US20160032419A1 - Method for selectively recovering the rare earths from an aqueous acid sulfate solution rich in aluminum and phosphates - Google Patents

Method for selectively recovering the rare earths from an aqueous acid sulfate solution rich in aluminum and phosphates Download PDF

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US20160032419A1
US20160032419A1 US14/776,249 US201414776249A US2016032419A1 US 20160032419 A1 US20160032419 A1 US 20160032419A1 US 201414776249 A US201414776249 A US 201414776249A US 2016032419 A1 US2016032419 A1 US 2016032419A1
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rare earth
earth metals
phosphates
aluminum
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Maxime VINCEC
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Eramet SA
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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
    • 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
    • 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 earth metals from an acidic aqueous sulfate solution additionally comprising phosphates and aluminum and possibly titanium, iron(III) and iron(II).
  • rare earth metals such as pyrochlore ores, comprising numerous elements of interest, sometimes in low proportions.
  • the rare earth metals are included among these elements.
  • the rare earth metals can also be produced from monazite, bastnaesite and loparite ores. These rare earth metals have numerous advantageous applications in various fields.
  • lanthanum (La) is a component of catalysts employed in the refining of hydrocarbons
  • Nd neodymium
  • Eu europium
  • Tb terbium
  • Yttrium (Y) is for its part used in YAG (Yttrium Aluminum Garnet) ceramics. It is thus advantageous to be able to extract them and to separate them from the other elements present.
  • Rare earth metals can be divided chemically into three groups:
  • the dissolution of the elements of value (Nb, rare earth metals (TR), Ta and U) is quantitative.
  • the leachate obtained comprises not only light, medium and heavy rare earth metals but also iron, in particular ferric iron (FeIII), aluminum (Al), titanium and phosphates (P).
  • FeIII ferric iron
  • Al aluminum
  • Ti titanium
  • P phosphates
  • This leaching is described in particular in the patent application WO 2012/093170.
  • the presence of aluminum and to a lesser extent of ferric iron interferes with the recovery of the rare earth metals and in particular of the medium and heavy rare earth metals.
  • the conventional and known reactions for the recovery of the rare earth metals do not make it possible to recover them all, in particular to recover the heavy rare earth metals, or the whole of the medium rare earth metals:
  • the inventors have noticed, surprisingly, that it is possible to recover, with a good yield, heavy rare earth metals despite the presence of ferric iron and in particular of aluminum in the starting solution.
  • it is necessary to selectively precipitate the aluminum by using the phosphates already present with neutralization at a very precise pH, provided that the aluminum is in excess with respect to the phosphates.
  • This stage makes it possible to purify (or deplete) the solution from (or in) aluminum and phosphates. It is subsequently sufficient to add phosphates to the solution obtained in order this time to precipitate the heavy rare earth metals.
  • the present invention thus relates to a process for the selective recovery of the rare earth metals from an acidic aqueous sulfate solution comprising phosphates, aluminum and heavy rare earth metals, and possibly medium rare earth metals, iron(II) and titanium, characterized in that it comprises the following successive stages:
  • rare earth metals REs
  • REs rare earth metals
  • Sc scandium
  • the rare earth metals are classified into three groups:
  • Stage a) of the process according to the present invention makes it possible to purify (or deplete) the solution from (of) phosphates, aluminum and titanium (if titanium is present) in order to obtain a solution containing the heavy rare earth metals and the possible medium rare earth metals from which at least 90% by weight of aluminum, of the phosphates and the possible titanium have been removed, advantageously at least 95% by weight, with respect to the total weight present at the start in the solution.
  • a solution containing the heavy rare earth metals and the possible medium rare earth metals from which at least 90% by weight of aluminum, of the phosphates and the possible titanium have been removed advantageously at least 95% by weight, with respect to the total weight present at the start in the solution.
  • the phosphate appears to precipitate preferentially in the form of aluminum phosphate AlPO 4 at a pH of between 3 and 4, advantageously of 3.5, preferentially to the rare earth metals phosphates.
  • the remaining aluminum will quantitatively precipitate in the form of aluminum hydroxide, which will make possible the removal of the remaining aluminum.
  • the phosphates are deficient with respect to the aluminum, the heavy rare earth metals and the possible medium rare earth metals will not precipitate or will not precipitate very much in the form of phosphates (at most 40-50%).
