CN107299234A - A kind of green method of the recovering rare earth from useless fluorescent material and application thereof - Google Patents
A kind of green method of the recovering rare earth from useless fluorescent material and application thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B59/00—Obtaining rare earth metals
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Abstract
The present invention relates to a kind of green method of the recovering rare earth from useless fluorescent material and application thereof, comprise the following steps：(1) useless fluorescent material is mixed with alkali, melts, obtain alkali fusion thing；(2) by the carry out water logging that added water in alkali fusion thing obtained by step (1), separation obtains water logging insoluble matter and infusion, and the water logging insoluble matter acid adding is carried out into acidleach, and separation obtains acidleach insoluble matter and pickle liquor；(3) rare earth ion in pickle liquor is extracted with extractant, obtains raffinate and be loaded with the extract of rare earth ion；Extractant includes：(A) quaternary phosphonium ionic liquid and/or quaternary ammonium salt ionic liquid；(B) neutral organophosphine acid esters；Using ionic liquid as extractant；(4) extract obtained by step (3) is stripped with water, obtains ionic liquid body phase and the aqueous phase containing rare earth ion.Final rare earth yield reaches more than 90wt%, and extraction process is without saponification, and no acid and alkali consumption does not produce ammonia nitrogen waste water, is that can realize complete back extraction with water.
Description
Technical field
The present invention relates to recovering rare earth technical field, more particularly to a kind of green method of the recovering rare earth from useless fluorescent material
And application thereof.
Background technology
It is one of important secondary resource of rare earth to discard the fluorescent material contained in old fluorescent lamp, according to containing for its middle rare earth
Amount, the consumption of fluorescent material middle rare earth represents about more than the 32% rare earth market share.Rare earth therein is reclaimed, not only
Problem of environmental pollution can be alleviated, and with objective economic interests.In addition, additionally aiding the wherein crucial rare earth element of solution
Equilibrium problem.Rare earth element is often total to association, and light rare earth, relative to heavy rare earth, the content in mineral is big.If in order to
Meet the use of certain indivedual rare earth element and largely produce, the excessive production of the rare earth element of other common associations will certainly be caused,
Therefore effective recovering rare earth element from secondary rare earth resources, realizes recycling for rare earth, with very important reality meaning
Justice.
CN101307391, which reports to reclaim using traditional acid phosphine extractant P204 or P507, obtains rare earth member in fluorescent lamp
Element, but this method produces ammonia nitrogen waste water pollution, and acid consumption is high in stripping process, does not meet energy resources saving and ecological environment
The new policy requirement of protection.
CN103924084A discloses valuable metal element in a kind of waste phosphor powder using season phosphine ionic liquid recovery
Method, it is proposed that reclaim fluorescent lamp rare earth elements, its cationic moiety using new difunctional ion liquid abstraction agent
For three hexyl myristyl quaternary phosphonium salts [P6,6,6,14]+, anion is two (2- ethylhexyls) phosphonic acids (P204) of deprotonation
Or 2- ethylhexyl phosphonic acid monos (2- ethylhexyls) ester (P507), the difunctional ion liquid abstraction agent formed be respectively [P6,
6,6,14] [P204], [P6,6,6,14] [P507].This kind of difunctionalization ion liquid abstraction agent, viscosity is big, sometimes solid in half
State, during extracting metals ion, it has to which diluent is used as using another ionic liquid or volatile organic solvent.Such as
Fruit using another ionic liquid as diluent, unavoidably in the presence of it is same the problem of, i.e., whether it participates in reaction, participates in instead
Whether seasonable be that diluent is isooctanol and kerosene in ion exchange mechanism, CN103924084A, belong to it is volatile,
Inert organic solvent, can only play diluting effect, the extracting power of such single ionic liquid extraction systems is in existing skill
It is difficult to make a breakthrough in art.
CN106148697A is disclosed a kind of rare earth synergistic extractant system and carried using the extraction system from nitric rare earth feed liquid
Take separation of rare earth elements.But, the system is to impurity element, such as Fe3+、Al3+、Si4+It is required that high.Fe, Al and Si can preferentially be extracted
Take, and then the extraction of rare earth can be influenceed, the rate of recovery and purity of rare earth are difficult to ensure.
