WO2014140492A1 - Procede de recuperation selective des terres rares d'une solution acide aqueuse de sulfate riche en aluminium et en phosphates - Google Patents
Procede de recuperation selective des terres rares d'une solution acide aqueuse de sulfate riche en aluminium et en phosphates Download PDFInfo
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- WO2014140492A1 WO2014140492A1 PCT/FR2014/050578 FR2014050578W WO2014140492A1 WO 2014140492 A1 WO2014140492 A1 WO 2014140492A1 FR 2014050578 W FR2014050578 W FR 2014050578W WO 2014140492 A1 WO2014140492 A1 WO 2014140492A1
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- rare earths
- phosphates
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- aluminum
- iron
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a process for the selective recovery of heavy, medium and light rare earths of an aqueous acidic sulfate solution further comprising phosphates and aluminum and optionally titanium, iron III and iron II.
- Rare earths are part of these elements. Rare earths can also be produced from monazite ore, bastnaesite and loparite. These rare earths have many applications of interest in various fields.
- lanthanum (La) is a component of catalysts used in hydrocarbon refining
- neodymium (Nd) is widely used in NdFeB magnets
- europium (Eu) and terbium (Tb) are dopants for plasmas and LCD screens.
- Yttrium (Y) is used in YAG (Yttrium Aluminum Garnet) ceramics. It is therefore interesting to be able to extract them and separate them from the other elements present.
- Rare earths can be chemically divided into three groups:
- scandium is not considered to be rare earths.
- scandium (Se) although often assimilated to the rare earth family, has a different chemical behavior of the elements of the lanthanide (rare earth) series.
- the demand for medium and heavy rare earths is higher than for light rare earths, whereas in general their content in ores is lower and they are more difficult to recover. It is therefore important to be able to find a method to recover them with a good return.
- the solution of valuable elements is quantitative.
- the leachate obtained not only contains light, medium and heavy rare earth elements but also iron, in particular ferric iron (Fe III), aluminum (Al), titanium and phosphates (P).
- Fe III ferric iron
- Al aluminum
- titanium and phosphates P
- This leaching is in particular described in the patent application WO 2012/093170.
- the presence of aluminum, and to a lesser extent ferric iron hinders the recovery of rare earths and in particular medium and heavy rare earths.
- the conventional and known rare earth recovery reactions do not make it possible to recover all of them, and in particular to recover the heavy rare earths, or the totality of the average rare earths:
- the patent application US2009 / 0272230 describes a process for recovering rare earths from monazite ores and apatite ores. These ores contain a lot of phosphates, aluminum and iron.
- the proposed method comprises:
- the inventors have surprisingly found that it is possible to recover with a good yield the heavy rare earths despite the presence of ferric iron, especially aluminum in the starting solution. To do this, they discovered that it was necessary to selectively precipitate aluminum using the phosphates already present by neutralization at a specific pH, provided that the aluminum is in excess of the phosphates. This step makes it possible to purify (or deplete) the solution of aluminum and phosphates. It is then sufficient to add phosphates to the solution obtained for this time to precipitate the heavy rare earths.
- the present invention thus relates to a process for selectively recovering rare earths from an aqueous acidic sulphate solution comprising phosphates, aluminum and heavy rare earths, and optionally rare earth metals, iron II and titanium, characterized in that it comprises the following successive steps:
- the term "rare earth (RE)” is understood to mean the rare earths chosen from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu + Y and their mixtures.
- scandium (Se) is not part of the rare earths according to the present invention.
- the rare earths are classified in three groups:
- LRE Light rare earths
- MRE Middle rare earths
- HRE Heavy rare earths
- Step a) of the process according to the present invention makes it possible to purify (or deplete) the solution of phosphates, aluminum and titanium (if the titanium is present) in order to obtain a solution containing heavy rare earths and any medium rare earths in which at least 90% by weight of aluminum, phosphates and any titanium have been removed, advantageously at least 95% by weight. mass, relative to the total mass initially present in the solution. Indeed, without being bound by the theory, it seems that the majority of phosphate, aluminum and any titanium (at least 90% by weight, preferably at least 95% by weight relative to the total mass present initially in the solution) precipitate.
- the phosphate appears to precipitate preferentially in the form of aluminum phosphate AIP0 4 at a pH of between 3 and 4, advantageously 3.5, preferably with rare earth phosphates.