  • the precipitation of the aluminum in the form of phosphates is quantitative.
  • the majority of the heavy rare earth metals and of the possible medium rare earth metals will remain in the sulfate solution (at least 50-60% by weight, with respect to the total weight of the initial acidic aqueous sulfate solution).
  • the base which can be used in stage 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 CO 3 , a basic magnesium compound, such as, for example, MgO or MgCO 3 , a basic calcium compound, such as, for example, CaCO 3 , CaO and Ca(OH) 2 , and their mixtures, more advantageously still chosen from MgCO 3 , a basic calcium compound and their mixtures.
  • a basic sodium compound such as, for example, NaOH or Na 2 CO 3
  • a basic magnesium compound such as, for example, MgO or MgCO 3
  • a basic calcium compound such as, for example, CaCO 3 , CaO and Ca(OH) 2
  • the base of stage a) is a basic calcium compound advantageously chosen from CaCO 3 , CaO, Ca(OH) 2 and their mixtures; advantageously, it is CaCO 3 .
  • This type of base is particularly advantageous as it is relatively inexpensive.
  • the use of such a base is possible since the precipitation in the form of gypsum entrains only predominantly the light rare earth metals, moderately the medium rare earth metals, and marginally the heavy rare earth metals.
  • the temperature of stage a) of the process according to the present invention is between 20 and 90° C.; in particular it is approximately 70° C.
  • the duration of stage a) is between 30 min and 6 h and it is advantageously 1 h.
  • Stage d) of the process according to the present invention is used to extract all the rare earth metals present in the solution by precipitation in the form of rare earth metal phosphates. Since the majority of the phosphates of the solution have already been removed during stage a) of the process according to the present invention (advantageously at least 90% by weight, advantageously at least 95% by weight, with respect to the total weight present at the start in the acidic aqueous sulfate solution), it is necessary to add it during stage d). The precipitation is then quantitative since there is virtually no more aluminum in the solution (advantageously, the solution contains less than 10% by weight of aluminum, with respect to the initial aqueous sulfate solution, advantageously less than 5% by weight).
  • the phosphate used in stage d) is chosen from Na 3 PO 4 , K 3 PO 4 , (NH 4 ) 3 PO 4 and their mixtures; in particular, it is Na 3 PO 4 .
  • the aqueous sulfate solution in stage d) has a pH of between 3 and 4, advantageously, it is 3.5.
  • the temperature of stage 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 boiling point.
  • the duration of stage d) is between 30 minutes and 2 hours.
  • it is less than or equal to 1 hour.
  • the acidic aqueous sulfate solution comprising phosphates, aluminum and heavy rare earth metals, and possibly medium rare earth metals, iron(II) and titanium, is the leachate obtained by acid attack on a pyrochlore ore in a sulfate medium, for example as described in the patent application WO 2012/093170.
  • this solution contains:
  • the acidic aqueous sulfate solution can 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).
  • Fe iron
  • the process according to the present invention comprises an additional stage g) of washing the precipitate obtained in stage f), advantageously by repulping with water, advantageously at ambient temperature.
  • stage f) or in stage g) The recovery of the heavy rare earth metals and of the possible medium rare earth metals from the precipitate obtained in stage f) or in stage g) can be carried out by methods well known to a person skilled in the art, such as, for example, purification by conversion into rare earth metal hydroxides.
  • the recovery yield of the heavy rare earth metals of the process according to the present invention is greater than 50%, advantageously greater than or equal to 60%.
  • the acidic aqueous sulfate solution comprising phosphates, aluminum, heavy rare earth metals and medium rare earth metals, and possibly iron(II) and titanium, additionally comprises light rare earth metals and an attempt is made to recover all the rare earth metals (medium, heavy and light).
  • the light rare earth metals are partially entrained by the precipitation of gypsum during stage a), if the precipitation is carried out with a basic calcium compound.
  • the process according to the present invention comprises, before stage a), a prior stage A) of double salt precipitation of the light rare earth metals (advantageously at least 85% by weight, in particular 90% by weight, with respect to the total weight of the medium rare earth metals present in the initial acidic aqueous sulfate solution), so as to recover an acidic aqueous sulfate solution depleted (or purified) in (or from) light rare earth metals (advantageously, at most, there remains 15% by weight of light rare earth metals, in particular 10% by weight, with respect to the total weight of the light rare earth metals present in the initial acidic aqueous sulfate solution) and comprising phosphates, aluminum, heavy rare earth metals and medium rare earth metals, and possibly iron(II) and titanium.
