CN104195336A - Extraction separation method for heavy rare earth elements - Google Patents

Extraction separation method for heavy rare earth elements Download PDF

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CN104195336A
CN104195336A CN201410482467.4A CN201410482467A CN104195336A CN 104195336 A CN104195336 A CN 104195336A CN 201410482467 A CN201410482467 A CN 201410482467A CN 104195336 A CN104195336 A CN 104195336A
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extraction
rare earth
methyl
tri
acid
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孙晓琦
王艳良
郭向广
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Xiamen Institute of Rare Earth Materials
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Xiamen Institute of Rare Earth Materials
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Abstract

The invention provides an extraction separation method for heavy rare earth elements. The extraction separation method comprises the following steps: mixing rare earth concentrates with inorganic acid to obtain a raw material liquid; using an organic phase comprising an extraction agent and a thinning agent to extract rare earth elements in the raw material liquid, wherein the extraction agent is a difunctional ionic liquid extraction agent, and the difunctional ionic liquid extraction agent comprises one deprotonated acid phosphine negative ion of quaternary ammonium positive ions and quaternary phosphonium positive ions. According to the method provided by the invention, in the extraction process, due to the fact that the quaternary ammonium positive ions or the quaternary phosphonium positive ions in the difunctional ionic liquid extraction agent are distributed in an organic phase and a water phase, the competitive effect of ionic liquid positive ions and rare earth ions is strengthened, and the extraction separation coefficient of heavy rare earth is improved. Moreover, in the subsequent extraction process, due to specific phase transfer effect of ions, a stripping agent is easier to enter the organic phase, and the reextraction rate is greatly improved.

Description

A kind of extraction separating method of heavy rare earth element
Technical field
The present invention relates to abstraction technique field, especially relate to a kind of extraction separating method of heavy rare earth element.
Background technology
Rare earth element refers to that ordination number is the lanthanon of 57-71 and the yttrium that ordination number is 39.Rare earth element is widely used in luminescent material now, telecommunications, magneticsubstance, metallurgy, the fields such as pottery.According to rare earth element atom electron structure and physicochemical property, and their symbiosis situation and different ionic radius in mineral can produce feature of different nature, and 17 kinds of rare earth elements are divided into two groups conventionally: light rare earths and heavy rare earths.
Heavy rare earths is called as " super industrial monosodium glutamate ", mainly comprises gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium.Because character and the lutetium of scandium element are close, also belong to heavy rare earths.Heavy rare earths reserves are few, and breach is large, are worth costliness, and substitutability is little.The production of global rare earth oxide compound mainly concentrates on light rare earths, and heavy rare earths proportion is very low, only accounts for 4% left and right of whole rare earth oxide output.In heavy rare earths resource few in number, the distinctive mineral of ionic Kuang Shi China, the whole world 70% above heavy rare earths is distributed in the ionic ore deposit of south China.Therefore, development environment close friend, efficiently heavy rare earths separating technology is most important for China's rare earth metallurgy industry.Terbium in heavy rare earth element, thulium, lutetium are rare products on market.Because character between heavy rare earth element is very similar, make to separate particularly difficulty.
In prior art, separating heavy rare earth mainly employing be the extraction agent separation method taking 2-ethylhexyl phosphonic acid-mono--2-(ethyl hexyl) ester (code name P507) as main body extraction agent.P507 extraction system there are the following problems need solve: 1. P507 is less to part rare earths separation coefficient, as Gd/Eu, Er/Y, Lu/Yb etc.; 2. heavy rare earth element back extraction acid concentration requires highly, and particularly Tm, Yb, Lu back extraction ratio are low, cause being difficult to obtain high-purity heavy rare earths product, in order to make product qualified, can only significantly increase extraction progression.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of extraction separating method of heavy rare earth element, and employing the method has improved extracting and separating coefficient, back extraction ratio is high.
The extraction separating method that the invention provides a kind of heavy rare earth element, comprises the following steps:
Rareearth enriching material and mineral acid are mixed to get to stock liquid;
The organic phase that comprises extraction agent and thinner described in use extracts the rare earth element in stock liquid;
Described extraction agent is difunctional ion liquid abstraction agent; Described difunctional ion liquid abstraction agent comprises quaternary ammonium cation with the acid phosphine negatively charged ion of a kind of and deprotonation in quaternary phosphine type positively charged ion.
