CN106929675A - It is a kind of to be enriched with 14 kinds of methods of rare earth element respectively - Google Patents
It is a kind of to be enriched with 14 kinds of methods of rare earth element respectively Download PDFInfo
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Abstract
The present invention provides a kind of 14 kinds of methods of rare earth element of enrichment respectively, belongs to rare-earth enrichment purification field.The method is with N in sulfuric acid system, N, N ', the oxygen glutaramide abbreviation TODGA of four octyl groups of N ' 3 is extractant, with kerosene as diluent, Enrichment purification respectively to the rare earth element in 14 kinds of unitary systems of rare earth element is realized by way of liquid-liquid extraction in different extraction acidity, extractant concentration, the dissolubility property extracted under volume ratio, extraction time, extraction times using rare earth element.The separation method that the present invention is provided is isolated and purified with universality to lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium this 14 kinds of rare earth elements, can be used for the treatment of environmental sample and experimental waste liquid containing a kind of rare earth element etc., practicality simple to operate, required separation equipment is few, and energy consumption is low, and extraction efficiency is high, TODGA can be recycled, and waste liquid is pollution-free, discharge capacity is few, meets the demand of environmental protection.
Description
Technical field
14 kinds of methods of rare earth element are enriched with respectively the present invention relates to a kind of, belong to rare-earth enrichment purification field.
Background technology
Rare earth be countries in the world today rebuild traditional industry, developing high-tech and the indispensable weight of national defence sophisticated technology
Want strategic resource.With the continuous breakthrough of the continuous progressive and application technology of science and technology, the value of single rare earth oxide is increasingly
Greatly.Rare earth element is obtained in fields such as oil, chemical industry, metallurgy, weaving, ceramics, glass, permanent-magnet materials and is widely applied.
At present industrial rare-earth separating with comparing more than method be to carry out multiple extract and separate using P204, P205, P507, but extraction
Take efficiency low, and it is harmful to environment.For modified technique, the utilization ratio of rare earth resources is improved, explore a kind of simple, efficient
Mischmetal separation method separation of rare earth elements seems extremely necessary, is that we probe into using new rare-earth extractant N, N this,
N ', the N octyl group -3- oxygen glutaramide abbreviation TODGA rare-earth separatings under sulphuric acid environment of '-four, and obtained highly desirable effect
Really.
Solvent extraction is the wide process for separation and purification of an application field, be widely used in hydrometallurgy, petrochemical industry,
The industrial circles such as non-ferrous metal metallurgy, nuclear fuel extraction purification, pharmacy and environmental protection, have become rare earth, non-ferrous metal work
Industry separates the important means for producing simple metal.Chemical-process is pursuing high efficiency, environment-friendly and zero-emission, solvent extraction point all the time
It is no exception from flow.Therefore, new more efficient, more environmentally friendly, more simple the making of solvent extraction and separation method of technique is probed into
Work reagent acid and alkali consumption declines, and industrial discharge is reduced, beneficial to environmental protection.
The content of the invention
The invention solves the problems that rare earth ion low separation efficiency, separation process complexity, the strict technical problem of extraction conditions, because
This provides a kind of 14 kinds of methods of rare earth element of enrichment respectively.
In order to achieve the above object, the technical scheme is that：It is a kind of to be enriched with 14 kinds of methods of rare earth element respectively, its
It is characterised by, with TODGA as extractant, with kerosene as diluent, it is right to be realized by way of liquid-liquid extraction in sulfuric acid system
The enrichment of contained rare earth element, comprises the following steps in system for handling containing certain rare earth element：
(1) early-stage preparations are tested：A solution：TODGA diluents are diluted with certain proportion, extraction agent solution is obtained；B is molten
Liquid：It is molten that the sulfate containing lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, 14 kinds of rare earth elements of yttrium is prepared respectively
Liquid, places after adjusting acidity with sulfuric acid, and cooling is standby, obtains solution to be separated；C solution：Hydrochloric acid and nitric acid needed for preparing back extraction
Mixed acid solution, place cooling, obtain back extraction nitration mixture；
(2) extract and separate：Using liquid-liquid extraction method, by a solution and b solution in step (1) with finite concentration than mixing
In separatory funnel, vibration shakes up, and rare earth ion is fully complexed with TODGA, stands, and separates organic phase and water phase, organic phase
Standby, rare earth ion is present in organic phase；
(3) it is stripped light rare earth：The rare earth element that b solution contains in step (1) is respectively lanthanum, cerium, praseodymium, 4 kinds of light rare earths of neodymium
During element, the organic phase in step (2) is taken in separatory funnel, mix with the c solution in step (1), using liquid-liquid extraction method
Light rare earth ion is transferred in water phase, that is, realize the enrichment to LREE using TODGA；
(4) it is stripped heavy rare earth：The rare earth element that b solution contains in step (1) be respectively europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,
When ytterbium, lutetium, 10 kinds of heavy rare earth elements of yttrium, take the organic phase in step (2) in separatory funnel, with step (1) in c solution and
Deionized water repeatedly mixes vibration and shakes up, and Heavy rare earth is transferred in water phase using liquid-liquid extraction method, that is, realize and use
Enrichments of the TODGA to heavy rare earth element.