  • the stage of double salt precipitation precipitates not only the light rare earth metals but also a portion of the medium rare earth metals (approximately 50% by weight, with respect to the total weight of the medium rare earth metals present in the initial acidic aqueous sulfate solution) and advantageously a minority of heavy rare earth metals (at most 15% by weight, in particular 10% by weight, with respect to the total weight of the heavy rare earth metals present in the initial acidic aqueous sulfate solution).
  • the acidic aqueous sulfate solution at least 50% by weight of the medium rare earth metals, with respect to the total weight of the medium rare earth metals present in the initial acidic aqueous sulfate solution, and advantageously at least 85% by weight of the heavy rare earth metals, in particular 90% by weight, with respect to the total weight of the heavy rare earth metals present in the initial acidic aqueous sulfate solution.
  • stage A) The process for the double salt precipitation of light rare earth metals of stage A) is well known to a person skilled in the art.
  • it concerns sodium, ammonium or potassium double salt precipitation, advantageously sodium double salt precipitation.
  • stage A) advantageously takes place by addition of sodium sulfate, which results in the formation of an insoluble rare earth metal compound according the following reaction:
  • the addition of Na + is carried out in excess with respect to the rare earth metals, so as to obtain a quantitative recovery of the light rare earth metals.
  • the precipitate is separated from the acidic aqueous sulfate solution depleted in light rare earth metals. It is advantageously washed, for example with water and a 5% Na 2 SO 4 solution.
  • the temperature of stage A) is between 50° C. and the boiling point, which is in particular 90° C.
  • the duration of stage A) is between 30 minutes and 3 hours. In particular, it is 1 hour.
  • the recovery yield of the light rare earth metals is greater than 85%, advantageously greater than or equal to 90%, of the medium rare earth metals is greater than 50% and of the heavy rare earth metals is greater than 10%.
  • the acidic aqueous sulfate solution comprising phosphates, aluminum and heavy rare earth metals, and possibly medium rare earth metals, light rare earth metals, titanium and iron(II), additionally comprises iron(III).
  • the content of iron(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 the iron(III) promotes the precipitation of phosphates in the form of ferric iron phosphates (FePO 4 ) during neutralization of the solution in stage a) of the process according to the present invention.
  • the ferric iron As the amount of phosphates is deficient with respect to Al and Fe(III) (molar ratio (Al+Fe(III))/P>1 since molar ratio Al/P>1), the ferric iron also precipitates in other forms than that of phosphate, in particular by precipitation of ferric iron hydroxides, during stage a). However, such a precipitation has a tendency to entrain other elements, such as rare earth metals, in the precipitate. In addition, in order to precipitate all the ferric iron, it is necessary to add an additional amount of base in stage a), which results in the formation of additional gypsum when a base such as a basic calcium compound is used.
  • this stage makes it possible to obtain a content of ferric iron (Fe(III)) ⁇ 1 g/l in the acidic aqueous sulfate solution obtained comprising phosphates, aluminum and heavy rare earth metals, and possibly medium rare earth metals, light rare earth metals, titanium and iron(II).
  • the recovery yield of the medium rare earth metals is >80%, advantageously greater than or equal to 85%.
  • the molar ratio Al/P of the acidic aqueous sulfate solution comprising phosphates, aluminum and heavy rare earth metals, and possibly medium rare earth metals, light rare earth metals, iron(II), iron(III) and titanium, is ⁇ 1. This means that the phosphates are in excess with respect to the aluminum.
  • stage C in order to be able to carry out the process according to the present invention, it is necessary to add a stage C), after the optional stages A) and B) and before stage a), of doping of the solution with aluminum, so as to obtain a molar ratio Al/P>1 which makes it possible to carry out stage a) of the process according to the present invention while minimizing the losses of heavy rare earth metals and of possible medium rare earth metals by precipitation in the form of phosphates.
  • FIG. 1 represents the precipitation yield (%) of the rare earth metals in the form of sodium and rare earth metal double sulfate salts as a function of the type of rare earth metal, obtained under the conditions of comparative example 1.
