CN102876894A - Method for extracting and separating rare earth elements in hydrochloric acid system - Google Patents

Method for extracting and separating rare earth elements in hydrochloric acid system Download PDF

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CN102876894A
CN102876894A CN2012103758214A CN201210375821A CN102876894A CN 102876894 A CN102876894 A CN 102876894A CN 2012103758214 A CN2012103758214 A CN 2012103758214A CN 201210375821 A CN201210375821 A CN 201210375821A CN 102876894 A CN102876894 A CN 102876894A
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rare earth
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陈继
郭琳
邓岳锋
兰景波
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a method for extracting and separating rare earth elements in a hydrochloric acid system. The method includes the steps: taking mono (2-ethylhexyl) phosphonate 2-ethylhexyl methoxy cinnamate trialkyl methyl ammonium or phosphonate (2-ethylhexyl) diester trialkyl methyl ammonium as an extracting agent; taking normal heptane as diluent; and extracting the rare earth elements in rare earth chloride water solution into the normal heptane. The extracting agent used in the method does not need to be saponified, extraction and reverse extraction acidity is low, and separation coefficient for the rare earth elements is high.

Description

A kind of extraction separating method of hydrochloric acid system rare earth elements
Technical field
The present invention relates to the abstraction technique field, more particularly, relate to a kind of extraction separating method of hydrochloric acid system rare earth elements.
Background technology
Rare earth element refers to that ordination number is that the lanthanon of 57-71 and ordination number are 39 yttrium.Rare earth element is widely used in luminescent material now, telecommunications, magneticsubstance, metallurgy, the fields such as pottery.And various rare earth elements are to mix to exist in mineral reserve, as: hamartite, monazite, xenotime and resinous shale etc.Therefore in order to obtain Rare Earth Elements Determination, the extracting and separating of rare earth element is studied widely and is used.Owing to have similar physics and chemistry character between each rare earth element, its separation brought certain difficulty.The solvent extraction and separation method has that treatment capacity is large, speed of response is fast, the advantage of good separating effect, and it is during domestic and international rare-earth industry is produced, and the main method of separation purification of rare earth element also is the main method of separating preparation high-purity single rare earth compound.For protection of the environment, rationally utilize the discharging of rare earth resources and restriction trade effluent, China has put into effect the discharging that " rare-earth industry pollutant emission standard " further limited each pollutent in 2011, require rare earth is carried out more green more efficient separation.
At present, single rare earth separates main acidic extractant P507(2-ethylhexyl phosphonic acid mono (2-ethylhexyl) ester or P204(two-(2-ethylhexyl) phosphoric acid of adopting) divide into groups to separate.Because comparing with traditional Neutral-neutral Extractants, acidic extractant has high separation factor.But acidic extractant will carry out first the saponification process when separating, this process can produce a large amount of ammonia nitrogen waste waters, and environment is had disadvantageous effect.Also have some mixed systems to be used for Rare Earth Separation, such as (technique .1998 of producing high-purity lutetium oxide by extracting separation method such as Liao Chunsheng, CN1192479A.) adopting saponification P507 is extraction agent, and the amine extractant N263 of interpolation 0.5 ~ 20% adopts single stage method continuous high-purity lutecium oxide of separation of produced from thulium, ytterbium, lutetium enriched substance or thick lutecium oxide in hydrochloric acid medium.Reach Chinese patent CN100352954C and reported a kind of technique of adding the extracting and separating heavy rare earth element of modifying agent, this technique is separated single rare earth with the system that P507 adds alcohol.Yet this class hybrid extraction system, the character such as the solubleness of each component there are differences, and can cause the extraction agent component to change after the long-time running, affect the effect of extracting of system.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of extraction separating method of hydrochloric acid system rare earth elements, and the extraction agent of employing need not saponification, and extraction back extraction acidity is low, and rare earth element is had higher separation factor.
In order to solve above technical problem, the invention provides the extraction separating method of a kind of rare earth element in the salt acid rare earth, may further comprise the steps:
Take di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl as extraction agent, take normal heptane as thinner, the rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane.
Preferably, extraction temperature is 20 ~ 50 ℃.
Preferably, comprise that also the NaCl solution take concentration as 0.2 ~ 1.5mol/L is salting-out agent.