- the remaining aluminum will precipitate quantitatively in the form of aluminum hydroxide, which will allow the removal of the remaining aluminum.
- the rare earths and the rare medium rare earths will not precipitate or very little in the form of phosphates (at most 40 - 50%).
- the precipitation of aluminum in the form of phosphates is quantitative.
- the majority of the rare earths and any medium rare earths will remain in the sulphate solution (at least 50-60% by weight relative to the total mass of the initial aqueous acid sulphate solution).
- the base usable in step a) of the process according to the present invention can be any base. It is advantageously chosen from NH 4 OH, KOH, a basic sodium compound, such as, for example, NaOH or Na 2 OC 3, a basic magnesium compound, such as, for example, MgO or MgCO 3 , a calcium compound.
- a basic sodium compound such as, for example, NaOH or Na 2 OC 3
- a basic magnesium compound such as, for example, MgO or MgCO 3
- a calcium compound such as for example CaCO 3 , CaO and Ca (OH) 2 , and mixtures thereof, even more advantageously selected from Mg 3> 3 a basic calcium compound and mixtures thereof.
- the base of step a) is a basic calcium compound, advantageously chosen from CaCO 3 , CaO, Ca (OH) 2 and mixtures thereof, advantageously it this is CaC0 3 .
- This type of base is particularly advantageous because it is inexpensive.
- the use of such a base is possible since the precipitation in the form of gypsum results in only the rare light rare earths, moderately rare earths averages, and marginally heavy rare earths.
- the temperature of step a) of the process according to the present invention is between 20 and 90 ° C, in particular it is about 70 ° C.
- the duration of step a) is between 30 min and 6 h and is advantageously 1 h.
- Step d) of the process according to the present invention serves to extract all the rare earths present in the solution by precipitation in the form of rare earth phosphates. Since the majority of the phosphates of the solution has already been removed during step a) of the process according to the present invention (advantageously at least 90% by weight, advantageously at least 95% by weight relative to the total mass initially present in the aqueous acid sulphate solution), it is necessary to add it during step d). The precipitation is then quantitative since there is virtually no aluminum in the solution (advantageously the solution contains less than 10% by weight of aluminum relative to the initial aqueous sulphate solution, advantageously less than 5% by weight).
- the phosphate used in step d) is chosen from Na 3 PO 4 , K 3 PO 4 , (NH 4 ) 3 PO 4 and mixtures thereof, in particular it is Na 3 PO 4 .
- the aqueous sulphate solution in step d) at a pH of between 3 and 4, advantageously 3.5.
- the temperature of step d) of the process according to the present invention is between 50 ° C. and the boiling point, which is advantageously 90 ° C., in particular it is between 70 ° C. and the point of boiling point. boiling.
- the duration of step d) is between 30 minutes and 2 hours.
- it is less than or equal to 1 hour.
- the aqueous sulphate acid solution comprising phosphates, aluminum and heavy rare earths, and optionally rare earth metals, iron II and titanium, is the leachate obtained by acid attack of a pyrochlore ore in sulfate medium, for example as described in patent application WO 2012/093170.
- this solution contains:
- Al at least 7 g / L, advantageously between 7 and 14 g / L;
- P between 1 and 6 g / l, advantageously between 3 and 6 g / l, in particular between 4 and 6 g / l;
- Medium and heavy TRs at least 100 mg / L, advantageously between 200 and 300 mg / L;
- Ti ⁇ 1 g / L, advantageously if it is present between 0.5 and 1 g / l.
- the aqueous acid sulfate solution may also contain iron (Fe) advantageously at least 50 g / l, advantageously between 50 and 70 g / l, in particular in the form of Fe II.
- the method according to the present invention comprises an additional step g) of washing the precipitate obtained in step f), advantageously by repulping with water, advantageously at room temperature.
- step f) or in step g) The recovery of heavy rare earths and possible rare earths from the precipitate obtained in step f) or in step g) can be carried out by methods well known to those skilled in the art, such as for example purification by conversion to hydroxides of rare earths.
- the recovery yield of the heavy rare earths of the process according to the present invention is greater than 50%, advantageously greater than or equal to 60%.
- the aqueous sulfate acid solution comprising phosphates, aluminum, rare earths and rare earths, and optionally iron II and titanium, comprises in addition to light rare earths and we seek to recover all rare earth (medium, heavy and light).
- the light rare earths are partially driven by the precipitation of gypsum during step a), if the latter is implemented with a basic calcium compound.
