CN103194627B - Method for removing aluminum in rare earth solution - Google Patents
Method for removing aluminum in rare earth solution Download PDFInfo
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- CN103194627B CN103194627B CN201310115287.8A CN201310115287A CN103194627B CN 103194627 B CN103194627 B CN 103194627B CN 201310115287 A CN201310115287 A CN 201310115287A CN 103194627 B CN103194627 B CN 103194627B
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- organic phase
- neodymium
- praseodymium
- praseodymium neodymium
- aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a method for removing aluminum in rare earth solution. The method is that a P507-kerosene-hydrochloric acid extraction system is utilized for implementing reverse extraction in steps based on the difference of distribution coefficients of praseodymium neodymium and aluminum in the back extraction process during the light rare-earth lanthanum-cerium/praseodymium-neodymium cascade extraction separation process, thus realizing the preferential separation of the praseodymium neodymium and aluminum. The method adopting inorganic acid with low-middle acidity as reverse liquid comprises the following steps of: firstly, adding a proper amount of inorganic acid with low-middle acidity as a back-extractant to enable the back-extraction rate of praseodymium neodymium to be 80%-90%, thus obtaining the qualified praseodymium neodymium solution; secondly, remaining the rest praseodymium neodymium and most of the aluminums in an organic phase, and carrying out 3 to 7 level cascade back extraction on the organic phase through the inorganic acid with acidity of 3.0 to 5.0mol/L; and thirdly, separating the praseodymium neodymium and the aluminum in the back extraction solution by the oxalate precipitation method. By adopting the method, the after-treatment amount in aluminum removal is greatly decreased, therefore, lots of aluminum removal agents can be saved, the production efficiency can be improved, and the production cost is also reduced.
Description
Technical field
The present invention relates to a kind of method removing aluminium in earth solution, particularly a kind of method removing aluminium in praseodymium neodymium earth solution
Background technology
It is the multi-metal complex mineral intergrowths such as rare earth, iron, niobium, thorium that baiyunebo concentrate is hidden, and genus hamartite and monazite are main (ratio is about 3: 1 ~ 4: 1), mixed type light rare earths ore deposit.Wherein, a kind of Al of typical sample ore in rare earth mineral intergrowth
2o
3content is 2.68%, can seem the height of content completely.When di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester-kerosene-hcl as extraction agent system is separated LaCe/PrNd rare earths material, due to aluminium a large amount of existence and in stripping section PrNd liquid outlet accumulation enrichment, this just causes the result that in praseodymium neodymium solution, aluminium is high.Aluminum removing method conventional in current production has chemical precipitation method, centrifuging, extraction process etc.Aforesaid method is many removes aluminium after feed liquid output, and production stage is complicated and the praseodymium neodymium feed liquid of output needs independent except aluminium, wastes in a large number except aurin tricarboxylic acid, not only increases production cost, and the waste water ratio of output comparatively refractory reason.
Summary of the invention
The present invention, in order to overcome the deficiency of current aluminum removing method, provides the aluminum removing method that a kind of technique is simple, with low cost.
The present invention extracts stripping section on production line at LaCe/PrNd to adopt substep reverse-extraction method, realizes being separated of praseodymium neodymium and aluminium.Namely first by the organic phase back extraction of load praseodymium neodymium and aluminium, back extraction ratio reaches 80% ~ 90%, obtains the qualified praseodymium chloride neodymium solution that aluminium content and the ratio of rare earth concentration are less than 500ppm; Carry out secondary back extraction to the organic phase of its surplus praseodymium neodymium of load and aluminium again, aluminium is separated with praseodymium neodymium by the strip liquor oxalate precipitation method obtained.Greatly reduce the aftertreatment amount except aluminium like this, not only save a large amount of except aurin tricarboxylic acid, improve production efficiency, and reduce production cost, is a kind of brand-new aluminum removing method.