Preferably, described rare earth element is one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
Preferably, described quaternary ammonium cation has formula (I) structure;
In formula (I), R 1, R 2, R 3and R 4independently selected from being selected from methyl, ethyl, butyl, hexyl, decyl or phenyl.
Preferably, described quaternary phosphine type positively charged ion has formula (II) structure;
In formula (II), R 1, R 2, R 3and R 4independently selected from being selected from methyl, ethyl, butyl, hexyl, decyl or phenyl.
Preferably, the acid phosphine negatively charged ion of described deprotonation is selected from 2,4 of deprotonation, 4-tri-methyl-amyl phosphonic acids-mono--2,4,4-tri-methyl-amyl ester, two (2,4,4-tri-methyl-amyl) phosphonic acids, 2,2,4-tri-methyl-amyl phosphonic acids-mono--2,2,4-tri-methyl-amyl ester, two (2,2,4-tri-methyl-amyl) phosphonic acids, 2,3,4-tri-methyl-amyl phosphonic acids-mono--2,3, one in 4-tri-methyl-amyl ester or two (2,3,4-tri-methyl-amyl) phosphonic acids.
Preferably, the mol ratio of the acid phosphine negatively charged ion of described quaternary ammonium cation and deprotonation is (0.9～1.1): (0.9:1.1); The mol ratio of the acid phosphine negatively charged ion of described quaternary phosphine type positively charged ion and deprotonation is (0.9～1.1): (0.9:1.1).
Preferably, the volume ratio of described extraction agent and thinner is (0.01～0.5): (0.99～0.5).
Preferably, described thinner is alkane or aromatic hydrocarbons.
Preferably, also comprise:
Use mineral acid to strip to the rare earth element in organic phase.
Preferably, described mineral acid is selected from the one in hydrochloric acid, nitric acid or sulfuric acid.
Compared with prior art, the invention provides a kind of extraction separating method of heavy rare earth element, comprise the following steps: rareearth enriching material and mineral acid are mixed to get to stock liquid; The organic phase that comprises extraction agent and thinner described in use extracts the rare earth element in stock liquid; Described extraction agent is difunctional ion liquid abstraction agent; Described difunctional ion liquid abstraction agent comprises quaternary ammonium cation with the acid phosphine negatively charged ion of a kind of and deprotonation in quaternary phosphine type positively charged ion.Method provided by the invention, in extraction process, because the quaternary ammonium cation Huo quaternary phosphine type positively charged ion of difunctional ion liquid abstraction agent all has distribution in organic phase and water, strengthen the Competition of ionic liquid positively charged ion and rare earth ion, improve heavy rare-earth extraction separation factor; Therefore, its selectivity for rare earth element is high, and with mineral acid, thinner combination, further improve the particularly separation factor of adjacent rare earth element of rare earth element, and in follow-up reextraction process, due to the distinctive the role of phase transfer of ionic liquid, reverse-extraction agent more easily enters organic phase, has greatly improved back extraction ratio.The inventive method without salting-out agent, can reach extracting and separating in extraction process.The surface phenomenon of extraction separating method provided by the invention in extraction process is good, and back extraction ratio is high, saved acid and alkali consumption.
Brief description of the drawings
The reextraction result figure that Fig. 1 provides for the embodiment of the present invention 2～8.
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 these are described is the restriction for further illustrating the features and advantages of the present invention instead of patent of the present invention being required.
The extraction separating method that the invention provides a kind of heavy rare earth element, comprises the following steps:
Rareearth enriching material and mineral acid are mixed to get to stock liquid;
The organic phase that comprises extraction agent and thinner described in use extracts the rare earth element in stock liquid;
Described extraction agent is difunctional ion liquid abstraction agent; Described difunctional ion liquid abstraction agent comprises quaternary ammonium cation with the acid phosphine negatively charged ion of a kind of and deprotonation in quaternary phosphine type positively charged ion.
First the present invention is mixed to get stock liquid by rareearth enriching material and mineral acid.The present invention does not limit for above-mentioned hybrid mode, hybrid mode well known to those skilled in the art.Described rareearth enriching material is for containing rare earth ion, and the particularly raw material of Heavy rare earth, can be mixture, can be also muriate or the vitriol of rare earth ion.The present invention does not limit this.
Described mineral acid is preferably hydrochloric acid, nitric acid and sulfuric acid, and more preferably hydrochloric acid and nitric acid, most preferably be hydrochloric acid.The concentration of described mineral acid is 10～18mol/L, and the concentration of concrete described concentrated hydrochloric acid is preferably 10～12mol/L, and the concentration of described concentrated nitric acid is preferably 14～16mol/L, and the concentration of the described vitriol oil is preferably 15～18mol/L.