Diluent is kerosene in the step (1), and its density is 0.8g/mL, and TODGA is 1 with the mass ratio of diluent：
(15~60).
The b solution of the step (1) is sulfate liquor, and its sulfuric acid concentration is 2.0~9.0mol/L, b after regulation acidity
Solution Rare Earth Ion is 1 with the substance withdrawl syndrome ratio of TODGA in a solution：(2~13)；The c solution of step (1) is back extraction
The aqueous phase solution for taking, it is nitric acid and hydrochloric acid mixed solution, and wherein concentration of hydrochloric acid is 0.5~6.0mol/L, and nitric acid rubs with hydrochloric acid
Your concentration ratio is 1：(1~10).
A solution mixed with b solution in the step (2) and shakes up oscillation extraction, duration of oscillation is 1~10 minute/time,
Extraction times are 2~5 times, and it is 1 that organic phase mutually extracts volume ratio with water：(0.7~3).
Back extraction condition is the volume ratio of strip liquor c solution and organic phase collected in step (2) in the step (3)
It is 1：(0.3~3), minute/time of oscillation extraction 1~10, resonance is swung 1~8 time.
Strip liquor is that one or both of c solution, deionized water are used alternatingly in the step (4), is stripped condition
It is c solution and the volume ratio of organic phase collected in step (2) is 1：(0.3~3), minute/time of oscillation extraction 1~10, altogether
Vibration 1~8 time；In deionized water and step (2) collected organic phase with volume ratio be (0.5~3)：1, oscillation extraction 1~5
Minute/time, resonance is swung 1~4 time, is not fixed using order when c solution is used alternatingly with deionized water.
According to the system of the presence Rare Earth Elements Determination after above method treatment, the extraction yield of solution Rare Earth Ion reaches
82%~100%, back extraction efficiency reaches 80%~99%, and the rate of recovery of solution Rare Earth Ion reaches 65.6%~99%.
The system for handling that the above method exists suitable for Rare Earth Elements Determination to lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium,
The independent enrichment of holmium, erbium, thulium, ytterbium, lutetium, yttrium this 14 kinds of rare earth elements.
Above-mentioned technical proposal of the invention has the beneficial effect that：
The isolation and purification method practicality simple to operate of above-mentioned 14 kinds of rare earth elements, extraction and stripping efficiency are high, sulfuric acid extraction
Environment meets industrial requirement, and the method is environmentally safe, can meet current social and Novel Extractant is utilized under sulfuric acid system
To the extraction demand of rare earth oxide.
Specific embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
A kind of to be enriched with 14 kinds of methods of rare earth element respectively, specific embodiment is as follows：
Embodiment 1
(1)：The preparation of rare earth sulfuric acid salting liquid：After taking the dissolving of 2.0g high purity lanthanum oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of lanthanum ion in the solution.
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：1.3mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 88.7mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 3.3mL concentrated sulfuric acids use is measured
21.7mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 11.3mL
Concentrated hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 250mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 18mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 1 minute is extracted 5 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 82% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 270mL is added
It is stripped, duration of oscillation 10 minutes, is stripped once, after point liquid, La3+It is present in lower floor's water phase of 270mL or so, uses
0.2mol/L EDTA solution is titrated, and it is more than 80% to obtain back extraction ratio.
Embodiment 2
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g high purity praseodymium oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/LEDTA solution, calculate the concentration of praseodymium ion in the solution.
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：5.0mLTODGA is pipetted to be diluted in
Extraction agent solution is obtained final product in 85.0mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 15mL concentrated sulfuric acids use is measured
10mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 112.5mL
Concentrated hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 148.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 45mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 10 minutes is extracted 2 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 86% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 30mL is added
It is stripped, duration of oscillation 1 minute, is stripped 8 times, after point liquid, La3+It is present in lower floor's water phase of 270mL or so, uses
0.2mol/L EDTA solution is titrated, and it is more than 85% to obtain back extraction ratio.
