably 2.5～3.5, is more preferably 2.8～3.5.Described rare earth ion is the rare earth ion of this area routine, and described rare earth ion is preferably La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+and Y
3+in one or more, more preferably for containing above-mentioned 15 kinds of rare earth ions.The method of described saponification and condition can be method and the condition of this area routine, and in the present invention, the method for described saponification preferably comprises the following step: by the aqueous solution of described extraction system and alkali.During the terminal of described saponification, in described extraction system, 30%～95% extraction agent is by saponification, and described per-cent refers to the per-cent that is accounted for extraction agent total mass by the quality of the extraction agent of saponification.Preferably, during the terminal of described saponification, in described extraction system, 40%～85% extraction agent is by saponification.Wherein, the volumetric molar concentration of the aqueous solution of described alkali is preferably 6mol/L～10mol/L, and described volumetric molar concentration refers to that the amount of substance of alkali accounts for the ratio of alkali aqueous solution cumulative volume.Described alkali can be the alkali of this area routine, is preferably mineral alkali and/or organic bases.Described mineral alkali is preferably sodium hydroxide and/or lithium hydroxide.Described organic bases is preferably ammoniacal liquor.
In step (1), the pH value of the water after described vibration balance is preferably 2.6～4.2, is more preferably 2.6～3.8.The organic phase of described extraction system is preferably 10:1～1:10 with being in a ratio of of water containing rare earth ion, is more preferably 5:1～1:5, and described comparing refers to the volume ratio of organic phase and water.The described volumetric molar concentration containing the rare earth ion in the water of rare earth ion can be the volumetric molar concentration of this area routine, be preferably 0.01mol/L～3.5mol/L, described volumetric molar concentration refers to that the amount of substance of rare earth ion accounts for the ratio containing the volume of the water of rare earth ion.The time of described vibration balance can be the time of this area routine, is preferably 5min～30min, is more preferably 30min.
In step (2), described aqueous acid can be the conventional aqueous acid using in this area.Acid in described aqueous acid is preferably mineral acid.Described mineral acid is preferably one or more in hydrochloric acid, sulfuric acid and nitric acid, is more preferably hydrochloric acid.The volumetric molar concentration of described aqueous acid is preferably 0.01mol/L～2.8mol/L, and described volumetric molar concentration refers to that sour amount of substance accounts for the ratio of aqueous acid cumulative volume.The organic phase of described supported rare earth ion is preferably 10:1～1:10 compared with aqueous acid, and described comparing refers to the volume ratio of organic phase and aqueous acid.After the EO of described mixing, preferably, also comprise the operation of the balance of vibrating.The time of described vibration balance can be the time of this area routine, is preferably 5min～30min.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
1, the pH value of the water of extraction system of the present invention is rare-earth separating ion efficiently in 2.5～4.5 scopes, average separation coefficient reaches 3.2～3.6, particularly separation to middle-weight rare earths (Sm, Eu, Gd), heavy rare earths (Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) is the best extraction system of counterweight Rare Earth Separation effect of finding at present.
2, extraction system of the present invention when extracting rare-earth ion saturated capacity for 0.14～0.17(saturated capacity be the amount of the portative rare earth ion of 1mol extraction agent), and be difficult for emulsification, be much better than similar extraction system (as Caynex272).
3, extraction system of the present invention; the acidity of its reextraction is low; especially the back extraction to Heavy rare earth; the volumetric molar concentration of hydrochloric acid is 0.5mol/L～2.8mol/L; far below existing extraction system (as: P507 extraction system is 6mol/L to the volumetric molar concentration of the hydrochloric acid in the back extraction of heavy rare earths); greatly save soda acid consumption, when reducing production costs, reduced pollutant emission, be conducive to protection of the environment.In addition it is complete by back extraction that extraction system of the present invention can make the rare earth ion in load organic phases, improved the purity of rare earth ion.
Accompanying drawing explanation
Fig. 1 is four grouping effect figure of embodiment 1 extraction system.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
Raw material in following embodiment, as do not illustrated, is purchase gained.