The present invention utilizes 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester-kerosene-hcl as extraction agent system in light rare earths lanthanum cerium/praseodymium neodymium cascade extraction process, the partition ratio difference in stripping process according to praseodymium neodymium and aluminium, carry out substep back extraction, realize preferentially being separated of praseodymium neodymium and aluminium.First, use middle Low acid mineral acid (example hydrochloric acid, nitric acid etc.) as anti-liquid, select suitable acid amount, make the back extraction ratio of praseodymium neodymium reach 80% ~ 90%, obtain qualified praseodymium neodymium solution.Next, praseodymium neodymium and most of aluminium of its surplus are retained in organic phase, the mineral acid of acidity 3.0 ~ 5.0mol/L (example hydrochloric acid, nitric acid etc.) is utilized to carry out 3 ~ 7 grades of tandem back extractions to this organic phase, be separated with praseodymium neodymium by aluminium in gained praseodymium neodymium stripping workshop with oxalate precipitation method, the praseodymium oxalate neodymium salt obtained enters lower step recovery process.
The present invention is achieved through the following technical solutions:
(1) 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester is mixed with kerosene, be mixed with organic phase A;
(2) above-mentioned organic phase A sodium hydroxide is carried out saponification, obtain organic phase B, in organic phase B, add praseodymium neodymium rare earth feed liquid again extract, obtain 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester organic phase, the i.e. organic phase C of supported rare earth and aluminium;
(3) carry out back extraction with inorganic acid solution to organic phase C, make back extraction ratio reach 80% ~ 90%, and obtain organic phase D and strip liquor A, now in strip liquor A, aluminium content is less than 500ppm with the ratio of rare earth REO concentration;
(4) above-mentioned organic phase D inorganic acid solution is carried out tandem back extraction, obtain strip liquor B, with oxalic acid to strip liquor B process, reclaim praseodymium oxalate neodymium.
Further, in organic phase A, the concentration of 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester is 1.4 ~ 1.6mol/L; The saponification deg of organic phase B is 0.40 ~ 0.54mol/L; Step (3) can be hydrochloric acid, nitric acid or sulphuric acid soln with inorganic acid solution used in step (4); Inorganic acid solution acidity used in step (3) and step (4) is 3.0 ~ 5.0mol/L; In step (4), tandem back extraction progression can be 3 ~ 7 grades; In step (4), aluminium content (Al in praseodymium oxalate neodymium
2o
3/ REO) be less than 0.01%.
Further, the hydrochloric acid of the preferred 5.0mol/L of inorganic acid solution used in step (3) and step (4).
Further, the concentration that the method that the present invention relates to is particularly useful for praseodymium neodymium rare earth feed liquid is the separation of aluminium in the earth solution of 1.50 ~ 1.71mol/L.
The present invention and existing earth solution, except compared with aluminum technology, save except aurin tricarboxylic acid, decrease artificial and production link, and waste water quantum of output is few and easily administer, and greatly reduce cost, and can reach well except aluminium effect.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
In figure, S: organic phase; OH
-: alkali lye; F: rare earth feed liquid; W: washing lotion; ST: anti-liquid; SR: strip liquor
Embodiment
Embodiment 1
2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester-kerosene organic phase B6L of preparation saponification deg 0.49mol/L, with it, 640mL is extracted containing the praseodymium neodymium earth solution that aluminium 0.016mol/L, REO concentration is 1.53mol/L, obtain the organic phase C of supported rare earth and aluminium.Be that the hydrochloric acid of 5mol/L carries out back extraction to aforesaid organic phase C by 528mL concentration, obtain organic phase D and praseodymium neodymium strip liquor A.Al in this praseodymium neodymium strip liquor A
2o
3concentration is 0.0017mol/L, and earth solution REO concentration is 1.64mol/L, and this praseodymium neodymium strip liquor A is the qualified product that aluminium content is less than 500ppm.With acid amount be 8ml, acidity is that the hydrochloric acid of 5mol/L carries out 5 grades of tandem back extractions to the organic phase D that praseodymium neodymium concentration is 0.04mol/L, every grade of organic phase 300mL, Al in the praseodymium neodymium strip liquor B obtained
2o
3for 0.016mol/L, rare earth concentration REO is 1.66mol/L.The praseodymium neodymium strip liquor B high to aluminium content with oxalic acid precipitates, and removes impurity aluminum, aluminium content (Al in obtained praseodymium oxalate neodymium
2o
3/ REO) for being less than 0.01%, meet product requirement.