Embodiment 3
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g high-purity neodymium oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/LEDTA solution, calculate the concentration of neodymium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：4mLTODGA is pipetted to be diluted in
Extraction agent solution is obtained final product in 86mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 56.5mL dense
Hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 205.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 30mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 5 minutes is extracted 3 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 95% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 90mL is added
It is stripped, duration of oscillation 5 minutes, is stripped 3 times, after point liquid, La3+It is present in lower floor's water phase of 270mL or so, uses
0.2mol/L EDTA solution is titrated, and it is more than 90% to obtain back extraction ratio.
Embodiment 4
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g high-purity cerium dioxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/LEDTA solution, calculate the concentration of cerium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：2.5mLTODGA is pipetted to be diluted in
Extraction agent solution is obtained final product in 87.5mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure the dense salt of 79mL
Acid and 9.0mL concentrated nitric acids, are diluted with 182mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 22mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 3 minutes is extracted 4 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 99.3% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 54mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 5 times, after point liquid, La3+It is present in lower floor's water phase of 270mL or so, uses
0.2mol/L EDTA solution is titrated, and it is more than 95% to obtain back extraction ratio.
Embodiment 5
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g high purity terbium oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/LEDTA solution, calculate the concentration of terbium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：1.5mLTODGA is pipetted to be diluted in
Extraction agent solution is obtained final product in 88.5mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 8mL concentrated sulfuric acids use is measured
17mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure the dense salt of 79mL
Acid and 9.0mL concentrated nitric acids, are diluted with 182mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 10mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 5 minutes is extracted 5 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 98% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 54mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 5 times, after point liquid, La3+It is present in lower floor's water phase of 270mL or so, uses
0.2mol/L EDTA solution is titrated, and it is more than 80% to obtain back extraction ratio.
Embodiment 6
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g Rare earth elements moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/LEDTA solution, calculate the concentration of dysprosium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：3.0mLTODGA is pipetted to be diluted in
Extraction agent solution is obtained final product in 87mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 12mL concentrated sulfuric acids use is measured
13mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure the dense salt of 34mL
Acid and 9.0mL concentrated nitric acids, are diluted with 227mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 30mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 2 minutes is extracted 3 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 95% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 270mL is added
It is stripped, duration of oscillation 10 minutes, is stripped 1 time, after point liquid, La3+It is present in lower floor's water phase of 270mL or so, uses
0.2mol/L EDTA solution is titrated, and it is more than 82% to obtain back extraction ratio.
Embodiment 7
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g high-purity yttrium oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/LEDTA solution, calculate the concentration of ruthenium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：2.0mLTODGA is pipetted to be diluted in
Extraction agent solution is obtained final product in 88.0mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 56.5mL dense
Hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 204.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 45mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 3 minutes is extracted 2 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 92% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 30mL is added
It is stripped, duration of oscillation 2 minutes, is stripped 8 times, after point liquid, La3+It is present in lower floor's water phase of 270mL or so, uses
0.2mol/L EDTA solution is titrated, and it is more than 85% to obtain back extraction ratio.
Embodiment 8
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g high-purity gadolinium oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of gadolinium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：3.5mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 86.5mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 90.4mL dense
Hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 170.6mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 15mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 6 minutes is extracted 5 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 98% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 54mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 5 times, then wash-out back extraction 1 time is carried out with 90ml deionized waters, duration of oscillation is
5 minutes, after point liquid, then it is stripped 2 times with 54mlc solution.After dividing liquid, La3+It is present in lower floor's water phase, uses 0.2mol/L EDTA
Solution is titrated, and it is more than 90% to obtain back extraction ratio.
Embodiment 9
(1)：The preparation of rare earth sulfuric acid solution：After taking the high-purity luteium oxide moderate amount of sulfuric acid dissolvings of 2.0g, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of lutetium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：5.0mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 85.0mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 6.6mL concentrated sulfuric acids use is measured
18.4mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 56.5mL
Concentrated hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 204.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 30mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 3 minutes is extracted 3 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 94% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 45mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 4 times, then wash-out back extraction is carried out with 45ml deionized waters twice, duration of oscillation
It is 2 minutes, after point liquid, then is stripped twice with 45mlc solution.After dividing liquid, La3+It is present in lower floor's water phase, uses 0.2mol/L
EDTA solution is titrated, and it is more than 95% to obtain back extraction ratio.