Extraction agent Caynex272: purchased from U.S. Qing Te company, can use after purifying.Purification process is according to document: Huang, K.L., Li, Z.G., Chen, L.L., 1994.Purification of2-ethylhexyl phosphonic acidmono-2-ethylhexyl ester by precipitation of cobalt (II) mono-(2-ethylhexyl)-2-ethylhexyl phosphate.J.Cent.South Univ.Technol. (Nat.Sci.) 25 (2), the content of the 3rd section of record of 252-256.(document page 2)
Extraction agent P507 and extraction agent P204: purchased from Luoyang Zhong Da Chemical Co., Ltd., can after purifying, use.Purification process is according to document: Yuan Chengye etc., and 1981, chemical journal, 881～894.(content of the 2nd section of record of reference literature page 4)
Water containing rare earth ion is that rare earth oxide is reacted with hydrochloric acid, makes rare earth chloride.Wherein, the valence state of rare earth ion is+3 valencys.
Embodiment 1
The volumetric molar concentration of extraction agent P227 in benzene is 0.2mol/L, wherein, containing the pH value in the water of rare earth ion, be 2.5, the volumetric molar concentration of water Rare Earth Ion is 0.01mol/L, salting-out agent are sodium-chlor, its volumetric molar concentration is 1mol/L, organic phase and water be in a ratio of 2:1, duration of oscillation is 20min.After the phase-splitting of vibration balance, analyze the rare earth ion concentration in water or reextraction organic phase, extraction data are in Table 1.Wherein, average separation coefficient is 3.16, and far above the data of finding report, as shown in Figure 1, so-called four divide into groups effects to its four groupings effect: La, Ce, Pr, Nd are first group; Sm, Eu, Gd are second group; Gd, Tb, Dy, Ho are the 3rd group; Y, Er, Tm, Yb, Lu are the 4th group, and wherein, Gd is the shared element of second group and the 3rd group.Separation factor maximum in four groupings between the 1st and the 2nd element of each grouping, the separation factor minimum between the 3rd and the 4th element, can find by Fig. 1, extraction agent P227 is better to the selectivity of rare earth ion, can effectively separate adjacent element.
Table 1
| Ion | Extraction is closed constant (Kex) | Separation factor (β) | Ion | Extraction is closed constant (Kex) | Separation factor (β) |
| La 3+ | 1.65×10 -7 | / | Tb 3+ | 6.00×10 -4 | 5.61 |
| Ce 3+ | 1.72×10 -6 | 10.42 | Dy 3+ | 0.0009 | 1.63 |
| Pr 3+ | 5.60×10 -6 | 3.35 | Ho 3+ | 0.0020 | 2.18 |
| Nd 3+ | 7.73×10 -6 | 1.38 | Y 3+ | 0.0039 | 1.93 |
| Sm 3+ | 4.77×10 -5 | 6.17 | Er 3+ | 0.0041 | 1.06 |
| Eu 3+ | 6.92×10 -5 | 1.45 | Tm 3+ | 0.013 | 3.11 |
| Gd 3+ | 1.07×10 -4 | 1.55 | Yb 3+ | 0.035 | 2.75 |
| / | / | / | Lu 3+ | 0.055 | 1.58 |
Embodiment 2
The volumetric molar concentration of the sodium salt of extraction agent P227 in kerosene is 0.2mol/L, wherein, containing the pH value in the water of rare earth ion, be 2.5, the volumetric molar concentration of water rare earth ion is 0.01mol/L, salting-out agent are sodium-chlor, its volumetric molar concentration is 1mol/L, and organic phase and water are in a ratio of 2:1, and duration of oscillation is 20min.After the phase-splitting of vibration balance, analyze the rare earth ion concentration in water or reextraction organic phase, extraction data are identical with the experimental result that embodiment 1 does, and data are in Table 1.Visible is basically identical by the result of extraction agent being carried out to saponification and the experimental data of not carrying out saponification, and this provides certain reference for industrial application.
Embodiment 3
The volumetric molar concentration of extraction agent P227 in n-dodecane is 0.5mol/L, wherein, containing the pH value in the water of rare earth ion, be 2.8, the volumetric molar concentration of water rare earth ion is 0.01mol/L, salting-out agent are sodium-chlor, its volumetric molar concentration is 1mol/L, and organic phase and water are in a ratio of 1:1, and duration of oscillation is 30min.After the phase-splitting of vibration balance, analyze the rare earth ion concentration in water or reextraction organic phase, extraction data are in Table 2.Wherein, average separation coefficient is 3.32, and far above the data of finding report, as shown in Figure 1, so-called four divide into groups effects to its four groupings effect: La, Ce, Pr, Nd are first group; Sm, Eu, Gd are second group; Gd, Tb, Dy, Ho are the 3rd group; Y, Er, Tm, Yb, Lu are the 4th group, and wherein, Gd is the shared element of second group and the 3rd group.Separation factor maximum in four groupings between the 1st and the 2nd element of each grouping, separation factor minimum between the 3rd and the 4th element, can find by Fig. 1, extraction agent P227 is better to the selectivity of rare earth ion, can effectively separate adjacent element, have higher application prospect.