The content of the invention
In view of the problem of existing in the prior art from fluorescent material Extraction of rare earth metallic element, including fluorescent material Extraction of rare earth gold
Belong to the ammonia nitrogen waste water of the generation in the prior art pollution of element, acid consumption is high in stripping process, not environmentally, and leaching rate is limited etc., this
The purpose of invention is to provide a kind of green method of the recovering rare earth from useless fluorescent material.
For up to this purpose, the present invention is adopted the following technical scheme that：
On the one hand, the present invention provides a kind of green method of the recovering rare earth from useless fluorescent material, and methods described includes as follows
Step：
(1) useless fluorescent material is mixed with alkali, melts, obtain alkali fusion thing；
(2) by the carry out water logging that added water in alkali fusion thing obtained by step (1), separation obtains water logging insoluble matter and infusion, by institute
State acid adding in water logging insoluble matter and carry out acidleach, separation obtains acidleach insoluble matter and pickle liquor；
(3) with the rare earth ion in pickle liquor obtained by extractant extraction step (2), obtain raffinate and be loaded with rare earth from
The extract of son；
Wherein, the extractant includes component A and B component：(A) quaternary phosphonium ionic liquid and/or quaternary ammonium salt ionic liquid；
(B) neutral organophosphine acid esters；
(4) extract obtained by step (3) is stripped with water, obtains ionic liquid body phase and the aqueous phase containing rare earth ion.
The present invention, can preferential substantial amounts of Al in removing system using the method for alkali fusion water logging3+, this is just somebody's turn to do directly to use
Ionic liquid synergistic extractant system recovering rare earth from the pickle liquor of the water logging slag obtained after alkali fusion water logging is provided convenience condition, nothing
The interference of impurity element need to be considered, the rate of recovery and purity of such rare earth can be protected.
Step (1) the of the present invention alkali preferably include in sodium carbonate, sodium hydroxide and sodium peroxide any one or extremely
Few two kinds combination, preferably sodium peroxide and/or sodium carbonate.
Preferably, the mass ratio of the alkali of step (1) the useless fluorescent material and alkali is 1:0.3~1, such as 1:0.3、1:0.4、
1:0.5、1:0.6、1:0.7、1:0.8、1:0.9 or 1:1 etc., preferably 1:0.5~0.8.
The temperature of step (1) the of the present invention melting is preferably 500~900 DEG C, such as 500 DEG C, 550 DEG C, 600 DEG C, 650
DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or DEG C 900 DEG C etc., preferably 700~850 DEG C；
Preferably, the time of step (1) described melting be 0.5~3h, such as 0.5h, 0.8h, 1h, 1.2h, 1.5h,
1.8h, 2h, 2.2h, 2.5h, 2.8h or 3h etc., preferably 1~2h.
The mass ratio of step (2) the alkali fusion thing of the present invention and the water is preferably 1:10~10:1, such as 1:10、1:8、
1:5、1:1、5:1、2:1、8:1 or 10:1 etc., preferably 1:5~5:1.
Water logging can be first by most amphoteric metal ion-transfer in fluorescent material to infusion, so that final contains
The pickle liquor impurity content of rare earth is few, is that further rare earth extraction separation alleviates pressure.Alkali fusion mistake can be water-washed away simultaneously
Unnecessary unreacted alkali in journey, reduces superacid consumption during follow-up acidleach.
Preferably, the temperature of step (2) described water logging be 20~80 DEG C, such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C,
45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc., preferably 50~80 DEG C.
Step (2) the of the present invention acid preferably includes nitric acid, preferably 2~8mol/L nitric acid, such as 2mol/L, 3mol/
L, 4mol/L, 5mol/L, 6mol/L, 7mol/L or 8mol/L etc., more preferably 3~5mol/L nitric acid.
Preferably, step (2) the water logging insoluble matter and the sour mass ratio are 1:10~10:1, such as 1:10、1:
8、1:5、1:1、5:1、2:1、8:1 or 10:1 etc., preferably 1:5~5:1.
In step (3) the of the present invention extractant quaternary ammonium salt ionic liquid preferably include [A336] [Cl] ionic liquid and/
Or [A336] [NO3] ionic liquid.
Preferably, in step (3) described extractant quaternary phosphonium ionic liquid include [P666,14] [Cl] and/or [P666,
14][NO3] ionic liquid.
Preferably, B component includes 2- ethylhexyls phosphonic acids two (2- ethylhexyls) ester in step (3) described extractant.