  • FIG. 2 represents the precipitation yield (%) of the aluminum or Gd (medium rare earth metal) 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 metal (La, Gd and Y) phosphates as a function of the pH, obtained under the conditions of comparative example 2.
  • FIG. 4 represents the precipitation yield (%) of medium and heavy rare earth metals and of the 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 represents the diagram of the process according to the present invention as used in example 3 (stages 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 earth metals, obtained under the conditions of example 3.
  • FIG. 8 represents the diagram of the process according to the present invention as used in example 4 (stages A), a), b), c), d), e) and f) according to the present invention)
  • DS rare earth metal and sodium sulfate double salts
  • MRE/HRE Medium Rare Earth Metal/Heavy Rare Earth Metal
  • FIG. 9 represents the diagram of the process according to the present invention as used in example 5 (stages A), B), a), b), c), d), e) and f) according to the present invention)
  • DS rare earth metal and sodium sulfate double salts
  • MRE/HRE Medium Rare Earth Metal/Heavy Rare Earth Metal
  • FIG. 10 represents the precipitation yield (%) of yttrium in the form of phosphates (that is to say, the losses of yttrium) and the residual concentration of aluminum (in g/l) in the solution as a function of the content of Fe(III) in g/l and of the amount of base Ca(OH) 2 added during the neutralization stage 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 earth metals Ce, Gd and Y and of Fe during stage d) of the process according to the present invention at a temperature of 100° C. for a period of time of 1 hour as a function of the molar ratio PO 4 /REs (example 6).
  • FIG. 12 represents the recovery yield (%) of the rare earth metals at each stage, obtained by using the process according to the present invention under the conditions of the example 6.
  • the solution (obtained by acid leaching in a sulfate medium of pyrochlore ore) on which this stage will be carried out exhibits the following composition:
  • the solubility of the rare earth metal double salts decreases with the increase in the atomic number of the element, resulting in a recovery of 50% of the medium rare earth metals and only 10% of the heavy rare earth metals for the Na contents under consideration.
  • the pyrochlore ore comprises a source of phosphates (originating in particular from the apatite): consequently, during the attack of sulfuric acid on the pyrochlore ore, all of these phosphates present are attacked and are reencountered in solution.
  • a typical solution on which the process according to the present invention has to be carried out comprises ⁇ 15 g/l of phosphates (PO 4 3 ⁇ ) for ⁇ 270 g/l of sulfates (SO 4 2 ⁇ ).
  • One of the main rare earth metal ore sources is monazite, a rare earth metal phosphate (REPO 4 ). This ore is attacked by the sulfate route and the recovery of the rare earth metals takes place in a simple way:
  • the operating conditions are as follows:
  • the precipitation conditions of comparative example 2 are repeated, with furthermore the addition (approximately 3 g/l more) of phosphates (in the form of Na 3 PO 4 ) in order to study the influence on the precipitation yield of the medium and heavy rare earth metals.
  • AlPO 4 precipitates before the medium and heavy rare earth metal phosphates and the aluminum is in marked excess with respect to the phosphates; thus, the least addition of phosphate promotes the precipitation of the aluminum phosphate.
  • the precipitation yields of the moderate and heavy rare earth metals and of the aluminum in the form of phosphates are represented in FIG. 4 . It is noticed that the precipitation of the aluminum is quantitative, whereas the precipitation of the medium and heavy rare earth metals is limited to 20-40% approximately.
  • This stage makes it possible to obtain a solution resulting from the attack on the pyrochlore ore containing the moderate and heavy rare earth metals which is purified (or depleted) from (or in) aluminum and phosphates. It thus makes it possible to purify (or deplete) the solution from (or in) aluminum and phosphate while limiting the the coprecipitation of the rare earth metals.
  • the objective is to selectively and quantitatively precipitate the rare earth metals present in low concentration in an aqueous sulfate solution containing virtually no more aluminum or phosphates.
  • the addition of phosphates is carried out in order to promote their precipitation.
  • composition of the solution for the precipitation tests on the rare earth metals is shown in table 2 below.
  • the precipitation of rare earth metal phosphates was carried out by addition of phosphates in the form of Na 3 PO 4 .
  • the precipitation yield of the rare earth metals are given in FIG. 5 .
  • the precipitation yields of the thulium and lutetium could not be calculated as these elements exhibited concentrations below the detection limits.