Table 2
| Ion | Extraction is closed constant (Kex) | Separation factor (β) | Ion | Extraction is closed constant (Kex) | Separation factor (β) |
| La 3+ | 1.67×10 -7 | / | Tb 3+ | 7.90×10 -4 | 5.81 |
| Ce 3+ | 2.08×10 -6 | 12.46 | Dy 3+ | 0.0013 | 1.65 |
| Pr 3+ | 7.24×10 -6 | 3.48 | Ho 3+ | 0.0028 | 2.18 |
| Nd 3+ | 1.00×10 -5 | 1.38 | Y 3+ | 0.0056 | 1.96 |
| Sm 3+ | 6.09×10 -5 | 6.07 | Er 3+ | 0.0056 | 1.00 |
| Eu 3+ | 8.77×10 -5 | 1.44 | Tm 3+ | 0.017 | 3.11 |
| Gd 3+ | 1.36×10 -4 | 1.55 | Yb 3+ | 0.048 | 2.77 |
| / | / | / | Lu 3+ | 0.075 | 1.58 |
Embodiment 4
The concentration of extraction agent P227 in n-dodecane is 1mol/L, containing the pH value in the water of rare earth ion, is 3, and water rare earth ion concentration is 0.05mol/L, salting-out agent are sodium-chlor, its volumetric molar concentration is 2mol/L, and organic phase and water are in a ratio of 1:1, and duration of oscillation is 30min.Extraction data are in Table 3, its average separation coefficient is 3.3, far above the data of finding report, its four groupings effect conforms to Fig. 1, the separation factor maximum in four groupings between the 1st and the 2nd element of each grouping, the separation factor minimum between the 3rd and the 4th element, by Fig. 1, can find, extraction agent P227 is better to the selectivity of rare earth ion, can effectively separate adjacent element, in pH value, is that 3 o'clock effects are better.
Table 3
| Ion | Extraction is closed constant (Kex) | Separation factor (β) | Ion | Extraction is closed constant (Kex) | Separation factor (β) |
| La 3+ | 6.70×10 -7 | / | Tb 3+ | 3.60×10 -3 | 3.09 |
| Ce 3+ | 8.42×10 -6 | 12.57 | Dy 3+ | 1.08×10 -2 | 3.01 |
| Pr 3+ | 2.41×10 -5 | 2.86 | Ho 3+ | 1.18×10 -2 | 1.09 |
| Nd 3+ | 3.972×10 -5 | 1.65 | Y 3+ | 2.73×10 -2 | 2.31 |
| Sm 3+ | 1.64×10 -4 | 4.14 | Er 3+ | 4.56×10 -2 | 1.67 |
| Eu 3+ | 3.37×10 -4 | 2.05 | Tm 3+ | 1.56×10 -1 | 3.43 |
| Gd 3+ | 1.17×10 -3 | 3.46 | Yb 3+ | 4.36×10 -1 | 2.79 |
| / | / | / | Lu 3+ | 1.01 | 2.32 |
Embodiment 5
The concentration of extraction agent P227 in n-dodecane is 1mol/L, containing the pH value in the water of rare earth ion, is 3.5, and water rare earth ion concentration is 0.05mol/L, salting-out agent are sodium-chlor, its volumetric molar concentration is 2mol/L, and organic phase and water are in a ratio of 1:2, and duration of oscillation is 30min.Extraction data are in Table 4, its average separation coefficient is 3.33, far above the data of finding report, its four groupings effect conforms to Fig. 1, the separation factor maximum in four groupings between the 1st and the 2nd element of each grouping, the separation factor minimum between the 3rd and the 4th element, by Fig. 1, can find, extraction agent P227 is better to the selectivity of rare earth ion, can effectively separate adjacent element, in pH value, is that 3.5 o'clock effects are better.