- the process according to the present invention comprises, before step a), a preliminary step A) of precipitation by double salt.
- light rare earths advantageousously at least 85% by weight, in particular 90% by weight, relative to the total mass of the rare earth elements present in the initial aqueous sodium sulfate solution
- an aqueous acidic solution of sulphate depleted (or purified) in light rare earths advantageousously at most 15% by weight remains of light rare earths, in particular 10% by weight, relative to the total mass of light rare earth elements present in the initial aqueous sulphate acid solution
- phosphates aluminum, rare earths and rare earths, and possibly iron II and titanium.
- the double-salt precipitation step precipitates not only light rare earths but also a part of the average rare earths (about 50% by weight relative to the total mass of the rare earth elements present in the initial aqueous sulphate acid solution). ) and advantageously, a minor of heavy rare earths (at most 15% by weight, in particular 10% by weight, relative to the total mass of the rare earths present in the initial aqueous acidic sulfate solution).
- the aqueous solution of at least 50% by weight of the average rare earth relative to the total mass of the rare earth elements present in the initial aqueous acidic sulphate solution, and advantageously at least 85% by weight, remains in the aqueous acid sulphate solution.
- heavy rare earth mass in particular 90% by weight, relative to the total mass of the rare earths present in the initial aqueous acid sulfate solution.
- the double rare earth salt precipitation method of step A) is well known to those skilled in the art.
- it is a double salt precipitation of sodium, ammonium or potassium, preferably double sodium salt.
- stage A) is carried out by addition of sodium sulphate, which leads to the formation of an insoluble rare earth compound according to the following reaction:
- the addition of Na + is carried out in excess of the rare earth so as to obtain a quantitative recovery of light rare earths.
- the precipitate is separated from the aqueous acid solution of light rare earth depleted sulfate. It is advantageously washed, for example with water and a 5% solution of Na 2 SO 4 .
- the temperature of step A) is between 50 ° C. and the boiling point, which is in particular 90 ° C.
- the duration of step A) is between 30 minutes and 3 hours. In particular it is 1 hour.
- the recovery yield of light rare earths is greater than 85%, advantageously greater than or equal to 90%, the average rare earth is greater than 50% and heavy rare earths is greater than 10%.
- the aqueous acid solution of sulphate comprising phosphates, aluminum and heavy rare earths, and possibly rare earths, rare earths, titanium and iron II further comprises iron III.
- the iron content III is less than or equal to 20 g / l, advantageously between 5 and 20 g / l, very advantageously between 10 and 20 g / l.
- the presence of iron III promotes the precipitation of phosphates in the form of ferric iron phosphates (FePO 4 ) during the neutralization of the solution in step a) of the process according to the present invention.
- ferric iron also precipitates in other forms than that phosphate, especially by precipitation of ferric iron hydroxides in step a). However, such precipitation tends to result in other elements such as rare earths in the precipitate.
- step B before step a) and after the optional step A), reducing iron III to iron II, advantageously by adding Fe ° (for example in the form of iron powder), SO2 or other reducing agent.
- this step makes it possible to obtain a ferric iron (Fe III) content of ⁇ 1 g / L in the aqueous acid solution of sulfate obtained comprising phosphates, aluminum and heavy rare earths, and possibly rare earths.
- the average rare earth recovery efficiency is> 80%, advantageously greater than or equal to 85%.
- step a) the molar ratio Al / P of the aqueous acid solution of sulphate comprising phosphates, aluminum and heavy rare earths, and possibly earth rare medium, light, iron II, iron III and titanium, is ⁇ 1. This means that phosphates are in excess of aluminum.
- step C in order to be able to implement the method according to the present invention, it is necessary to add a step C), after the possible steps A) and B) and before step a), of doping the solution with of aluminum so as to obtain a molar ratio AI / P> 1 which makes it possible to implement step a) of the process according to the present invention while minimizing the losses of rare earth elements and possible rare earths by precipitation in the form of phosphates.
- FIG. 1 represents the precipitation yield (%) of rare earths in the form of double sodium sulphate salts and rare earths depending on the type of rare earths, obtained under the conditions of Comparative Example 1.
- FIG. 2 represents the precipitation yield (%) of aluminum or Gd (medium rare earth) phosphates as a function of the pH, obtained under the conditions of Comparative Example 2.