The ratio of the quality of described rareearth enriching material and the volume of mineral acid is preferably 10:(1～8), more preferably 10:(2～7), most preferably be 10:(3～6).
The organic phase that comprises extraction agent and thinner described in use extracts the rare earth element in stock liquid.Be specially, extraction agent and mixing diluents are obtained to organic phase.Invention does not limit for above-mentioned hybrid mode, hybrid mode well known to those skilled in the art.
Rare earth element of the present invention is one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
Extraction agent of the present invention is difunctional ion liquid abstraction agent; Described difunctional ion liquid abstraction agent comprises quaternary ammonium cation with the acid phosphine negatively charged ion of a kind of and deprotonation in quaternary phosphine type positively charged ion.
Preferably, described quaternary ammonium cation has formula (I) structure;
In formula (I), preferred R 1, R 2, R 3and R 4be selected from methyl, ethyl, butyl, hexyl, decyl or phenyl, preferred R 1be selected from methyl, butyl, hexyl or decyl, R 2, R 3and R 4independently selected from butyl, hexyl, decyl or phenyl.
Preferably, described quaternary phosphine type positively charged ion has formula (II) structure;
In formula (II), preferred R 1, R 2, R 3and R 4be selected from methyl, ethyl, butyl, hexyl, decyl or phenyl, preferred R 1be selected from methyl, butyl, hexyl or decyl, R 2, R 3and R 4independently selected from butyl, hexyl, decyl or phenyl.
The acid phosphine negatively charged ion of described deprotonation is preferably selected from 2,4 of deprotonation, 4-tri-methyl-amyl phosphonic acids-mono--2,4,4-tri-methyl-amyl ester, two (2,4,4-tri-methyl-amyl) phosphonic acids, 2,2,4-tri-methyl-amyl phosphonic acids-mono--2,2,4-tri-methyl-amyl ester, two (2,2,4-tri-methyl-amyl) phosphonic acids, 2,3,4-tri-methyl-amyl phosphonic acids-mono--2,3, one in 4-tri-methyl-amyl ester or two (2,3,4-tri-methyl-amyl) phosphonic acids.
In the present invention, the mol ratio of the acid phosphine negatively charged ion of described quaternary ammonium cation and deprotonation is (0.9～1.1): (0.9:1.1); The mol ratio of the acid phosphine negatively charged ion of described quaternary phosphine type positively charged ion and deprotonation is (0.9～1.1): (0.9:1.1).
The present invention is not particularly limited the source of described ionic liquid, can buy from the market, also can be according to acid-base neutralisation reaction preparation well known to those skilled in the art [such as the preparation method of a ZL201210120559.9 quaternary amines ionic liquid] or ion exchange method preparation [such as the extraction separating method of a ZL201410333408.0 rare earth].
In the present invention, described thinner is preferably alkane or aromatic hydrocarbons, more preferably the one in aviation kerosene, sulfonated kerosene, 260# solvent oil or toluene.In the present invention, the volume ratio of described extraction agent and thinner is preferably (0.01～0.5): (0.99～0.5), more preferably (0.1～0.4): (0.90～0.4).
Obtain after above-mentioned raw materials liquid and organic phase, use described organic phase to extract the rare earth element in stock liquid.
The present invention preferably also comprises: use mineral acid to strip to the rare earth element in organic phase.Described mineral acid is preferably hydrochloric acid, nitric acid and sulfuric acid, and more preferably hydrochloric acid and nitric acid, most preferably be hydrochloric acid.The present invention does not limit for the concentration of described mineral acid, is preferably 0.03～0.4mol/L, more preferably 0.05～0.3mol/L.
The temperature of extraction of the present invention is preferably 20 DEG C～35 DEG C, more preferably 23 DEG C～30 DEG C.Described extraction time is preferably 5～10min; Described reextraction temperature is preferably 20 DEG C～35 DEG C, and more preferably 23 DEG C～30 DEG C, described back-extraction time is preferably 5～10min.The pH value of described control extraction feed liquid is preferably 0.5～4, and more preferably 1～3.
After extraction separation process completes, mixed rare-earth elements in raffinate or stripping workshop that the present invention obtains preferably utilizes ICP-MS method to measure, specifically with reference to the mensuration of 15 rare earth oxide partition amounts of GB/T 18114.8-2010 rare earth ore concentrate chemical analysis method the 8th part.