Preferably, described rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane is specially:
N-heptane solution, salting-out agent and the aqueous solution of rare earth chloride of the agent of quaternary ammonium salt ion liquid abstraction are mixed, rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane, and the agent of described quaternary ammonium salt ion liquid abstraction is di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl.
Preferably, the concentration of the n-heptane solution of described quaternary ammonium salt ion liquid abstraction agent is 0.01 ~ 0.08mol/L.
Preferably, the concentration of described aqueous solution of rare earth chloride is 7 ~ 11 * 10 -4Mol/L.
Preferably, the rare earth element in the aqueous solution of rare earth chloride is extracted to normal heptane after, the pH value of control aqueous solution of rare earth chloride is 1 ~ 5.
Preferably, also comprise:
Utilize hydrochloric acid soln that the rare earth element that is extracted in the normal heptane is stripped.
Preferably, the concentration of described hydrochloric acid soln is 0.03 ~ 0.20mol/L.
Preferably, described rare earth element is one or more among La Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the Y.
The invention provides a kind of extraction separating method of hydrochloric acid system rare earth elements, may further comprise the steps:, as extraction agent the rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane take di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl ([A336] [P507]) or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl ([A336] [P204]).Compared with prior art, because being positively charged ion and the negatively charged ion in di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl and phosphonic acids two (2-ethylhexyl) the ester trialkyl ammonium methyl, the agent of quaternary ammonium salt ion liquid abstraction all forms neutral complex molecule with the rare earth ion reaction, and, synergistic effect in positively charged ion in the agent of quaternary ammonium salt ion liquid abstraction and negatively charged ion exist in extraction earth elements process, thus separation factor to rare earth element improved.Therefore, extraction separating method provided by the invention is good in the extraction process Interfacial Phenomenon, produces without emulsification, need not that the extraction agent saponification is had higher separation factor to rare earth element, especially several light rare earthss is had high extracting and separating effect.In addition, the extraction separating method of rare earth element provided by the invention extraction acidity is low, and back extraction acidity is low, less acid-consuming.
Description of drawings
Fig. 1 is the scattergram of [A336] [P507] of providing of the embodiment of the invention 13 ~ 27 solution equilibria pH value and rare earth ion distribution ratio during as extraction agent;
Fig. 2 is the scattergram of [A336] [P204] of providing of the embodiment of the invention 28 ~ 42 solution equilibria pH value and rare earth ion distribution ratio during as extraction agent;
Fig. 3 is [A336] [P507] of providing of the embodiment of the invention 43 ~ 45 salting-out agent concentration and rare earth partition ratio graphic representation during as extraction agent;
Fig. 4 is [A336] [P204] of providing of the embodiment of the invention 46 ~ 48 salting-out agent concentration and rare earth partition ratio graphic representation during as extraction agent;
Fig. 5 is [A336] [P507] of providing of the embodiment of the invention 49 ~ 52 HCl strength of solution and supported rare earth ion back extraction ratio graphic representation during as extraction agent;
Fig. 6 is [A336] [P204] of providing of the embodiment of the invention 53 ~ 56 HCl strength of solution and supported rare earth ion back extraction ratio graphic representation during as extraction agent;
The NaCl concentration that Fig. 7 embodiment of the invention 57 provides is to the percentage extraction influence curve.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that the just restriction for further specifying the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
The invention provides a kind of extraction separating method of hydrochloric acid system rare earth elements, may further comprise the steps:
Take di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl as extraction agent, take normal heptane as thinner, the rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane.
Because existing acidic extractant separates Rare Earth Elements Determination and needs saponification in acid system, and tying up to the long-time running meeting, some mixing acid gonosome causes change of component, so the present invention is that di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl ([A336] [P507]) or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl ([A336] [P204]) are as extraction agent take the agent of quaternary ammonium salt ion liquid abstraction, in hydrochloric acid system, separate single rare earth, can avoid the saponification process also need not consider the change of component of long-time running, this process extraction acidity is low, and rare earth element is had higher separation factor.
The inventor finds that extraction agent can be subject to the impact (NO of system negatively charged ion on the extracting and separating of rare earth ion 3 -, Cl -Or SO 4 2-) because these negatively charged ion can form different extracted specieses with rare earth ion and extraction agent in extraction process, and because negatively charged ion is different, so that the optimum pH value of rare earth ion and extraction agent combination changes.