Embodiment 2
2-ethylhexyl phosphonic acid list (2-ethylhexyl) the ester organic phase B25L of preparation saponification deg 0.48mol/L, extracts the praseodymium neodymium feed liquid that 2595mL aluminium content 0.020mol/L, REO are 1.54mol/L with it, obtains organic phase C.By the hydrochloric acid back extraction organic phase C that 2183mL concentration is 5mol/L, obtain organic phase D and praseodymium neodymium strip liquor A.Al in this praseodymium neodymium strip liquor A
2o
3for 0.00037mol/L, REO concentration is 1.63mol/L, this strip liquor is the qualified product that aluminium content is less than 500ppm.With acid amount be 18ml, acidity is that the hydrochloric acid of 5mol/L carries out 6 grades of tandem back extractions to the organic phase D that praseodymium neodymium concentration is 0.0296mol/L, every grade of organic phase 1000mL, Al in the praseodymium neodymium strip liquor B obtained
2o
3for 0.015mol/L, rare earth concentration REO is 1.67mol/L.With oxalic acid, praseodymium neodymium strip liquor B is precipitated, remove impurity aluminum, aluminium content (Al in obtained praseodymium oxalate neodymium
2o
3/ REO) for being less than 0.01%, meet product requirement.
Embodiment 3
The P507 organic phase B6L of preparation saponification deg 0.50mol/L, extracts the praseodymium neodymium feed liquid that 638mL aluminium content 0.038mol/L, REO are 1.5336mol/L with it, obtains organic phase C.By the hydrochloric acid back extraction organic phase C that 528mL concentration is 5mol/L, obtain organic phase D and praseodymium neodymium strip liquor A.Containing Al in this praseodymium neodymium strip liquor A
2o
3for 0.00056mol/L, REO are 1.64mol/L, this praseodymium neodymium strip liquor A is the qualified product that aluminium content is less than 500ppm.Now contain praseodymium neodymium 0.0189mol/L in organic phase D.Be that the 5mol/L hydrochloric acid of 4mL carries out 7 grades of tandem back extractions to organic phase D, every grade of organic phase 300mL, Al in the praseodymium neodymium strip liquor B obtained by acid amount
2o
3for 0.022mol/L, rare earth concentration REO is 1.67mol/L.With oxalic acid, praseodymium neodymium strip liquor B is precipitated, remove impurity aluminum, aluminium content (Al in obtained praseodymium oxalate neodymium
2o
3/ REO) for being less than 0.01%, meet product requirement.
Embodiment 4
The P507 organic phase B25L of preparation saponification deg 0.48mol/L, extracts the praseodymium neodymium feed liquid that 2600mL aluminium content 0.038mol/L, REO are 1.5343mol/L with it, obtains organic phase C.By the hydrochloric acid back extraction organic phase C that 2183mL concentration is 5mol/L, obtain organic phase D and praseodymium neodymium strip liquor A, Al in this praseodymium neodymium strip liquor A
2o
3for 0.00048mol/L, REO are 1.64mol/L, this praseodymium neodymium strip liquor A is the qualified product that aluminium content is less than 500ppm.Now contain praseodymium neodymium 0.016mol/L in organic phase D.Be that the 5mol/L hydrochloric acid of 10mL carries out 5 grades of tandem back extractions to organic phase C, every grade of organic phase 1000mL, Al in the praseodymium neodymium strip liquor B obtained by acid amount
2o
3for 0.0237mol/L, rare earth concentration REO is 1.66mol/L.With oxalic acid, praseodymium neodymium strip liquor B is precipitated, remove impurity aluminum, aluminium content (Al in obtained praseodymium oxalate neodymium
2o
3/ REO) for being less than 0.01%, meet product requirement.
Analytical results shows: the aluminium cost that removes per ton is no more than 680 yuan (in praseodymium neodymium oxide).It save except aurin tricarboxylic acid, decrease artificial and production link, except aluminium cost is low, technique is simple, strong operability, and can reach well except aluminium effect.