  • the precipitation of the light, medium and heavy rare earth metals is quantitative (approximately 90%, with the exception of praseodymium at 70%).
  • stage a The conditions used for the precipitation of the aluminum phosphate (stage a) of the process) are as follows:
  • stage d The conditions used for the precipitation of the rare earth metals phosphates (stage d) of the process) are as follows:
  • FIG. 6 The diagram of the process used is represented in FIG. 6 .
  • the recovery yield of the rare earth metals for the scheme of the process provided is represented in FIG. 7 .
  • the precipitation yields for the thulium and lutetium could not be calculated as these elements exhibited concentrations below the detection limits.
  • the process makes it possible to recover the rare earth metals in the phosphate form with very good yields from a solution initially containing large amounts of iron, aluminum and phosphorus.
  • the loss of rare earth metals during the neutralization can be reduced by optimization of the conditions for precipitation of AlPO 4 .
  • the recovery yields of the light rare earth metals vary between 50 and 60% and the medium and heavy rare earth metals are recovered with a yield of 65 to 75%.
  • a precipitation of light rare earth metal double salts (according to comparative example 1) is thus carried out as first stage. Subsequently, we can expel the phosphates and the aluminum in a first step in order to obtain a solution containing the medium and heavy rare earth metals, purified from or depleted in Al and P. Doping at that moment with phosphates should make it possible to precipitate the medium and heavy rare earth metal phosphates.
  • the initial acidic aqueous sulfate solution has the following composition:
  • stage by stage balance shows that:
  • Stage D Optimization of the Loss of the Rare Earth Metals During the Stage of Al/P Precipitation (Stage D)) by Decreasing the Concentration of Fe(III): (Implementation of the Process According to the Present Invention: Stages A), B), a), b), c), d), e) and f))
  • ferric iron Fe(III)
  • upstream solution acidic aqueous sulfate solution comprising the rare earth metals
  • reaction conditions are as follows: temperature 70° C.; reaction time 2 hours; base used: Ca(OH) 2 ; composition of the initial aqueous sulfate solution: Fe: 50 to 70 g/l, such as 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; REs: 1 to 3 g/l; Th: 0.1 to 0.3 g/l; SO 4 : 250 to 300 g/l.
  • Fe 50 to 70 g/l, such as 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
  • REs 1 to 3 g/l
  • Th 0.1 to 0.3 g/l
  • SO 4 250 to 300 g/l.
  • the composition of the typical solution obtained after purification from Al and P is shown in table 4 below.
  • the RE concentrations are capable of varying to +/ ⁇ 20%.
  • Fe(II) ferrous iron phosphate is more soluble than MRE/HRE phosphate and has to precipitate at a higher pH.
  • n(Fe) n(Fe(II)) and n(Fe)/n(REs) ⁇ 500.
  • the operating conditions can be optimized in order to decrease the amount of reactions to be added.
  • the first precipitation test have been carried out at an SA of 100, which is totally unacceptable from an economic viewpoint.
  • the precipitation yield (%) of the rare earth metals (Ce, Gd and Y) and of iron in the aqueous solution as a function of the PO 4 /REs SA is monitored, as illustrated in FIG. 11 .
  • the operating conditions of stage 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 SA makes it possible to precipitate all of the rare earth metals with little ferrous iron. This is made possible by virtue of a high temperature (100° C.) and a deliberately short residence time ( ⁇ 1 h) which makes it possible to limit the reoxidation of Fe(II) to give Fe(III) over time and thus to limit the use of the PO 4 groups which are present to precipitate an Fe(III) phosphate.
  • the yields (%) obtained at each stage are represented in FIG. 12 , i.e. 95% for the light rare earth metals, 85% for the medium rare earth metals and 75% for the heavy rare earth metals.
  • the loss of rare earth metals during the stage of precipitation of Al and P (stage a) of the process according to the present invention) is thus deduced therefrom: 5% for the light rare earth metals, 15% for the medium rare earth metals and 25% for the heavy rare earth metals.
US14/776,249 2013-03-15 2014-03-13 Method for selectively recovering the rare earths from an aqueous acid sulfate solution rich in aluminum and phosphates Abandoned US20160032419A1 (en)

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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
FR1352349 2013-03-15
PCT/FR2014/050578 WO2014140492A1 (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

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SE1551224A1 (sv) 2015-09-23
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