Table 4
| Ion | Extraction is closed constant (Kex) | Separation factor (β) | Ion | Extraction is closed constant (Kex) | Separation factor (β) |
| La 3+ | 8.36×10 -7 | / | Tb 3+ | 7.51×10 -3 | 5.45 |
| Ce 3+ | 7.65×10 -6 | 9.15 | Dy 3+ | 1.74×10 -2 | 2.32 |
| Pr 3+ | 2.36×10 -5 | 3.08 | Ho 3+ | 3.07×10 -2 | 1.76 |
| Nd 3+ | 2.87×10 -5 | 1.22 | Y 3+ | 4.48×10 -3 | 1.46 |
| Sm 3+ | 1.48×10 -4 | 5.15 | Er 3+ | 8.28×10 -2 | 1.85 |
| Eu 3+ | 5.86×10 -4 | 3.96 | Tm 3+ | 2.76×10 -1 | 3.33 |
| Gd 3+ | 1.38×10 -3 | 2.35 | Yb 3+ | 7.89×10 -1 | 2.86 |
| / | / | / | Lu 3+ | 2.11 | 2.67 |
Embodiment 6
The concentration of extraction agent P227 in kerosene is 2mol/L, containing the pH value in the water of rare earth ion, is 3.5, and water rare earth ion concentration is 0.5mol/L, and salting-out agent are that sodium chloride concentration is 2mol/L, and organic phase and water are in a ratio of 1:3, and duration of oscillation is 30min.Its separating effect to rare earth ion is better, can reach data shown in table 4, its average separation coefficient is 3.33, and far above the data of finding report, its four groupings effect conforms to Fig. 1, separation factor maximum in four groupings between the 1st and the 2nd element of each grouping, separation factor minimum between the 3rd and the 4th element, can find by Fig. 1, extraction agent P227 is better to the selectivity of rare earth ion, can effectively separate adjacent element, be that 3.5 o'clock effects are better in pH value.
Embodiment 7
The concentration of extraction agent P227 in kerosene is 2.5mol/L, containing the pH value in the water of rare earth ion, is 4.5, and water rare earth ion concentration is 0.5mol/L, salting-out agent are sodium-chlor, its volumetric molar concentration is 4mol/L, and organic phase and water are in a ratio of 5:1, and duration of oscillation is 10min.Its separating effect to rare earth ion is better, can reach data shown in table 2, and its average separation coefficient is 3.32, and far above the data of finding report, its four groupings effect conforms to Fig. 1.
Embodiment 8
Back extraction acid effect
The extraction agent using is P227, thinner is n-dodecane, the concentration of P227 is 1mol/L, to after organic phase saponification, fully contact repeatedly with the water containing rare earth ion, until water Rare Earth Ion concentration no longer changes, now organic phase is saturated, saturated organic phase is stripped with the hydrochloric acid of different concns, experimental data is as shown in table 4, by table 5 data, find, the reextraction acidity of this extraction system is lower, the heavy rare earths Tm of difficult reextraction, Yb, Lu is all complete by back extraction when the volumetric molar concentration of hydrochloric acid is 1mol/L～1.8mol/L, reextraction successful is better than P507 and C272, be the reextraction found at present the best containing phosphine organic extractant.Simultaneously, P227 to light, in, the reextraction of Heavy rare earth can adopt staging treating, at concentration of hydrochloric acid, can effectively isolate La, Ce, Pr, Nd during lower than 0.1mol/L, concentration of hydrochloric acid separates middle-weight rare earths Sm, Eu, Gd, Tb, Dy between 0.1mol/L～0.5mol/L time, separates Heavy rare earth Y, Ho～Lu when concentration of hydrochloric acid is greater than 0.8mol/L.
Table 5
Comparative example 1
Its structure of extraction agent Caynex272 is
with P227 structural similitude, the concentration in n-dodecane is 0.5mol/L, containing the pH value in the water of rare earth ion, is 2.8, water rare earth ion concentration is 0.01mol/L, and salting-out agent are sodium-chlor, and its volumetric molar concentration is 1mol/L, organic phase and water are in a ratio of 1:1, and duration of oscillation is 30min.Extraction data are in Table 5, and its separation efficiency to heavy rare earths is poor compared with P227.Its average separation coefficient is 2.31, far below the average separation coefficient of P227, by the data of table 6, also can find, study the Kex of extraction agent extracting rare-earth all with the ordination number of lanthanon, increase, i.e. dwindling of ionic radius and rising.Near contiguous P-C atom, the existence of side chain, has reduced to a certain extent percentage extraction, but has been not that every kind of structure can obtain the high-performance as P227.Can not effectively separate adjacent element.