Preferably, the volume ratio of component A and B component is 1 in step (3) described extractant:4~4:1, such as 1:4、1:3、
1:2、2:3、1:1、3:2、2:1、3:1 or 4:1 etc., preferably 1.5:3.5~1:1.
Preferably, step (3) extractant and the volume ratio of the pickle liquor are 1:20~10:1, such as 1:20、1:
15、1:10、1:8、1:5、1:1、5:1、2:1、8:1 or 10:1 etc., preferably 1:5~5:1.
Preferably, during step (3) described extraction, the ionic strength of aqueous phase is 0.5~5mol/L, for example
0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or
5mol/L etc., preferably 2.0~4.0mol/L.There is synergy between the ionic strength and pH value of aqueous phase.When the ion of aqueous phase
When intensity is less than 0.5mol/L, extraction yield is relatively low, and when the ionic strength of aqueous phase is higher than 5mol/L, extraction system viscosity is too big,
It is not easy to the operation of extraction；In addition, when pH value is less than 2, extraction declines, and when pH value is more than 5.5, rare earth easily occurs and common
The hydrolysis problem for the other metal ions deposited.Thus it is guaranteed that pH value is 2 while the ionic strength of aqueous phase is 0.5~5mol/L
~5.5, it is ensured that rare earth has higher extraction yield.
Preferably, during step (3) described extraction, the pH value of aqueous phase is 2~5.5, such as 2,2.2,2.5,2.8,
3rd, 3.2,3.5,3.8,4,4.5,5,5.2 or 5.5 etc., preferably 3~3.5.
Preferably, also include before step (3) described extraction：Salting-out agents are added in the pickle liquor.
Preferably, the salting-out agents include sodium nitrate and/or lithium nitrate.
Preferably, the addition of the salting-out agents is that the concentration for making it in feed liquid is 0.5~5mol/L, for example
0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or
5mol/L etc., preferably 2.0~4.0mol/L.
The volume ratio of step (4) the of the present invention water and the extract is preferably 1:1~10, such as 1:1、1:2、1:3、
1:4、1:5、1:6、1:7、1:8、1:9 or 1:10 etc., preferably 1:1~5.
Ionic liquid body phase obtained by step (4) of the present invention is preferably returned to step (3) and recycled as extractant.
As currently preferred technical scheme, methods described comprises the following steps：
(1) it is 1 according to mass ratio by useless fluorescent material and alkali:0.3~1 mixing, 500~900 DEG C of 1~3h of melting, obtains alkali
Fusant；
(2) it is 1 according to mass ratio:10~10:1 will add water in alkali fusion thing obtained by step (1) carries out water logging in 20~80 DEG C,
Separation, obtains water logging insoluble matter and infusion, is 1 according to the mass ratio of water logging insoluble matter and acid:10~10:1 by the water logging
Acid adding carries out acidleach in insoluble matter, and separation obtains acidleach insoluble matter and pickle liquor；
(3) salting-out agents sodium nitrate and/or lithium nitrate are added in the pickle liquor, make its concentration in feed liquid for 0.5~
5mol/L, with the rare earth ion in extractant extraction pickle liquor, the volume ratio of the extractant and the pickle liquor is 1:20~
10:1, the ionic strength of aqueous phase is 0.5~5mol/L, and pH value is 2~5.5, obtains raffinate and is loaded with the extraction of rare earth ion
Take liquid；
Wherein, it is 1 that the extractant, which includes volume ratio,:4~4:1 component A and B component：(A) quaternary phosphonium ionic liquid
And/or quaternary ammonium salt ionic liquid；The quaternary ammonium salt ionic liquid includes [A336] [Cl] ionic liquid and/or [A336] NO3] from
Sub- liquid；The quaternary phosphonium ionic liquid includes [P666,14] [Cl] and/or [P666,14] [NO3] ionic liquid；(B) it is neutral
Organophosphonate；
(4) extract obtained by step (3) is stripped with water, the volume ratio of the water and the extract is 1:10~
1:1, ionic liquid body phase and the aqueous phase containing rare earth ion are obtained, the ionic liquid body phase return to step (3) is circulated as extractant
Utilize.