According to the present invention, described [A336] [P507] has the structure shown in the formula I; [A336] [P204] has the structure shown in the formula II
Figure BDA00002221265500041
The technical scheme that the present invention provides take the Chinese patent literature of application number as 201210120559.9 is synthetic di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl and phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl respectively.Wherein, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl ([A336] [P507]) preferably is prepared as follows:
With 5.6g, 0.10mol potassium hydroxide is dissolved in 56ml ethanol, obtains alkali alcosol, and with 40g, take by weighing 0.1mol aliquat 336 and be added dropwise in the above-mentioned alkali alcosol, stirring at room 1 hour, filtering Repone K precipitation must be clarified ionic liquid [A336] [OH]; 0.08molP507 is added the 0.1mol[A336 obtained] in [OH], stirring at room 2 hours is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent ethanol then, product vacuum-drying obtains [A336] [P507].
In addition, the preparation method of phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl ([A336] [P204]) is specially: after preparing according to the method described above [A336] [OH], 0.08molP204 is added the 0.1mol[A336 obtained] in [OH], stirring at room 1 hour, get upper strata ionic liquid organic phase, wash 3 times with deionized water, then vacuum distillation recovered solvent ethanol, product vacuum-drying obtains [A336] [P204].
According to the present invention, described rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane is specially: n-heptane solution, salting-out agent and the aqueous solution of rare earth chloride of the agent of quaternary ammonium salt ion liquid abstraction are mixed, rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane, and the agent of described quaternary ammonium salt ion liquid abstraction is di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl.Preferably, the n-heptane solution of described quaternary ammonium salt ion liquid abstraction agent, salting-out agent and aqueous solution of rare earth chloride also preferably include after mixing: be to shake under 25 ℃ of constant temperature in temperature, preferred concussion 1 hour, measure the concentration of the rare earth element of aqueous phase, and then calculate percentage extraction and the partition ratio of rare earth element.
In addition, the NaCl that the present invention also preferably includes take concentration as 0.2 ~ 1.5mol/L is salting-out agent, and the concentration that this NaCl is is preferably 0.5 ~ 1.2mol/L, more preferably 0.6 ~ 1.0mol/L.When concentration during less than 0.2mol/L, the rare earth ion percentage extraction is very low, is difficult for detecting and calculating; When concentration during greater than 1.5mol/L, rare earth ion is extracted fully simultaneously, and same being difficult for detected and calculate.In addition, extraction temperature can produce on the extracting and separating result of rare earth element certain impact, the too high or too low extracting and separating that all is unfavorable for rare earth element of extraction temperature.The extraction temperature that the present invention adopts is preferably 20 ~ 50 ℃, more preferably 20 ~ 30 ℃.The concentration of the n-heptane solution of above-mentioned quaternary ammonium salt ion liquid abstraction agent is preferably 0.01 ~ 0.08mol/L, more preferably 0.03 ~ 0.06mol/L, more preferably 0.05mol/L.
There is no particular restriction for the rare earth element in the described aqueous solution of rare earth chloride in the present invention, can be Rare Earth Elements Determination well known to those skilled in the art or multiple rare earth element, as preferred version, described rare earth element is one or more among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the Y.In addition, the concentration of described aqueous solution of rare earth chloride is preferably 7 ~ 11 * 10 -4Mol/L, more preferably 7 ~ 8 * 10 -4Mol/L most preferably is 7.5 * 10 -4Mol/L.
After according to the method described above the rare earth element in the aqueous solution of rare earth chloride being extracted to normal heptane, the balance pH value of preferably controlling aqueous solution of rare earth chloride is 1 ~ 5.In addition, the present invention also preferably includes: utilize hydrochloric acid soln that the rare earth element that is extracted in the normal heptane is stripped.Preferably, the concentration of described hydrochloric acid soln is 0.03 ~ 0.20mol/L, more preferably 0.1 ~ 0.2mol/L.When concentration during less than 0.03mol/L, some rare earth ion back extraction ratio is lower, is difficult for detecting and calculating.