Rare Earth Elements Determination adopts 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
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.
Method provided by the invention, in extraction process, because the quaternary ammonium cation Huo quaternary phosphine type positively charged ion in difunctional ion liquid abstraction agent all has distribution in organic phase and water, strengthen the Competition of ionic liquid positively charged ion and rare earth ion, improve heavy rare-earth extraction separation factor; Therefore, its selectivity for rare earth element is high, and with mineral acid, thinner combination, further improve the particularly separation factor of adjacent rare earth element of rare earth element, and in follow-up reextraction process, due to the distinctive the role of phase transfer of ionic liquid, reverse-extraction agent more easily enters organic phase, has greatly improved back extraction effect.The inventive method without salting-out agent, can reach extracting and separating in extraction process.The surface phenomenon of extraction separating method provided by the invention in extraction process is good, and back extraction ratio is high, saved acid and alkali consumption, also can reduce extraction progression.
Embodiment 1
Synthetic RTIL-based extraction agent: get 0.6 mole of Diethylaminoethyl, three n-hexyl ammoniums [N1666] [Br], be dissolved in 1L methyl alcohol, add strongly basic anion exchange resin, bromide anion is exchanged into hydroxide ion, obtains hydroxide methyl three n-hexyl ammoniums [N1666] [OH].By 0.6 mole 2,4,4-tri-methyl-amyl phosphonic acids-mono--2,4,4-tri-methyl-amyl ester (code name P572) is added dropwise in [N1666] [OH] of generation, completes deprotonation, obtains RTIL-based extraction agent [N1666] [P572].
Preparation organic phase: [N1666] [P572] mixed with sulfonated kerosene, composition organic phase, the volume ratio of organic phase intermediate ion liquid base extraction agent and sulfonated kerosene is 0.1:0.9.
Preparation raw material liquid: get Tm-Yb-Lu enriched substance, add dilute hydrochloric acid, be mixed with stock liquid, it consists of ∑ REO=0.02 mol/L, NaCl=0.5 mol/L, pH=2.2, Tm:Yb:Lu=10:80:10.
Single-stage extraction: the organic phase that is 1:1 by volume ratio is mixed with stock liquid, extracts under room temperature, and extraction progression is 1 grade.After extraction, calculate adjacent element separation factor β, known when under precondition, the separation factor β of RTIL-based extraction agent to Tm and Yb yb/Tm=3.2, to the separation factor β of Yb and Lu lu/Yb=1.8.
Comparative example 1～2
Preparation organic phase: get respectively P572 and P507, mix with sulfonated kerosene, composition organic phase, in organic phase, the volume ratio of extraction agent and sulfonated kerosene is 0.1:0.9.
Preparation raw material liquid: get Tm-Yb-Lu enriched substance, add dilute hydrochloric acid, be mixed with stock liquid, it consists of ∑ REO=0.02 mol/L, NaCl=0.5 mol/L, pH=2.2, Tm:Yb:Lu=10:80:10.
Single-stage extraction: the organic phase that is 1:1 by volume ratio is mixed with stock liquid, extracts under room temperature, and extraction progression is 1 grade.After extraction, calculate adjacent element separation factor β.Under the same terms, P572 and P507 are respectively 2.9 and 2.3 to the separation factor of Tm and Yb, are 1.7 and 1.6 to the separation factor of Yb and Lu.
Comparative example 3
Preparation organic phase: get P572 and [N1666] [Br] composition mixed extractant of equimolar amount, then mix composition organic phase with sulfonated kerosene, P572, [N1666] [Br] are 0.05:0.05:0.9 with the volume ratio of sulfonated kerosene.
Preparation raw material liquid: get Tm-Yb-Lu enriched substance, add dilute hydrochloric acid, be mixed with stock liquid, it consists of ∑ REO=0.02 mol/L, NaCl=0.5 mol/L, pH=2.2, Tm:Yb:Lu=10:80:10.
The organic phase that is 1:1 by volume ratio is mixed with stock liquid, under room temperature, extracts, and extraction progression is 1 grade.After extraction, calculate adjacent element separation factor β, under the same terms, P572 and the separation factor β of [N1666] [Br] composition mixed extractant to Tm and Yb yb/Tm=2.8, to the separation factor β of Yb and Lu lu/Yb=1.7.