- FIG. 3 represents the precipitation yield (%) of the light, medium and heavy rare earth phosphates (La, Gd and Y) as a function of the pH, obtained under the conditions of Comparative Example 2.
- FIG. 4 represents the precipitation yield (%) of the medium and heavy rare earths and aluminum in the form of phosphates, obtained under the conditions of example 1 during stage a) of the process according to the present invention.
- Fig. 6 shows the scheme of the method according to the present invention as used in Example 3 (steps a), b), c), d), e) and f) according to the present invention).
- FIG. 7 represents the recovery yield (%) of the light, medium and heavy rare earths, obtained under the conditions of example 3.
- Fig. 8 shows the scheme of the method according to the present invention as used in Example 4 (steps A), a), b), c), d), e) and f) according to the present invention)
- SD double salts of rare earth and sodium sulphates
- FIG. 9 represents the diagram of the method according to the present invention as used in example 5 (steps A), B), a), b), c), d), e) and f) according to the present invention )
- SD double salts of rare earth and sodium sulphates
- FIG. 10 shows the precipitation yield (%) of yttrium in the form of phosphates (i.e. yttrium losses) and residual aluminum concentration (in g / L) in the solution as a function of the content of Fe (III) in g / L and the amount of base Ca (OH) 2 added during the neutralization step a) according to the present invention under the following conditions: 70 ° C., 2 hours (example 5) ).
- FIG. 11 represents the precipitation yield (%) of the rare earths Ce, Gd and Y and of Fe during stage d) of the process according to the present invention at the temperature of 100 ° C. for a duration of 1 hour depending on PO4 / TR molar ratio (Example 6).
- FIG. 12 represents the recovery yield (%) of the rare earths at each stage, obtained by using the process according to the present invention under the conditions of example 6.
- the solution (obtained by acid leaching in sulphate pyrochlore ore medium) on which this step will be implemented has the following composition:
- the solubility of the double rare earth salts decreases with the increase of the atomic number of the element, from which a recovery of 50% of the rare earths rare and only 10% of the rare earths heavy for the Na contents considered.
- Comparative Example 2 Use of phosphates present in solution for precipitating rare earth phosphates
- the pyrochlore ore contains a source of phosphates (from apatite in particular): consequently, during the sulfuric attack of the ore pyrochlore, all of these phosphates present are attacked and are found in solution.
- a solution type to which must be implemented the method according to the present invention contains ⁇ 15 g / L of phosphate (P0 4 3) to ⁇ 270 g / L of sulfates (S0 4 2).
- TRP0 4 a rare earth phosphate
- the solution obtained after etching contains mainly rare earth and thorium sulphates / phosphates ( ⁇ 30 g / L of TR for ⁇ 6 g / l of Th)
- a neutralization with an ammonia-type base makes it possible to increase the pH of the solution to 1.5-2, in a range where the rare earth phosphates are insoluble. A rare earth phosphate is then obtained with good purity.
- the thorium can be separated from the rare earths by a double neutralization: precipitation of ThPO 4 before pH 1.5, then precipitation of TRPO 4 at pH 2.
- the operating conditions are as follows:
- Comparative Example 3 Doping of the Phosphate Solution to Promote the Precipitation of Medium and Heavy Rare Earths The precipitation conditions of Comparative Example 2 are repeated, with in addition an addition (approximately 3 g / L in addition) of phosphates (under form of Na 3 PO 4 ) to study the influence on precipitation efficiency of medium and heavy rare earths.
- Example 1 Implementation of step a) of the process according to the present invention
- the precipitation yields of medium and heavy rare earths and aluminum in the form of phosphates are represented in FIG. 4. Note that the precipitation of aluminum is quantitative, whereas that of the medium and heavy rare earths is limited to 20 - About 40%.
- This step makes it possible to obtain a solution resulting from the attack of the pyrochlore ore containing the medium and heavy rare earths purified (or depleted) of aluminum and phosphates. It therefore makes it possible to purify (or deplete) the aluminum and phosphate solution while limiting the coprecipitation of the rare earths.
- the presence in solution of phosphates from the ore matrix has thus been used to precipitate aluminum by neutralization in the form of aluminum phosphate, the rest of the aluminum precipitating in the form of aluminum hydroxide, these precipitations being selective with respect to the rare earths.
- - Phosphates are in default with respect to aluminum: the molar ratio Al / P is greater than 1;
- the medium was concentrated in sulphates in order to promote the complexation of the rare earth sulphates.