After extraction separation process was finished, the raffinate that the present invention obtains or the rare earth element in the stripping workshop preferably utilized arsenazo (III) colorimetric method for determining.Percentage extraction (E), the calculation formula of partition ratio (D) and separation factor (β) is as follows:
E ( % ) = ( C aq , o - C aq ) C aq , o × 100
Figure BDA00002221265500062
β = D 1 D 2
Wherein, C Aq, oAnd C AqBe respectively starting point concentration and the equilibrium concentration of water rare earth ion, V AqAnd V OrgBe respectively the volume of water and organic phase.
In sum, the present invention adopts [A336] [P507] or [A336] [P204] as extraction agent, and normal heptane is applied to the separation of hydrochloric acid system middle-weight rare earths as thinner, has following features: extraction acidity is low, less acid-consuming; Surface phenomenon well produces without emulsification; Extraction agent need not saponification, need not to add other auxiliary agent, the characteristics of saving cost and rare earth being had high separation factor.
Embodiment 1
With 5.6g, 0.10mol potassium hydroxide is dissolved in 56ml ethanol, obtains alkali alcosol, and with 40g, take by weighing 0.1mol aliquat 336 and be added dropwise in the above-mentioned alkali alcosol, stirring at room 1 hour, filtering Repone K precipitation must be clarified ionic liquid [A336] [OH]; 0.08mol P507 is added the 0.1mol[A336 obtained] in [OH], stirring at room 2 hours is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent ethanol then, product vacuum-drying obtains [A336] [P507].
Embodiment 2
With 5.6g, 0.10mol potassium hydroxide is dissolved in 56ml ethanol, obtains alkali alcosol, and with 40g, take by weighing 0.1mol aliquat 336 and be added dropwise in the above-mentioned alkali alcosol, stirring at room 1 hour, filtering Repone K precipitation must be clarified ionic liquid [A336] [OH]; 0.08mol P204 is added the 0.1mol[A336 obtained] in [OH], stirring at room 1 hour is got upper strata ionic liquid organic phase, wash 3 times with deionized water, vacuum distillation recovered solvent ethanol then, product vacuum-drying obtains [A336] [P204].
Embodiment 3
[A336] [P507] extracting and separating single rare earth ion.
With the aqueous solution that [A336] [P507] n-heptane solution and the 5.0mL of 1.0mL0.05mol/L contains NaCl and La (III), wherein NaCl concentration is 1.0mol/L in the aqueous solution, and La (III) concentration is 7.5 * 10 -4Mol/L after temperature is to shake 1h under 25 ℃ of constant temperature, measures aqueous phase La (III) concentration, and then calculates percentage extraction and the partition ratio of La (III).
Embodiment 4 ~ 7
Adopt the extracting process identical with embodiment 3, obtain respectively Ce (III), Pr (III), Nd (III), percentage extraction and the partition ratio of Sm (III).According to system balance pH=2.50, calculate the partition ratio (β) between the different rare earth ions, the results are shown in Table 1.
Table 1 is the separation factor between the rare earth ion during as extraction agent with [A336] [P507]
RE(III) Ce Pr Nd Sm
La 2.03 2.62 24.92 117.12
Ce 1.29 12.28 57.70
Pr 9.52 44.74
Nd 4.70
As can be seen from Table 1, the partition ratio between the above light rare earth ion is larger, and therefore, extraction separating method provided by the invention has higher separation factor to light rare earths.
Embodiment 8
[A336] [P204] extracting and separating single rare earth ion.
With [A336] [P204] n-heptane solution of 1.0mL0.05mol/L, the aqueous solution that 5.0mL contains NaCl and La (III), wherein NaCl concentration is 1.0mol/L in the aqueous solution, and La (III) concentration is 7.5 * 10 -4Mol/L after temperature is to shake 1h under 25 ℃ of constant temperature, measures aqueous phase La (III) concentration, and then calculates percentage extraction and the partition ratio of La (III).
Embodiment 9 ~ 12
Adopt the extracting process identical with embodiment 8, obtain respectively Ce (III), Pr (III), Nd (III), percentage extraction and the partition ratio of Sm (III).According to system balance pH=2.50, calculate the partition ratio (β) between the different rare earth ions, the results are shown in Table 2.