Second aspect, the invention provides the purposes of method as described in relation to the first aspect, methods described is used to reclaim useless fluorescence
Powder middle rare earth, the high bisulfate waste liquor middle rare earth of enrichment, the useless neodymium-iron-boron magnetic material middle rare earth of recovery.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention firstly provides the scheme that alkali fusion, water logging and ionic liquid synergistic extractant system are cooperateed with mutually, realize useless glimmering
The efficient leaching of light powder middle rare earth metallic element, the rate of recovery reaches more than 90wt%, and purity reaches more than 91wt%；By to extraction bar
The optimization of part, using pH value and the synergy of ionic strength, further increases the leaching rate of thulium.
(2) extraction process of the present invention is without saponification, and no acid and alkali consumption does not produce ammonia nitrogen waste water, it is easy to be stripped, with water
To realize back extraction completely, physical phenomenon is good.
Brief description of the drawings
Fig. 1 is the exemplary process diagram of the green method of the recovering rare earth of the present invention from useless fluorescent material.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.But following realities
Example is only the simple example of the present invention, does not represent or limit the scope of the present invention, protection scope of the present invention
It is defined by claims.
Embodiment 1
A kind of green method of the recovering rare earth from useless fluorescent material, step is as follows：
1) by 40wt% rouge and powder, 25wt% blue powders, the useless fluorescent material of the green powder compositions of 35wt% and sodium hydroxide according to quality
Than for 1:0.3 mixing, 500 DEG C of melting 3h, obtains alkali fusion thing；
2) it is 1 according to mass ratio:10 by step 1) adding water in gained alkali fusion thing carries out water loggings in 80 DEG C, and separation obtains water
Insoluble matter and infusion are soaked, is 1 according to the mass ratio of water logging insoluble matter and 2mol/L nitric acid:10 enter acid adding in water logging insoluble matter
Row acidleach, separation, obtains acidleach insoluble matter and pickle liquor；
3) with the rare earth ion in extractant extraction pickle liquor, the volume ratio of the extractant and the pickle liquor is 1:
20, the ionic strength of aqueous phase is 0.5mol/L, and pH value is 2, obtains raffinate and is loaded with the extract of rare earth ion；
Wherein, it is 1 that extractant, which includes volume ratio,:4 [A336] [Cl] ionic liquid and (the 2- second of 2- ethylhexyls phosphonic acids two
Base hexyl) ester；
4) by step 3) gained extract is stripped with water, and the volume ratio of the water and the extract is 1:10, obtain
To ionic liquid body phase and the aqueous phase containing rare earth ion.
Embodiment 2
A kind of green method of the recovering rare earth from useless fluorescent material, step is as follows：
1) by 40wt% rouge and powder, 25wt% blue powders, the useless fluorescent material of the green powder compositions of 35wt% and sodium carbonate according to mass ratio
For 1:1 mixing, 900 DEG C of melting 0.5h, obtains alkali fusion thing；
2) it is 10 according to mass ratio:1 by step 1) adding water in gained alkali fusion thing carries out water loggings in 20 DEG C, and separation obtains water
Insoluble matter and infusion are soaked, is 10 according to the mass ratio of water logging insoluble matter and 8mol/L nitric acid:1 enters acid adding in water logging insoluble matter
Row acidleach, separation, obtains acidleach insoluble matter and pickle liquor；
3) salting-out agents sodium nitrate is added in the pickle liquor, it is 5mol/L to make its concentration in feed liquid, is extracted with extractant
Take the rare earth ion in pickle liquor, the volume ratio of the extractant and the pickle liquor is 10:1, the ionic strength of aqueous phase is
5mol/L, pH value is 5.5, obtains raffinate and is loaded with the extract of rare earth ion；
Wherein, it is 4 that extractant, which includes volume ratio,:1 [A336] [NO3] ionic liquid and the (2- of 2- ethylhexyls phosphonic acids two
Ethylhexyl) ester；
4) by step 3) gained extract is stripped with water, and the volume ratio of the water and the extract is 1:1, obtain
Ionic liquid body phase and the aqueous phase containing rare earth ion.