Embodiment 10
(1)：The preparation of rare earth sulfuric acid solution：After taking the high-purity ytterbium oxide moderate amount of sulfuric acid dissolvings of 2.0g, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of ytterbium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：2.5mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 87.5mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 135.6mL
Concentrated hydrochloric acid and 13.5mL concentrated nitric acids, are diluted with 120.9mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 30mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 2 minutes is extracted 3 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 96% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 90mL is added
It is stripped, duration of oscillation 5 minutes, is stripped 2 times, then wash-out back extraction 3 times is carried out with 90ml deionized waters, duration of oscillation is
1 minute, after point liquid, then it is stripped 1 time with 90mlc solution.After dividing liquid, La3+It is present in lower floor's water phase, uses 0.2mol/L EDTA
Solution is titrated, and it is more than 90% to obtain back extraction ratio.
Embodiment 11
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g HIGH PURITY THULIUM OXIDEs moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of thulium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：3.8mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 86.2mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 12mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 67.5mL dense
Hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 193.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 30mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 2 minutes is extracted 3 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, obtains extraction yield more than 95%.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 54mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 5 times, then wash-out back extraction 2 times, duration of oscillation is carried out with 180ml deionized waters
It is 5 minutes, after point liquid, then is stripped once with 54mLc solution.After dividing liquid, La3+It is present in lower floor's water phase, uses 0.2mol/L
EDTA solution is titrated, and it is more than 96% to obtain back extraction ratio.
Embodiment 12
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g high-purity europium oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of europium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：2.5mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 87.5mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 67.5mL dense
Hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 193.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 30mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 5 minutes is extracted 3 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, obtains extraction yield close to 100%.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 54mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 5 times, then wash-out back extraction 2 times, duration of oscillation is carried out with 270mL deionized waters
It is 1 minute, after point liquid, then is stripped once with 54mLc solution.Finally eluted with 270mL deionized waters again.After dividing liquid, La3+
It is present in lower floor's water phase, is titrated with 0.2mol/L EDTA solution, it is more than 99% to obtain back extraction ratio.
Embodiment 13
(1)：The preparation of rare earth sulfuric acid solution：After taking the high-purity erbium oxide moderate amount of sulfuric acid dissolvings of 2.0g, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of erbium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：2.5mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 87.5mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 67.5mL dense
Hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 193.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 30mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 2 minutes is extracted 3 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 97% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 90mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 2 times, then wash-out back extraction is carried out with 90mL deionized waters twice, duration of oscillation
It is 3 minutes, after point liquid, then is stripped 1 time with 90mLc solution, is finally eluted with 90mL deionized waters again.After dividing liquid, La3+Deposit
It is in lower floor's water phase, to be titrated with 0.2mol/L EDTA solution, it is more than 94% to obtain back extraction ratio.
Embodiment 14
(1)：The preparation of rare earth sulfuric acid solution：After taking the dissolving of 2.0g Holmium Oxides moderate amount of sulfuric acid, cooling is settled to
In 250mL volumetric flasks, shake up.Titrated with 0.2mol/L EDTA solution, calculate the concentration of holmium ion in the solution；
(2)：The preparation of extraction agent solution, solution to be separated and back extraction nitration mixture：A solution：2.5mL TODGA are pipetted to be diluted in
Extraction agent solution is obtained final product in 87.5mL kerosene.B solution：The solution that 5mL steps (1) treatment is obtained is taken, 10mL concentrated sulfuric acids use is measured
15mL deionized waters dilute, and mix with 5mL rare earth sulfuric acid solutions after cooling and obtain final product solution to be separated.C solution：Measure 80.5mL dense
Hydrochloric acid and 9.0mL concentrated nitric acids, are diluted with 180.5mL deionized waters, obtain being stripped nitration mixture.
(3)：Extract and separate：The b solution that 30mL steps (2) are obtained is poured into separatory funnel, 45mL steps (2) is measured and is obtained
To a solution pour into separatory funnel and extracted, duration of oscillation 4 minutes is extracted 2 times, La3+It is present in organic phase, merges
Collect organic phase.Water is titrated with 0.02mol/LEDTA solution, and it is more than 95% to obtain extraction yield.
(4)：Back extraction operation：(3) are collected the 90mL organic phases for obtaining to pour into separatory funnel, the c solution of 54mL is added
It is stripped, duration of oscillation 3 minutes, is stripped 5 times, then wash-out back extraction is carried out with 90mL deionized waters twice, duration of oscillation
It is 1 minute, after point liquid, then is stripped once with 54mLc solution, is finally eluted twice with 90mL deionized waters again.After dividing liquid, La3+
It is present in lower floor's water phase, is titrated with 0.2mol/L EDTA solution, it is more than 97% to obtain back extraction ratio.