Table 2 is the separation factor between the rare earth ion during as extraction agent with [A336] [P204]
RE(III) Ce Pr Nd Sm
La 1.14 1.49 8.35 34.58
Ce 1.31 7.34 30.40
Pr 5.61 23.25
Nd 4.14
As can be seen from Table 2, the partition ratio between the above light rare earth ion is larger, and therefore, extraction separating method provided by the invention has higher separation factor to light rare earths.
Embodiment 13
Solution equilibria pH value is on the impact of [A336] [P507] extraction single rare earth ionic distribution ratio.
1.0mL0.05mol/L [A336] [P507] n-heptane solution and the 5.0mL aqueous solution that contains NaCl and La (III), wherein NaCl concentration is 1.0mol/L in the aqueous solution, La (III) concentration is 7.5 * 10 -4Mol/L is to shake 1h under 25 ℃ of constant temperature in temperature, measures respectively the rear water balance pH value of concussion and corresponding aqueous phase La (III) concentration.Calculate distribution ratio.When solution equilibria pH value not simultaneously, distribution ratio can change.
Embodiment 14 ~ 27
Adopt the extracting process identical with embodiment 13, obtain respectively Ce (III), Pr (III), Nd (III), Sm (III), Eu (III), Gd (III), Tb (III), Dy (III), Ho (III), Er (III), Tm (III), Yb (III), the distribution ratio of Lu (III) and Y (III) namely obtains the partition ratio of different rare earth ions when different pH value.
Fig. 1 is the scattergram of [A336] [P507] solution equilibria pH value and rare earth ion distribution ratio during as extraction agent, and as can be seen from the figure, when balance pH value increased, the partition ratio of rare earth ion increased.Obtain by measuring balance pH value, balance pH value is in 1 to 5 scope, and each different rare earth ions can be finished extraction process, and the extraction acidity of this extraction agent is lower.
Embodiment 28
Solution equilibria pH value is on the impact of [A336] [P204] extraction single rare earth ionic distribution ratio.
With the aqueous solution that [A336] [P204] n-heptane solution and the 5.0mL of 1.0mL0.05mol/L contains NaCl and La (III), wherein NaCl concentration is 1.0mol/L in the aqueous solution, and La (III) concentration is 7.5 * 10 -4Mol/L is to shake 1h under 25 ℃ of constant temperature in temperature, measures respectively the rear water balance pH value of concussion and corresponding aqueous phase La (III) concentration.Calculate distribution ratio.When solution equilibria pH value not simultaneously, distribution ratio can change.
Embodiment 29 ~ 42
Adopt the extracting process identical with embodiment 28, obtain respectively Ce (III), Pr (III), Nd (III), Sm (III), Eu (III), Gd (III), Tb (III), Dy (III), Ho (III), Er (III), Tm (III), Yb (III), the distribution ratio of Lu (III) and Y (III) namely obtains the partition ratio of different rare earth ions when different pH value.
Fig. 2 is the scattergram of [A336] [P204] solution equilibria pH value and rare earth ion distribution ratio during as extraction agent, and as can be seen from the figure, when balance pH value increased, the partition ratio of rare earth ion increased.Obtain by measuring balance pH value simultaneously, balance pH value is in 1 to 5 scope, and each different rare earth ions can be finished extraction process, and the extraction acidity of this extraction agent is lower.
Embodiment 43
Salting-out agent concentration is on the impact of [A336] [P507] extraction single rare earth ion.
With [A336] [P507] n-heptane solution of 1.0mL 0.05mol/L, 5.0mL contains the aqueous solution of NaCl and La (III), and wherein NaCl concentration is 0.2 ~ 1.5mol/L in the aqueous solution, and La (III) concentration is 7.5 * 10 -4Mol/L is to shake 1h under 25 ℃ of constant temperature in temperature, measures respectively the concentration that salting-out agent concentration is not shaken rear aqueous phase La (III) simultaneously.Dispensed is than working as salting-out agent concentration not simultaneously, and partition ratio can change.
Embodiment 44 ~ 45
Adopt the extracting process identical with embodiment 43, obtain respectively the partition ratio of Sm (III) and Dy (III), the results are shown in Figure 3.
As can be seen from Figure 3, when salting-out agent concentration increased, partition ratio improved, and therefore added salting-out agent and helped to extract and carry out.
Embodiment 46
Salting-out agent concentration is on the impact of [A336] [P204] extraction single rare earth ion.