Embodiment 2～8
Preparation load organic phases: [N1666] [P572] prepared by embodiment 1 mixes with sulfonated kerosene, composition organic phase, the volume ratio of organic phase intermediate ion liquid base extraction agent and sulfonated kerosene is 0.02:0.98.With LuCl 3extract, the charge capacity in organic phase is 0.53g/L.
Preparation anti-stripping agent: configure a series of hydrochloric acid as anti-stripping agent, concentration is respectively 0.05,0.1,0.125,0.15,0.2,0.25,0.3 mol/L.
Single-stage is stripped: the load organic phases that is 1:1 by volume ratio is mixed with anti-stripping agent, under room temperature, strips, and reextraction progression is 1 grade.After extraction, calculate stripping rate.Result as shown in Figure 1, the reextraction result figure that Fig. 1 provides for the embodiment of the present invention 2～8.As seen from Figure 1, after RTIL-based extraction agent load heavy rare earths, be easy to strip.In the time that back extraction acid reaches 0.3 mol/L, it approaches completely the back extraction of lutetium.
Embodiment 9-12
Synthetic RTIL-based extraction agent: get 0.6 mole of Tetrabutylammonium bromide [N4444] [Cl], be dissolved in 0.4 liter of ethanol, drip 305 milliliters of 2 moles every liter potassium hydroxide-ethanol solution, stir after 0.5 hour and filter Repone K precipitation, obtain tetrabutylammonium [N4444] [OH].By [N4444] [OH] and 2,3,4-tri-methyl-amyl phosphonic acids-mono--2,3,4-tri-methyl-amyl ester (code name P573) mixes, and completes deprotonation, obtains RTIL-based extraction agent [N4444] [P573].
Preparation organic phase: [N4444] [P573] mixed with sulfonated kerosene, composition organic phase, the volumetric molar concentration of organic phase intermediate ion liquid base extraction agent is 0.03 mole every liter.
Preparation raw material liquid: get respectively GdCl 3, TbCl 3, DyCl 3, HoCl 3, ErCl 30.0045 mole every liter, adjust pH 2.2.
Single-stage extraction: organic phase is mixed with volume ratio 1:1 with stock liquid, extract 10 minutes under room temperature, extraction progression is 1 grade.After extraction, calculate adjacent element separation factor β, result is as shown in table 1, the adjacent element separation factor that the extracting process that table 1 provides for the embodiment of the present invention 9～12 obtains.
The adjacent element separation factor that the extracting process that table 1 embodiment of the present invention 9～12 provides obtains
Separation factor [N4444][P573]
βTb/Gd 1.53
βDy/Tb 1.36
βHo/Dy 2.89
βEr/Ho 1.60
Comparative example 4-7
Preparation organic phase: P507 is mixed with sulfonated kerosene, composition organic phase, obtaining volumetric molar concentration is 0.03 mole every liter.
Preparation raw material liquid: get respectively GdCl 3, TbCl 3, DyCl 3, HoCl 3, ErCl 30.0045 mole every liter, adjust pH 2.2.
Single-stage extraction: organic phase is mixed with volume ratio 1:1 with stock liquid, extract 10 minutes under room temperature, extraction progression is 1 grade.After extraction, calculate adjacent element separation factor β, result is as shown in table 2, the adjacent element separation factor that the extracting process that table 2 provides for comparative example 3～6 of the present invention obtains.
The adjacent element separation factor that the extracting process that table 2 comparative example 4～7 of the present invention provides obtains
Separation factor P507
βTb/Gd 1.26
βDy/Tb 1.25
βHo/Dy 1.50
βEr/Ho 1.30
Embodiment 13
Synthetic RTIL-based extraction agent: get 0.6 mole of Diethylaminoethyl triphenyl phosphonium [P1 (Ph) 3] [Br], be dissolved in 1L methyl alcohol, add strongly basic anion exchange resin, bromide anion is exchanged into hydroxide ion, obtains hydroxide Jia base triphenyl phosphonium [P1 (Ph) 3] [OH].By 0.6 mole 2,2,4-tri-methyl-amyl phosphonic acids-mono--2,2,4-tri-methyl-amyl ester (code name P574) is added dropwise in generation [P1 (Ph) 3] [OH], completes deprotonation, obtains RTIL-based extraction agent [P1 (Ph) 3] [P574].
Preparation organic phase: [P1 (Ph) 3] [P574] mixed with sulfonated kerosene, composition organic phase, the volume ratio of organic phase intermediate ion liquid base extraction agent and sulfonated kerosene is 0.15:0.85.