Claims (1)
1. remove a method for aluminium in praseodymium neodymium earth solution, it is characterized in that comprising the steps:
(1) 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester is mixed with kerosene, be mixed with organic phase A;
(2) above-mentioned organic phase A sodium hydroxide is carried out saponification, obtain organic phase B, in organic phase B, add REO is again that the praseodymium neodymium rare earth feed liquid of 1.50 ~ 1.71 mol/L extracts, obtain 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester organic phase, the i.e. organic phase C of supported rare earth and aluminium;
(3) carry out back extraction with inorganic acid solution to organic phase C, make back extraction ratio reach 80% ~ 90%, and obtain organic phase D and strip liquor A, now in strip liquor A, aluminium content is less than 500ppm with the ratio of rare earth REO concentration;
(4) above-mentioned organic phase D inorganic acid solution is carried out tandem back extraction, obtain strip liquor B, with oxalic acid to strip liquor B process, reclaim praseodymium oxalate neodymium.
2. the method removing aluminium in praseodymium neodymium earth solution as claimed in claim 1, is characterized in that: in organic phase A, the concentration of 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester is 1.4 ~ 1.6mol/L.
3. the method removing aluminium in praseodymium neodymium earth solution as claimed in claim 1 or 2, is characterized in that: in step (2), the saponification deg of organic phase B is 0.40 ~ 0.54 mol/L.
4. the method removing aluminium in praseodymium neodymium earth solution as claimed in claim 1 or 2, is characterized in that: step (3) is 3.0 ~ 5.0mol/L with inorganic acid solution acidity used in step (4).
5. the method removing aluminium in praseodymium neodymium earth solution as claimed in claim 4, it is characterized in that: in step (4), tandem back extraction progression can be 3 ~ 7 grades.
6. the method for aluminium in the removal praseodymium neodymium earth solution as described in claim 1,2 or 5, is characterized in that: step (3) and inorganic acid solution used in step (4) can be hydrochloric acid, nitric acid or sulphuric acid soln.
7. the as claimed in claim 6 method removing aluminium in praseodymium neodymium earth solution, is characterized in that: inorganic acid solution used in step (3) and step (4) is the hydrochloric acid of 5.0mol/L.
8. in the removal praseodymium neodymium earth solution as described in claim 1,2,5 or 7, the method for aluminium, is characterized in that: in step (4), in praseodymium oxalate neodymium, aluminium content is less than 0.01%.
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| CN201310115287.8A CN103194627B (en) | 2013-04-07 | 2013-04-07 | Method for removing aluminum in rare earth solution |
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| CN103194627B true CN103194627B (en) | 2015-01-07 |
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| CN104313325B (en) * | 2014-09-29 | 2017-01-18 | 乐山盛和稀土股份有限公司 | Method for removing impurity-aluminum in CeFCO3 rare earth ore leaching process |
| CN105624440B (en) * | 2016-01-25 | 2017-10-03 | 江西理工大学 | One kind complex-precipitation aluminum removing method from earth solution |
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| US5258167A (en) * | 1990-06-01 | 1993-11-02 | Lion Corporation | Extractant for rare earth metal and method for extracting the same |
| CN101319275B (en) * | 2007-06-04 | 2010-11-10 | 北京有色金属研究总院 | Process for solvent extraction separation purification of rare earth element |
| CN101781706A (en) * | 2009-01-15 | 2010-07-21 | 有研稀土新材料股份有限公司 | Process for separating rare-earth element by extraction |
| CN101994004B (en) * | 2009-08-11 | 2012-07-11 | 北京有色金属研究总院 | Process for extracting and separating rare-earth elements |
| CN101705380B (en) * | 2009-11-30 | 2013-10-23 | 有研稀土新材料股份有限公司 | Method for recovering rare earth from rare earth-containing aluminum-silicon materials |
| CN102011020B (en) * | 2009-12-14 | 2012-09-05 | 包头市玺骏稀土有限责任公司 | Method for recovering rare earth elements from neodymium-iron-boron wastes |
| CN101974690B (en) * | 2010-09-28 | 2012-05-23 | 龙南县南裕稀土资源综合利用有限责任公司 | Process for recovering rare earth from waste water from rare earth mine exploitation by precipitation-extraction method |
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