Embodiment 3
A kind of green method of the recovering rare earth from useless fluorescent material, step is as follows：
1) by 40wt% rouge and powder, 25wt% blue powders, the useless fluorescent material of the green powder compositions of 35wt% and sodium peroxide according to quality
Than for 1:0.8 mixing, 700 DEG C of melting 2h, obtains alkali fusion thing；
2) it is 1 according to mass ratio:5 by step 1) adding water in gained alkali fusion thing carries out water loggings in 50 DEG C, and separation obtains water logging
Insoluble matter and infusion, are 1 according to the mass ratio of water logging insoluble matter and 3mol/L nitric acid:5 will add in the water logging insoluble matter
Acid carries out acidleach, and separation obtains acidleach insoluble matter and pickle liquor；
3) salting-out agents sodium nitrate is added in the pickle liquor, it is 1mol/L to make its concentration in feed liquid, is extracted with extractant
Take the rare earth ion in pickle liquor, the volume ratio of the extractant and the pickle liquor is 1:5, the ionic strength of aqueous phase is
4.0mol/L, pH value is 3, obtains raffinate and is loaded with the extract of rare earth ion；
Wherein, it is 1.5 that extractant, which includes volume ratio,:3.5 [P666,14] [Cl] and (the 2- second of 2- ethylhexyls phosphonic acids two
Base hexyl) ester；
4) by step 3) gained extract is stripped with water, and the volume ratio of the water and the extract is 1:1, obtain
Ionic liquid body phase and the aqueous phase containing rare earth ion, the ionic liquid body phase return to step 3) recycled as extractant.
Embodiment 4
A kind of green method of the recovering rare earth from useless fluorescent material, step is as follows：
1) by 40wt% rouge and powder, 25wt% blue powders, the useless fluorescent material of the green powder compositions of 35wt% and sodium peroxide according to quality
Than for 1:0.5 mixing, 850 DEG C of melting 1h, obtains alkali fusion thing；
2) it is 5 according to mass ratio:1 by step 1) adding water in gained alkali fusion thing carries out water loggings in 80 DEG C, and separation obtains water logging
Insoluble matter and infusion, are 5 according to the mass ratio of water logging insoluble matter and 5mol/L nitric acid:1 will add in the water logging insoluble matter
Acid carries out acidleach, and separation obtains acidleach insoluble matter and pickle liquor；
3) salting-out agents lithium nitrate is added in the pickle liquor, it is 3.0mol/L to make its concentration in feed liquid, uses extractant
The volume ratio of rare earth ion in extraction pickle liquor, the extractant and the pickle liquor is 5:1, the ionic strength of aqueous phase is
2.0mol/L, pH value is 3.5, obtains raffinate and is loaded with the extract of rare earth ion；
Wherein, it is 1 that extractant, which includes volume ratio,:1 [P666,14] [NO3] ionic liquid and 2- ethylhexyls phosphonic acids two
(2- ethylhexyls) ester；
4) by step 3) gained extract is stripped with water, and the volume ratio of the water and the extract is 1:5, obtain
Ionic liquid body phase and the aqueous phase containing rare earth ion, the ionic liquid body phase return to step 3) recycled as extractant.
Embodiment 5
A kind of green method of the recovering rare earth from useless fluorescent material, step is as follows：
1) by 40wt% rouge and powder, 25wt% blue powders, the useless fluorescent material of the green powder compositions of 35wt% and sodium peroxide according to quality
Than for 1:0.6 mixing, 800 DEG C of melting 1.5h, obtains alkali fusion thing；
2) it is 1 according to mass ratio:1 by step 1) adding water in gained alkali fusion thing carries out water loggings in 65 DEG C, and separation obtains water logging
Insoluble matter and infusion, are 1 according to the mass ratio of water logging insoluble matter and 4mol/L nitric acid:1 will add in the water logging insoluble matter
Acid carries out acidleach, and separation obtains acidleach insoluble matter and pickle liquor；
3) salting-out agents lithium nitrate is added in the pickle liquor, it is 3.0mol/L to make its concentration in feed liquid, uses extractant
The volume ratio of rare earth ion in extraction pickle liquor, the extractant and the pickle liquor is 1:1, the ionic strength of aqueous phase is
3.0mol/L, pH value 3.5 obtains raffinate and is loaded with the extract of rare earth ion；
Wherein, it is 2 that extractant, which includes volume ratio,:3 [A336] [NO3] ionic liquid and the (2- of 2- ethylhexyls phosphonic acids two
Ethylhexyl) ester；
4) by step 3) gained extract is stripped with water, and the volume ratio of the water and the extract is 1:3, obtain
Ionic liquid body phase and the aqueous phase containing rare earth ion, the ionic liquid body phase return to step 3) recycled as extractant.
Comparative example 1
With differing only in for embodiment 5：Save step 2) in water logging step.