Preparation raw material liquid: get Tm-Yb-Lu solution, adjusting pH is 2.5, makes stock liquid.It consists of ∑ REO=0.025 mol/L, NaCl=0.2 mol/L, pH=2.5, Tm:Yb:Lu=10:80:10.
Single-stage extraction: the organic phase that is 1:1 by volume ratio is mixed with stock liquid, extracts under room temperature, and extraction progression is 1 grade.After extraction, calculate adjacent element separation factor β, known when under precondition, the separation factor β of RTIL-based extraction agent to Tm and Yb yb/Tm=3.1, to the separation factor β of Yb and Lu lu/Yb=1.75.
Above the extraction separating method of a kind of rare earth element provided by the invention is described in detail; having applied specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment is just 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 premise without departing from the principles 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 the claims in the present invention.

Claims (10)

1. an extraction separating method for heavy rare earth element, comprises the following steps:
Rareearth enriching material and mineral acid are mixed to get to stock liquid;
The organic phase that comprises extraction agent and thinner described in use extracts the rare earth element in stock liquid;
Described extraction agent is difunctional ion liquid abstraction agent; Described difunctional ion liquid abstraction agent comprises quaternary ammonium cation with the acid phosphine negatively charged ion of a kind of and deprotonation in quaternary phosphine type positively charged ion.
2. extraction separating method according to claim 1, is characterized in that, described rare earth element is one or more of Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y.
3. extraction separating method according to claim 1, is characterized in that, described quaternary ammonium cation has formula (I) structure;
In formula (I), R 1, R 2, R 3and R 4independently selected from being selected from methyl, ethyl, butyl, hexyl and decyl or phenyl.
4. extraction separating method according to claim 1, is characterized in that, described quaternary phosphine type positively charged ion has formula (II) structure;
In formula (II), R 1, R 2, R 3and R 4independently selected from being selected from methyl, ethyl, butyl, hexyl and decyl or phenyl.
5. extraction separating method according to claim 1, is characterized in that, the acid phosphine negatively charged ion of described deprotonation is selected from 2 of deprotonation, 4,4-tri-methyl-amyl phosphonic acids-mono--2,4,4-tri-methyl-amyl ester, two (2,4,4-tri-methyl-amyl) phosphonic acids, 2,2,4-tri-methyl-amyl phosphonic acids-mono--2,2,4-tri-methyl-amyl ester, two (2,2,4-tri-methyl-amyl) phosphonic acids, 2,3,4-tri-methyl-amyl phosphonic acids-mono--2,3,4-tri-methyl-amyl ester or two (2,3,4-tri-methyl-amyl) one in phosphonic acids.
6. extraction separating method according to claim 1, is characterized in that, the mol ratio of the acid phosphine negatively charged ion of described quaternary ammonium cation and deprotonation is (0.9～1.1): (0.9:1.1); The mol ratio of the acid phosphine negatively charged ion of described quaternary phosphine type positively charged ion and deprotonation is (0.9～1.1): (0.9:1.1).
7. extraction separating method according to claim 1, is characterized in that, the volume ratio of described extraction agent and thinner is (0.01～0.5): (0.99～0.5).
8. extraction separating method according to claim 1, is characterized in that, described thinner is alkane or aromatic hydrocarbons.
9. extraction separating method according to claim 1, is characterized in that, also comprises:
Use mineral acid to strip to the rare earth element in organic phase.
10. extraction separating method according to claim 1, is characterized in that, described mineral acid is selected from the one in hydrochloric acid, nitric acid or sulfuric acid.
CN201410482467.4A 2014-09-19 2014-09-19 Extraction separation method for heavy rare earth elements Pending CN104195336A (en)

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CN109517985A (en) * 2019-01-11 2019-03-26 东北大学 A method of light rare earth elements is separated using difunctional ion liquid abstraction
US10428405B2 (en) 2015-05-25 2019-10-01 Xiamen Institute Of Rare Earth Materials Extractant and method for extracting and separating yttrium
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CN113106271A (en) * 2021-04-06 2021-07-13 中国科学院过程工程研究所 Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid
US11149356B2 (en) 2017-12-19 2021-10-19 Battelle Energy Alliance, Llc Methods of forming metals using ionic liquids
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CN104862504A (en) * 2015-05-15 2015-08-26 厦门稀土材料研究所 Synergic extraction agent for heavy rare earth elements and extraction separation method of synergic extraction agent
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