- medium and heavy rare earth phosphates precipitate at a slightly higher pH and are therefore less lost with AIP0 4 .
- the objective is to selectively and quantitatively precipitate the rare earths present in low concentration in an aqueous solution of sulfate containing almost no aluminum or phosphates.
- the precipitation of rare earth phosphates was carried out by adding phosphates in the form of Na 3 PO 4 .
- step a The conditions used for the precipitation of aluminum phosphate (step a) of the process are as follows:
- step d The conditions used for the precipitation of rare earth phosphates (step d) of the process are as follows:
- This process makes it possible to recover the rare earths in phosphate form with very good yields in a solution initially containing significant amounts of iron, aluminum and phosphorus.
- the loss of rare earths during the neutralization can be reduced by optimizing the precipitation conditions of AIP0 4 .
- the recovery yields of light rare earths vary between 50 and 60%, and medium and heavy rare earths are recovered with a yield of 65 to 75%.
- Precipitation of rare earths in the form of phosphates is therefore:
- EXAMPLE 4 Precipitation of light rare earths in the form of double salts + purge of phosphates by precipitation of aluminum + doping with phosphates to recover non-precipitated medium and heavy rare earths (implementation of the process according to the present invention: steps A ), (a), (b), (c), (d), (e) and (f))
- a precipitation of double salts of light rare earths (according to Comparative Example 1) is therefore carried out in the first stage. Then, we can purge the phosphates and the aluminum at first in order to obtain a solution containing the medium and heavy rare earths, purified or depleted in Al and P. A doping at that time in phosphates should make it possible to precipitate the phosphates of medium and heavy rare earths.
- the initial solution of acidic aqueous sulphate has the following composition:
- Fe 50 to 70 g / L such that Fe (III) at ⁇ 10 - 20 g / L
- the rare earths remaining in solution precipitate with an excess of added phosphate (molar ratio n (PO 4 ) / n (TR) ⁇ 100 with a yield of 100%).
- ferric iron (Fe III) coming from the upstream solution (acidic aqueous solution of sulphate including the rare earths) generates two phenomena:
- ferric iron Since the quantity of phosphates is in clear defect compared to Al, Fe (III), Th, LRE, ferric iron also precipitates in other forms than that phosphate, in particular by precipitation of ferric iron hydroxides, known to pump many elements in solution;
- reaction conditions are as follows: temperature 70 ° C .; reaction time 2 hours; base used: Ca (OH) 2 , composition of the aqueous initial sulphate solution: Fe: 50 to 70 g / L such that Fe (III) at ⁇ 10 - 20 g / L; Al: 8 to 14 g / L; P: 4 to 6 g / L; Mn: 5 to 7 g / L; TR: 1 to 3 g / L; Th: 0.1 to 0.3 g / L; S0 4 : 250 to 300 g / L.
- the operating conditions could be optimized to reduce the quantity of reagents to be added.
- the first precipitation tests were carried out at a SQ of 100, which is economically unacceptable.
- the precipitation yield (%) of the rare earths (Ca, Gd and Y) and iron in the aqueous solution is monitored according to the QS PO 4 / TR as illustrated in FIG. 11.
- the operating conditions of the step d ) are as follows: temperature 100 ° C; residence time: 1 hour, phosphate: Na 3 PO 4 .
- the selectivity of the reaction is excellent: a low QS makes it possible to precipitate all the rare earths with little ferrous iron. This is allowed thanks to a high temperature (100 ° C) and a deliberately short residence time ( ⁇ lh) which makes it possible to limit the reoxidation of Fe (II) to Fe (III) over time, and thus to limit the use of PO 4 present to precipitate a Fe (III) phosphate.
Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CA2906251A CA2906251A1 (fr) | 2013-03-15 | 2014-03-13 | Procede de recuperation selective des terres rares d'une solution acide aqueuse de sulfate riche en aluminium et en phosphates |
SE1551224A SE1551224A1 (sv) | 2013-03-15 | 2014-03-13 | Method for selectively recovering the rare earths from an aqueous acid sulphate solution rich in aluminium and phosphates |
US14/776,249 US20160032419A1 (en) | 2013-03-15 | 2014-03-13 | Method for selectively recovering the rare earths from an aqueous acid sulfate solution rich in aluminum and phosphates |
CN201480026836.7A CN105229178B (zh) | 2013-03-15 | 2014-03-13 | 从富含铝和磷酸根的酸性硫酸盐水溶液中选择性地回收稀土金属的方法 |
BR112015023619A BR112015023619A2 (pt) | 2013-03-15 | 2014-03-13 | processo para recuperação seletiva dos metais raros a partir de uma solução de sulfato ácido e aquosa rica em alumínio e fosfatos |
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FR1352349 | 2013-03-15 | ||
FR1352349A FR3003270B1 (fr) | 2013-03-15 | 2013-03-15 | Procede de recuperation selective des terres rares d'une solution acide aqueuse de sulfate riche en aluminium et en phosphates |
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US (1) | US20160032419A1 (fr) |
CN (1) | CN105229178B (fr) |
BR (1) | BR112015023619A2 (fr) |
CA (1) | CA2906251A1 (fr) |
FR (1) | FR3003270B1 (fr) |
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CN106521166B (zh) * | 2016-11-29 | 2018-09-18 | 湖南埃格环保科技有限公司 | 一种利用含铜污泥湿法浸出溶液制备铜粉和硫酸亚铁的方法 |
JP6733533B2 (ja) * | 2016-12-16 | 2020-08-05 | 日立金属株式会社 | R−t−b系焼結磁石の製造方法 |
US11155897B2 (en) | 2017-11-09 | 2021-10-26 | University Of Kentucky Research Foundation | Low-cost selective precipitation circuit for recovery of rare earth elements from acid leachate of coal waste |
WO2019099859A1 (fr) * | 2017-11-17 | 2019-05-23 | Ii-Vi Delaware, Inc. | Récupération sélective de métaux des terres rares à partir d'une suspension acide ou d'une solution acide |
KR102091804B1 (ko) * | 2018-03-16 | 2020-03-20 | 한국화학연구원 | 폐 re:yag 결정으로부터 희토류 성분의 회수방법 |
CN112088224B (zh) * | 2018-05-03 | 2023-05-30 | 阿拉弗拉资源有限公司 | 稀土的回收方法 |
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CN101602519A (zh) * | 2008-06-12 | 2009-12-16 | 北京有色金属研究总院 | 一种萃取分离负载有机相直接制备稀土化合物的工艺 |
FR2944276B1 (fr) * | 2009-04-14 | 2011-04-01 | Rhodia Operations | Procede de recuperation des terres rares a partir d'un melange solide contenant un halophosphate et un compose d'une ou plusieurs terres rares |
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2013
- 2013-03-15 FR FR1352349A patent/FR3003270B1/fr active Active
-
2014
- 2014-03-13 SE SE1551224A patent/SE1551224A1/sv not_active Application Discontinuation
- 2014-03-13 BR BR112015023619A patent/BR112015023619A2/pt not_active IP Right Cessation
- 2014-03-13 CN CN201480026836.7A patent/CN105229178B/zh not_active Expired - Fee Related
- 2014-03-13 US US14/776,249 patent/US20160032419A1/en not_active Abandoned
- 2014-03-13 WO PCT/FR2014/050578 patent/WO2014140492A1/fr active Application Filing
- 2014-03-13 CA CA2906251A patent/CA2906251A1/fr not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090272230A1 (en) * | 2008-05-02 | 2009-11-05 | Arafura Resources Limited | Recovery of Rare Earth Elements |
FR2970265A1 (fr) * | 2011-01-06 | 2012-07-13 | Areva Nc | Mise en solution et recuperation d'au moins un element nb, ta et d'au moins un autre element u, terres rares a partir de minerais et concentres |
Non-Patent Citations (1)
Title |
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KUL M ET AL: "Rare earth double sulfates from pre-concentrated bastnasite", HYDROMETALLURGY, ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM, NL, vol. 93, no. 3-4, 1 August 2008 (2008-08-01), pages 129 - 135, XP022757951, ISSN: 0304-386X, [retrieved on 20071122], DOI: 10.1016/J.HYDROMET.2007.11.008 * |
Also Published As
Publication number | Publication date |
---|---|
CN105229178A (zh) | 2016-01-06 |
BR112015023619A2 (pt) | 2017-07-18 |
FR3003270A1 (fr) | 2014-09-19 |
CN105229178B (zh) | 2017-05-03 |
CA2906251A1 (fr) | 2014-09-18 |
FR3003270B1 (fr) | 2015-04-17 |
US20160032419A1 (en) | 2016-02-04 |
SE1551224A1 (sv) | 2015-09-23 |
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