Table 6
| Ion | Extraction is closed constant (Kex) | Separation factor (β) | Ion | Extraction is closed constant (Kex) | Separation factor (β) |
| La 3+ | 9.13×10 -9 | / | Tb 3+ | 5.47×10 -4 | 3.55 |
| Ce 3+ | 1.46×10 -8 | 1.6 | Dy 3+ | 1.22×10 -3 | 1.46 |
| Pr 3+ | 8.80×10 -7 | 2.75 | Ho 3+ | 2.76×10 -3 | 2.27 |
| Nd 3+ | 4.05×10 -7 | 0.46 | Y 3+ | 3.64×10 -3 | 1.32 |
| Sm 3+ | 1.53×10 -6 | 3.78 | Er 3+ | 5.36×10 -3 | 1.47 |
| Eu 3+ | 2.73×10 -6 | 1.78 | Tm 3+ | 0.016 | 2.91 |
| Gd 3+ | 1.54×10 -5 | 5.64 | Yb 3+ | 0.034 | 2.12 |
| / | / | / | Lu 3+ | 0.041 | 1.22 |
Comparative example 2
Extraction agent P507, its structure is
concentration in n-dodecane is 1mol/L, containing the pH value in the water of rare earth ion, is 3, and water rare earth ion concentration is 0.05mol/L, and salting-out agent are sodium-chlor, and its volumetric molar concentration is 1mol/L, and organic phase and water are in a ratio of 1:1, and duration of oscillation is 30min.Extraction data are in Table 7, and its separation efficiency to heavy rare earths is poor compared with P227.Its average separation coefficient is 2.15, because pH value is higher, the percentage extraction of later element T b-Lu, the Y of Gd is all greater than 99%, and the separating effect between element is poor, and the extraction agent that is not therefore every kind of structure can be obtained the high-performance as P227 within the scope of specific pH value.
Table 7
| Ion | Extraction is closed constant (Kex) | Separation factor (β) | Ion | Extraction is closed constant (Kex) | Separation factor (β) |
| La 3+ | 4.71×10 -3 | / | Tb 3+ | 4.33 | 3.44 |
| Ce 3+ | 9.09×10 -3 | 1.93 | Dy 3+ | 6.32 | 1.46 |
| Pr 3+ | 4.06×10 -2 | 4.46 | Ho 3+ | 8.03 | 1.27 |
| Nd 3+ | 4.09×10 -2 | 1.01 | Y 3+ | 8.19 | 1.02 |
| Sm 3+ | 1.24×10 -1 | 3.72 | Er 3+ | 8.76 | 1.07 |
| Eu 3+ | 2.16×10 -1 | 1.74 | Tm 3+ | 8.85 | 1.01 |
| Gd 3+ | 1.26 | 5.84 | Yb 3+ | 9.91 | 1.12 |
| / | / | / | Lu 3+ | 10.01 | 1.01 |
Comparative example 3
Extraction agent P204, its structure is
concentration in n-dodecane is 1mol/L, containing the pH value in the water of rare earth ion, is 3, and water rare earth ion concentration is 0.05mol/L, and salting-out agent are sodium-chlor, and its volumetric molar concentration is 1mol/L, and organic phase and water are in a ratio of 1:1, and duration of oscillation is 30min.Experiment finds, P204 is when the extraction of this pH value scope, and except the percentage extraction of La is 97.4%, other element all 100% is extracted in organic phase, there is no separating effect between rare earth ion, and not to be useful in pH value be to separate rare earth ion at 3 o'clock to this extraction agent as seen.
Effect embodiment
The comparison of the saturated capacity of different extraction agents, its step comprises: organic phase (comprising extraction agent and thinner) is carried out to saponification, then carry out multiple-contact with the water containing rare earth ion, after the concentration of water rare earth ion no longer changes, show that this system is saturated.The concentration of organic phase is 1mol/L, and thinner is dodecane, wherein, organic phase and water be in a ratio of 1:2, containing the pH value of the water of rare earth ion, be 3.0, the time of the balance of vibrating is 30min, after multiple oscillation, the saturated capacity of different extraction agents is in Table 8.Data show that the saturated capacity of P227 is larger, and complete when saturated, there will not be the phenomenon of emulsification, and point phase velocity is fast, is better than other extraction systems such as P227.