Comparative example 2
Difference with embodiment 5 is：By step 3) in extractant replace with after [A336] [P204] diluted with octane
Concentration is 0.5mol/L extraction phase, and by step 4) in water replace with 0.01mol/L nitric acid.
Comparative example 3
With differing only in for embodiment 5：Step 3) in aqueous phase ionic strength be 0.25mol/L.
Comparative example 4
With differing only in for embodiment 5：Step 3) in aqueous phase pH value be 1.
Containing for aqueous phase Rare Earth Ion of the gained containing rare earth ion in each embodiment and comparative example is detected with ICP-OES methods
Amount, show that the leaching rate of fluorescent material Rare Earth Ion is as shown in table 1.
Table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The rate of recovery | 95.4wt% | 95.6wt% | 96.1wt% | 96.3wt% | 97.4wt% |
| Purity | 99.2wt% | 99.5wt% | 98.9wt% | 99.1wt% | 99.6wt% |
| Comparative example | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| The rate of recovery | 82.1wt% | 62.4wt% | 90.5wt% | 90.6wt% | |
| Purity | 85.3wt% | 90.5wt% | 91.2wt% | 92.5wt% |
Comparative example 1 eliminates water logging step, it is impossible to effectively removes the Al elements in leachate, causes final rare earth metal
Element recovery rate is only 82.1wt%, and purity also only has 85.3wt%, and the rate of recovery and purity are far below embodiment 5.When comparative example 2
When the traditional liquid-liquid extraction constituted with [A336] [P204] and octane replaces ion liquid abstraction, extraction yield is low under the same terms,
Only 72.4wt%, and back extraction can hardly be realized with water, it can only be stripped with acid, and its extraction yield is far below embodiment
5.To sum up, the scheme cooperateed with mutually present invention firstly provides alkali fusion, water logging and ionic liquid synergistic extractant system is to realize useless fluorescent material
The efficient leaching of middle rare earth metallic element, wherein, alkali fusion, water logging and ionic liquid synergistic extractant system cooperate, and lack or replace
A wherein step will significantly reduce the rate of recovery and purity of final thulium.
The aqueous ion intensity of extraction step, which deviates, in comparative example 3 extracts step in scope preferred for this invention, comparative example 4
Rapid aqueous pH values deviate scope preferred for this invention, then the rate of recovery of comparative example 3~4 is rolled over significantly compared to embodiment 5
Button.In addition, when pH is bigger than normal compared with the application, even if there is suitable ionic strength, also resulting in rare earth and non-rare-earth precipitation, extraction is difficult
To carry out；When ionic strength is bigger than normal compared with the application, system viscosity is excessive can not carry out experimental implementation.To sum up, the present invention is by right
The optimization of extraction conditions, using pH value and the synergy of ionic strength, further increases the leaching rate of thulium.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of green method of the recovering rare earth from useless fluorescent material, it is characterised in that methods described comprises the following steps：
(1) useless fluorescent material is mixed with alkali, melts, obtain alkali fusion thing；
(2) by the carry out water logging that added water in alkali fusion thing obtained by step (1), separation obtains water logging insoluble matter and infusion, by the water
Soak acid adding in insoluble matter and carry out acidleach, separation obtains acidleach insoluble matter and pickle liquor；
(3) with the rare earth ion in pickle liquor obtained by extractant extraction step (2), obtain raffinate and be loaded with rare earth ion
Extract；
Wherein, the extractant includes component A and B component：(A) quaternary phosphonium ionic liquid and/or quaternary ammonium salt ionic liquid；(B)
Neutral organophosphine acid esters；
(4) extract obtained by step (3) is stripped with water, obtains ionic liquid body phase and the aqueous phase containing rare earth ion.
2. the method as described in claim 1, it is characterised in that step (1) described alkali includes sodium carbonate, sodium hydroxide and peroxide
Change in sodium any one or at least two combination, preferably sodium peroxide and/or sodium carbonate；
Preferably, the mass ratio of step (1) the useless fluorescent material and alkali is 1:0.3~1, preferably 1:0.5~0.8.
3. method as claimed in claim 1 or 2, it is characterised in that the temperature of step (1) described melting is 500~900 DEG C,
It is preferred that 700~850 DEG C；
Preferably, the time of step (1) described melting is 0.5~3h, preferably 1~2h.