The above is certain preferred embodiments of the invention, it is noted that for the ordinary skill of the art
For personnel, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improve and moisten
Decorations also should be regarded as protection scope of the present invention.
Claims (6)
- It is 1. a kind of to be enriched with 14 kinds of methods of rare earth element respectively, it is characterised in that：It is dilution with kerosene with TODGA as extractant Agent, contained rare earth unit in realizing to the system for handling containing certain rare earth element by way of liquid-liquid extraction in sulfuric acid system Element Enrichment purification, the system for handling that the method exists suitable for Rare Earth Elements Determination to lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, terbium, The independent enrichment of dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium this 14 kinds of rare earth elements, comprises the following steps：(1) early-stage preparations are tested：A solution：TODGA diluents are diluted with certain proportion, extraction agent solution is obtained；B solution：Point Lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, 14 kinds of sulfate liquors of rare earth element of yttrium Pei Zhi not contained, used Placed after sulfuric acid regulation acidity, cooling is standby, obtains solution to be separated；C solution：The mixing of hydrochloric acid and nitric acid needed for preparing back extraction Acid solution, places cooling, obtains back extraction nitration mixture；(2) extract and separate：Using liquid-liquid extraction method, a solution and b solution in step (1) are mixed in point with finite concentration ratio In liquid funnel, vibration shakes up, and rare earth ion is fully complexed with TODGA, stands, and separates organic phase and water phase, and organic phase is standby, Rare earth ion is present in organic phase；(3) it is stripped light rare earth：The rare earth element that b solution contains in step (1) is respectively lanthanum, cerium, praseodymium, 4 kinds of LREEs of neodymium When, the organic phase in step (2) is taken in separatory funnel, mix with the c solution in step (1), made gently using liquid-liquid extraction method Rare earth ion is transferred in water phase, that is, realize the enrichment to LREE using TODGA；(4) it is stripped heavy rare earth：The rare earth element that b solution contains in step (1) be respectively europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, When lutetium, 10 kinds of heavy rare earth elements of yttrium, take the organic phase in step (2) in separatory funnel, with step (1) in c solution and go Ionized water repeatedly mixes vibration and shakes up, and Heavy rare earth is transferred in water phase using liquid-liquid extraction method, that is, realize and use Enrichments of the TODGA to heavy rare earth element.
- 2. it is according to claim 1 it is a kind of respectively be enriched with 14 kinds of methods of rare earth element, it is characterised in that the step (1) diluent is kerosene in, and its density is 0.8g/mL, and TODGA is 1 with the mass ratio of diluent：(15~60).
- 3. it is according to claim 1 it is a kind of respectively be enriched with 14 kinds of methods of rare earth element, it is characterised in that the step (1) b solution is sulfate liquor, and its sulfuric acid concentration is 2.0~9.0mol/L, b solution Rare Earth Ion and a after regulation acidity The substance withdrawl syndrome ratio of TODGA is 1 in solution：(2~13)；The c solution of step (1) is the aqueous phase solution of back extraction, and it is Nitric acid and hydrochloric acid mixed solution, wherein concentration of hydrochloric acid are 0.5~6.0mol/L, and nitric acid is 1 with the molar concentration rate of hydrochloric acid：(1~ 10)。
- 4. it is according to claim 1 it is a kind of respectively be enriched with 14 kinds of methods of rare earth element, it is characterised in that the step (2) a solution mixed with b solution in and shakes up oscillation extraction, duration of oscillation is 1~10 minute/time, and extraction times are 2~5 Secondary, it is 1 that organic phase mutually extracts volume ratio with water：(0.7~3).
- 5. it is according to claim 1 it is a kind of respectively be enriched with 14 kinds of methods of rare earth element, it is characterised in that the step (3) back extraction condition is strip liquor c solution and the volume ratio of organic phase collected in step (2) is 1 in：(0.3~3), shakes Minute/time of extraction 1~10 is swung, resonance is swung 1~8 time.
- 6. it is according to claim 1 it is a kind of respectively be enriched with 14 kinds of methods of rare earth element, it is characterised in that the step (4) strip liquor is that one or both of c solution, deionized water are used alternatingly in, and back extraction condition is c solution and step (2) In the volume ratio of collected organic phase be 1：(0.3~3), minute/time of oscillation extraction 1~10, resonance is swung 1~8 time；Deionization In water and step (2) collected organic phase with volume ratio be (0.5~3)：1, minute/time of oscillation extraction 1~5, resonance swings 1~ 4 times, do not fixed using order when c solution is used alternatingly with deionized water.
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