With the aqueous solution that [A336] [P204] n-heptane solution and the 5.0mL of 1.0mL0.05mol/L contains NaCl and La (III), wherein NaCl concentration is 0.2 ~ 1.5mol/L in the aqueous solution, and La (III) concentration is 7.5 * 10 -4Mol/L is to shake 1h under 25 ℃ of constant temperature in temperature, measures respectively the concentration that salting-out agent concentration is not shaken rear aqueous phase La (III) simultaneously.Dispensed is than working as salting-out agent concentration not simultaneously, and partition ratio can change.
Embodiment 47 ~ 48
Adopt the extracting process identical with embodiment 46, obtain respectively the partition ratio of Sm (III) and Dy (III), the results are shown in Figure 4.
As can be seen from Figure 4, when salting-out agent concentration increased, partition ratio improved, and therefore added salting-out agent and helped to extract and carry out.
Embodiment 49
HCl solution is to the back extraction experiment of [A336] [P507] of supported rare earth ion.
Be that the HCl solution of 0.03 ~ 0.20mol/L mixes with 5.0mL concentration respectively with [A336] [P507] n-heptane solution of 1.0mL load La (III) ion, be to shake 1h under 25 ℃ of constant temperature in temperature, mensuration is during by the back extraction of different concns stripping workshop, the back extraction ratio of La (III) ion.
Embodiment 50 ~ 52
Adopt the step of embodiment 49 to test, obtain respectively Ce (III), the percentage extraction of Pr (III) and Nd (III) the results are shown in Figure 5.
As can be seen from Figure 5, to substantially fully back extraction of light rare earth ion, back extraction acidity is low when HCl concentration reaches 0.20mol/L, and the back extraction process is easy.
Embodiment 53
HCl solution is to the back extraction experiment of [A336] [P204] of supported rare earth ion.
Be that the HCl solution of 0.03 ~ 0.20mol/L mixes with 5.0mL concentration respectively with [A336] [P204] n-heptane solution of 1.0mL load La (III) ion, be to shake 1h under 25 ℃ of constant temperature in temperature, mensuration is during by the back extraction of different concns stripping workshop, the back extraction ratio of La (III) ion.
Embodiment 54 ~ 56
Adopt the step of embodiment 53 to test, obtain respectively Ce (III), the percentage extraction of Pr (III) and Nd (III) the results are shown in Figure 6.
As can be seen from Figure 6, to substantially fully back extraction of light rare earth ion, back extraction acidity is low when HCl concentration reaches 0.20mol/L, and the back extraction process is easy.
Embodiment 57
Extraction agent [A336] [P507] is to the separation factor of mishmetal.
Press the composition in Baotou rare earth ore deposit, be made into and contain La (III), Ce (III), the mixing solutions of Pr (III) and Nd (III).[A336] [P507] n-heptane solution and the 5.0mL mixing solutions of 1.0mL 0.05mol/L are mixed, and NaCl concentration is 1.0mol/L in the described mixing solutions, La (III), and Ce (III), Pr (III), Nd (III) is respectively 2.5 * 10 -4Mol/L, 4.5 * 10 -4Mol/L, 1.7 * 10 -4Mol/L and 2.1 * 10 -4Mol/L after temperature is to shake 1h under 25 ℃ of constant temperature, measures water La (III), Ce (III), the concentration of Pr (III) and Nd (III) is calculated percentage extraction, the separation factor between the different rare earth ions (β), the results are shown in Table 3, as can be seen from Table 3, in mixed system, La (III), Ce (III), the separation factor of Pr (III) and Nd (III) is larger.
Separation factor between the table 3 mixed system Rare Earth Ion
Figure BDA00002221265500121
Embodiment 58
When different anions existed, extraction agent [A336] [P507] was to the extraction of mishmetal.