Table 8
Claims (15)
1. an extraction system, is characterized in that comprising organic phase and water, and described organic phase comprises thinner and suc as formula the extraction agent shown in I; Described water comprises rare earth ion, and the pH value in described water is 2.5～4.5;
Wherein, M is hydrogen, alkalimetal ion or ammonium positive ion.
2. extraction system as claimed in claim 1, is characterized in that, the pH value in described water is 2.5～3.5.
3. extraction system as claimed in claim 2, is characterized in that, the pH value in described water is 2.8～3.5.
4. extraction system as claimed in claim 1, is characterized in that, described alkalimetal ion is sodium ion or potassium ion; Described ammonium positive ion is NH
4 +; Described thinner is one or more in sulfonated kerosene, aero oil, kerosene, benzene, toluene, heptane and n-dodecane; The volumetric molar concentration of described extraction agent in thinner is 0.2mol/L～2.5mol/L.
5. extraction system as claimed in claim 1, is characterized in that, described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+and Y
3+in one or more.
6. extraction system as claimed in claim 1, is characterized in that, the organic phase of described extraction system and water be in a ratio of 10:1～1:10, described comparing refers to the volume ratio of organic phase and water; The volumetric molar concentration of the rare earth ion in described water is 0.01mol/L～3.5mol/L.
7. extraction system as claimed in claim 1, is characterized in that, also comprises salting-out agent in described extraction system.
8. extraction system as claimed in claim 7, is characterized in that, described salting-out agent are sodium-chlor and/or sodium perchlorate.
9. an extracting process, is characterized in that comprising the following steps: the extraction system vibration balance by as described in claim 1～8 any one.
10. extracting process as claimed in claim 9, is characterized in that, the time of described vibration balance is 5min～30min.
11. 1 kinds of reextraction methods, is characterized in that comprising the following steps:
(1) by the organic phase of the extraction system as described in claim 1～8 any one after saponification, and mixes containing the water of rare earth ion, the balance of vibrating, obtains the organic phase of supported rare earth ion; Wherein, the pH value of the described water containing rare earth ion is 2.5～4.5;
(2) organic phase of described supported rare earth ion is mixed with aqueous acid.
12. reextraction methods as claimed in claim 11, is characterized in that, in step (1), the pH value of the described water containing rare earth ion is 2.5～3.5; Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+and Y
3+in one or more; The method of described saponification comprises the following step: by the aqueous solution of described extraction system and alkali.
13. reextraction methods as claimed in claim 12, is characterized in that, during the terminal of described saponification, in described extraction system, 30%～95% extraction agent is by saponification; The volumetric molar concentration of the aqueous solution of described alkali is 6mol/L～10mol/L; Described alkali is mineral alkali and/or organic bases.
14. reextraction methods as claimed in claim 11, is characterized in that, in step (1), the pH value of the water after described vibration balance is 2.6～4.2; The organic phase of described extraction system and the 10:1～1:10 that is in a ratio of containing the water of rare earth ion, described comparing refers to the volume ratio of organic phase and water; The described volumetric molar concentration containing the rare earth ion in the water of rare earth ion is 0.01mol/L～3.5mol/L; The time of described vibration balance is 5min～30min.