4. the method as described in any one of claims 1 to 3, it is characterised in that the matter of step (2) the alkali fusion thing and the water
Amount is than being 1:10~10:1, preferably 1:5~5:1；
Preferably, the temperature of step (2) described water logging is 20~80 DEG C, preferably 50~80 DEG C.
5. the method as described in any one of Claims 1 to 4, it is characterised in that step (2) acid includes nitric acid, preferably 2~
The nitric acid of 8mol/L nitric acid, more preferably 3~5mol/L；
Preferably, step (2) the water logging insoluble matter and the sour mass ratio are 1:10~10:1, preferably 1:5~5:1.
6. the method as described in any one of Claims 1 to 5, it is characterised in that quaternary ammonium salt ion in step (3) described extractant
Liquid includes [A336] [Cl] ionic liquid and/or [A336] [NO3] ionic liquid；
Preferably, quaternary phosphonium ionic liquid includes [P666,14] [Cl] and/or [P666,14] in step (3) described extractant
[NO3] ionic liquid；
Preferably, B component includes 2- ethylhexyls phosphonic acids two (2- ethylhexyls) ester in step (3) described extractant；
Preferably, the volume ratio of component A and B component is 1 in step (3) described extractant:4~4:1, preferably 1.5:3.5~1:
1；
Preferably, step (3) extractant and the volume ratio of the pickle liquor are 1:20~10:1, preferably 1:5~5:1；
Preferably, during step (3) described extraction, the ionic strength of aqueous phase is 0.5~5mol/L, preferably 2.0~
4.0mol/L；
Preferably, during step (3) described extraction, the pH value of aqueous phase is 2~5.5, preferably 3~3.5；
Preferably, also include before step (3) described extraction：Salting-out agents are added in the pickle liquor；
Preferably, the salting-out agents include sodium nitrate and/or lithium nitrate；
Preferably, the addition of the salting-out agents is that the concentration for making it in feed liquid is 0.5~5mol/L, preferably 2.0~
4.0mol/L。
7. the method as described in any one of claim 1~6, it is characterised in that the body of step (4) water and the extract
Product is than being 1:1~10, preferably 1:1~5.
8. the method as described in any one of claim 1~7, it is characterised in that ionic liquid body phase return to step obtained by step (4)
(3) recycled as extractant.
9. the method as described in any one of claim 1~8, it is characterised in that methods described comprises the following steps：
(1) it is 1 according to mass ratio by useless fluorescent material and alkali:0.3~1 mixing, 500~900 DEG C of 1~3h of melting, obtains alkali fusion thing；
(2) it is 1 according to mass ratio:10~10:1 will add water in alkali fusion thing obtained by step (1) carries out water logging in 20~80 DEG C, point
From, obtain water logging insoluble matter and infusion, according to water logging insoluble matter with acid mass ratio be 1:10~10:1 by the water logging not
Acid adding carries out acidleach in molten thing, and separation obtains acidleach insoluble matter and pickle liquor；
(3) salting-out agents sodium nitrate and/or lithium nitrate are added in the pickle liquor, it is 0.5~5mol/ to make its concentration in feed liquid
L, with the rare earth ion in extractant extraction pickle liquor, the volume ratio of the extractant and the pickle liquor is 1:20~10:1,
The ionic strength of aqueous phase is 0.5~5mol/L, and pH value is 2~5.5, obtains raffinate and is loaded with the extract of rare earth ion；
Wherein, it is 1 that the extractant, which includes volume ratio,:4~4:1 component A and B component：(A) quaternary phosphonium ionic liquid and/or
Quaternary ammonium salt ionic liquid；The quaternary ammonium salt ionic liquid includes [A336] [Cl] ionic liquid and/or [A336] [NO3] ionic liquid
Body；The quaternary phosphonium ionic liquid includes [P666,14] [Cl] and/or [P666,14] [NO3] ionic liquid；(B) it is neutral organic
Phosphonate ester；
(4) extract obtained by step (3) is stripped with water, the volume ratio of the water and the extract is 1:10~1:1,
Ionic liquid body phase and the aqueous phase containing rare earth ion are obtained, the ionic liquid body phase return to step (3) recycles as extractant.
10. such as the purposes of any one of claim 1~9 methods described, it is characterised in that methods described is used to reclaim useless fluorescent material
Middle rare earth, the high bisulfate waste liquor middle rare earth of enrichment, the useless neodymium-iron-boron magnetic material middle rare earth of recovery.
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