Configuration contains La (III), Ce (III), Pr (III), Nd (III), Y (III), the vitriol mixing solutions of Gd (III) and Yb (III).La in the mixing solutions (III), Ce (III), Pr (III), Nd (III), Y (III), the concentration of Gd (III) and Yb (III) is respectively 4.6 * 10 -4Mol/L, 7.1 * 10 -4Mol/L, 1.8 * 10 -4Mol/L, 2.5 * 10 -4Mol/L, 0.4 * 10 -4Mol/L, 0.1 * 10 -4Mol/L and 2.6 * 10 -4Mol/L, this solution middle-weight rare earths total concn is 1.93 * 10 -3Mol/L.[A336] [P507] n-heptane solution and the 4.0mL mentioned solution of 1.0mL0.02mol/L are mixed, wherein NaCl concentration is 0.01 ~ 1.0mol/L in the aqueous solution, be to shake 30min under 25 ℃ of constant temperature in temperature, measure aqueous phase rare earth total concn after the simultaneously concussion of salting-out agent NaCl concentration.Calculate percentage extraction.When NaCl concentration not simultaneously, percentage extraction can change.The results are shown in Figure 7.
As can be seen from Figure 7, when having multiple negatively charged ion in the aqueous solution, when salting-out agent NaCl concentration increased, percentage extraction improved, and the percentage extraction of the Rare Earths salt in the mixed anion system increases.
Embodiment 59
Extraction agent [A336] [P507] is to the extraction cycle experiment of La (III).
For reusability and the stability of investigating extraction agent, the aqueous solution that contains NaCl and La (III) with [A336] [P507] n-heptane solution and the 5.0mL of 1.0mL0.05mol/L, wherein NaCl concentration is 1.0mol/L in the aqueous solution, and La (III) concentration is 7.5 * 10 -4Mol/L, be to shake 1h under 25 ℃ of constant temperature in temperature, measure aqueous phase La (III) concentration after the concussion, calculate percentage extraction, then with concentration be the HCl of 0.1mol/L as reverse-extraction agent, the metal ion on the extraction agent of load La (III) is separated with extraction agent [A336] [P507].Reuse this extraction agent and continue above-mentioned experiment, the value of extraction agent percentage extraction sees Table 4 after obtaining circulating several times, and as can be seen from Table 4, extraction agent percentage extraction after having carried out 4 cycling extractions is substantially constant, so this extraction agent good stability can be reused.
Table 4 extraction agent [A336] [P507] is to the extraction cycle experiment of La (III)
Figure BDA00002221265500131
More than the extraction separating method of a kind of rare earth element provided by the invention is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.

Claims (10)

1. the extraction separating method of a hydrochloric acid system rare earth elements is characterized in that, may further comprise the steps:
Take di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl as extraction agent, take normal heptane as thinner, the rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane.
2. extraction separating method according to claim 1 is characterized in that, the temperature of described extraction is 20 ~ 50 ℃.
3. extraction separating method according to claim 1 is characterized in that, comprises that also the NaCl solution take concentration as 0.2 ~ 1.5mol/L is salting-out agent.
4. extraction separating method according to claim 3 is characterized in that, described rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane is specially:
N-heptane solution, salting-out agent and the aqueous solution of rare earth chloride of the agent of quaternary ammonium salt ion liquid abstraction are mixed, the rare earth element in the aqueous solution of rare earth chloride is extracted in the normal heptane;
The agent of described quaternary ammonium salt ion liquid abstraction is di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester trialkyl ammonium methyl or phosphonic acids two (2-ethylhexyl) ester trialkyl ammonium methyl.
5. extraction separating method according to claim 4 is characterized in that, the concentration of the n-heptane solution of described quaternary ammonium salt ion liquid abstraction agent is 0.01 ~ 0.08mol/L.
6. extraction separating method according to claim 1 is characterized in that, the concentration of described aqueous solution of rare earth chloride is 7 ~ 11 * 10 -4Mol/L.
7. extraction separating method according to claim 1 is characterized in that, the rare earth element in the aqueous solution of rare earth chloride is extracted to normal heptane after, control aqueous solution of rare earth chloride the pH value be 1 ~ 5.
8. extraction separating method according to claim 1 is characterized in that, also comprises:
Utilize hydrochloric acid soln that the rare earth element that is extracted in the normal heptane is stripped.
9. extraction separating method according to claim 8 is characterized in that, the concentration of described hydrochloric acid soln is 0.03 ~ 0.20mol/L.
10. extraction separating method according to claim 1 is characterized in that, described rare earth element is one or more among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the Y.
CN2012103758214A 2012-09-29 2012-09-29 Method for extracting and separating rare earth elements in hydrochloric acid system Pending CN102876894A (en)

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