15. reextraction methods as claimed in claim 11, is characterized in that, in step (2), the acid in described aqueous acid is mineral acid; The volumetric molar concentration of described aqueous acid is 0.01mol/L～2.8mol/L; The organic phase of described supported rare earth ion and aqueous acid be in a ratio of 10:1～1:10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410010398.7A CN103725880B (en) | 2014-01-09 | 2014-01-09 | A kind of extraction system, extracting process and reextraction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410010398.7A CN103725880B (en) | 2014-01-09 | 2014-01-09 | A kind of extraction system, extracting process and reextraction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103725880A true CN103725880A (en) | 2014-04-16 |
| CN103725880B CN103725880B (en) | 2016-04-13 |
Family
ID=50450170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410010398.7A Active CN103725880B (en) | 2014-01-09 | 2014-01-09 | A kind of extraction system, extracting process and reextraction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103725880B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105177322A (en) * | 2015-09-07 | 2015-12-23 | 中国科学院上海有机化学研究所 | Extracting agent, extraction system and application |
| CN107675000A (en) * | 2017-09-05 | 2018-02-09 | 中国科学院长春应用化学研究所 | Regulate and control heavy rare-earth extraction separating technology extraction equilibrium acidity and the method for extracting series |
| CN108760995A (en) * | 2018-07-26 | 2018-11-06 | 万宝矿产有限公司 | A kind of indirect determination method of copper extraction organic phase sample effective concentration |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828026A (en) * | 2012-09-27 | 2012-12-19 | 信丰县包钢新利稀土有限责任公司 | Method for extracting and separating rare earth element by utilizing acidic extractant |
-
2014
- 2014-01-09 CN CN201410010398.7A patent/CN103725880B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828026A (en) * | 2012-09-27 | 2012-12-19 | 信丰县包钢新利稀土有限责任公司 | Method for extracting and separating rare earth element by utilizing acidic extractant |
Non-Patent Citations (1)
| Title |
|---|
| 余晓皎 等: "二(2-乙基己基)膦酸萃取不同介质中 Pr3+的研究", 《稀有金属材料与工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105177322A (en) * | 2015-09-07 | 2015-12-23 | 中国科学院上海有机化学研究所 | Extracting agent, extraction system and application |
| CN107675000A (en) * | 2017-09-05 | 2018-02-09 | 中国科学院长春应用化学研究所 | Regulate and control heavy rare-earth extraction separating technology extraction equilibrium acidity and the method for extracting series |
| CN108760995A (en) * | 2018-07-26 | 2018-11-06 | 万宝矿产有限公司 | A kind of indirect determination method of copper extraction organic phase sample effective concentration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103725880B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Recovery of rare earth elements from simulated fluorescent powder using bifunctional ionic liquid extractants (Bif‐ILEs) | |
| CN102382982B (en) | Method for separating rare earth ions by extraction of liquid-liquid-liquid three-phase system | |
| CN103055539B (en) | Method for extracting lithium salts in lithium-containing brine | |
| CN105536537B (en) | A kind of method of extract and separate lithium isotope | |
| CN102618736A (en) | Extraction seperation method of rare-earth element | |
| CN110392742A (en) | With deep congruent melting solvent extraction rare earth element | |
| CN103523804A (en) | Method for extracting lithium salt from lithium-contained brine by using extraction process | |
| Ni et al. | A cleaner strategy for comprehensive recovery of waste SmCo magnets based on deep eutectic solvents | |
| CN106367622A (en) | High-efficient and green ion-absorbed-type rear earth extraction method by adopting aluminum sulfate as leaching agent | |
| CN105177322A (en) | Extracting agent, extraction system and application | |
| CN103725880B (en) | A kind of extraction system, extracting process and reextraction method | |
| CN104195336A (en) | Extraction separation method for heavy rare earth elements | |
| CN105238926A (en) | Extraction separation method for yttrium | |
| CN105712383A (en) | Method for removing calcium and magnesium impurities in lithium-rich solution by extraction process | |
| CN105063382A (en) | Separation method of La, Ce, Pr and Nd mixed rare earth ions | |
| CN104357675A (en) | Method for extracting lithium from salt lake brine | |
| CN106048221A (en) | Method for extracting light rare earth elements in acidic solution by using ionic liquid [OMIM] BF4 | |
| CN102876893A (en) | Method for extracting and separating rare earth elements in sulfuric acid system | |
| CN103768945A (en) | Method for extraction separating of lithium isotope by virtue of sol-gel material | |
| CN109355502A (en) | A method of extracting lithium ion from acid system | |
| CN113736995A (en) | Application of carboxylic acid compound as extracting agent and metal ion extraction method | |
| CN102453800B (en) | Method for recovering rare earth elements from waste catalytic cracking catalyst containing rare earth elements | |
| CN112458319A (en) | Method for separating heavy rare earth elements based on ionic liquid extraction system | |
| CN104195335A (en) | Extraction separation method for heavy rare earth elements | |
| Tunsu et al. | Perspectives for the recovery of critical elements from future energy-efficient refrigeration materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |