• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Procedure for obtaining a renewable resource of metals from acid mine water, and corresponding installation. The procedure is intended to obtain a renewable resource of metals, in particular rare earths and yttrium, from acid mine waters, based on carrying out a neutralization of the acid solution rich in metals up to a ph value of 4, by means of addition of an adequate quantity of alkaline reagent, after which a massive precipitation is carried out under the new hydrochemical conditions of iron, arsenic, chromium, molybdenum and vanadium, followed by a neutralization of the previous solution, up to a value of ph of 5.5, finally carrying out a massive precipitation under the new hydrochemical conditions of aluminum, copper, rare earth and yttrium. This procedure is carried out by means of an installation in which there is a tank (1) which receives the acidic water and an alkaline reagent (3), followed by a settling basin (4) in which rich sludges are precipitated in the bottom. Generated metals (10), and after said raft (4) a second tank (5) that receives the mixed water with the addition of an alkaline reagent (6), so that the acidic water mixed with that alkaline reagent reaches a second raft decanter (7), where the precipitation of metal-rich sludge occurs (10 '), metal-rich sludge can be recovered through the extraction systems (9, 9') provided in the decanter ponds (4, 7). ). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2550526A1
    申请号:ES201430510
    申请日:2014-04-07
    公开日:2015-11-10
    发明作者:Jose Miguel NIETO LIÑÁN；Francisco MACÍAS SUÁREZ；Rafael PÉREZ LÓPEZ；Manuel A. CARALLO MONGE；Carlos Tomás AYORA IBÁÑEZ
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad de Huelva；
    IPC主号:
    专利说明:


    Procedure for obtaining a renewable resource of metals from acid mine waters, and corresponding installation. OBJECT OF THE INVENTION

    The present invention relates to a process for obtaining a renewable resource of metals, in particular rare earths and yttrium, from acidic mine waters.
    It is also the object of the invention to install the procedure in question.

    Unlike conventional mining (extractive mining), which extracts non-renewable resources, the object of the present invention can be considered renewable in the medium and long term because the generation of acidic waters is guaranteed for the following reasons: 1) society needs metallic resources to maintain and improve its level of development, 2) to obtain these resources mining activity is inevitable which generates acidic mine waters, and 3) the generation of these acidic waters will be active during the period of mine activity and for hundreds to thousands of years once this activity ceases. twenty
    BACKGROUND OF THE INVENTION

    The lanthanide series is the group of chemical elements that follow lanthanum in group IIIB of the periodic table. Their atomic distinction is that they occupy the electronic sublevel 4f. In the beginning, only these elements with atomic numbers 58 to 71 are lanthanides. However, many chemicals include lanthanum (La 57) in the series, as it has properties similar to lanthanides, although it does not complete the sublevel 4f. For the purposes of the present invention, it will be considered that the 15 elements of the lanthanide series group are: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, 30 tulio, yerbium and Lutetium
    Lanthanide elements are also commonly referred to as "Rare Earths" due to their presence in oxide mixtures. They are not rare elements (except for the promise, which only has radioactive isotopes) and its absolute abundance in the lithosphere is relatively high.
    Rare Earths are found in high concentrations in several economically important minerals such as: Bastaesnite (Ce, La) (CO3) F; Monacita (Ce, La, Nd, Th) PO4; Cerite ((Ca, Mg) 2 (Ce) 8 (SiO4) 7.3H2O); Xenotima YPO4; Gadolinite (Ce, La, Nd, Y) 2FeBe2 [O | SiO4] 2. Rare earths are also found as trace elements in common rock-forming minerals, in which they replace the major ions. The 40 Rare Earths can be found in inclusions of apatite, zircon, alanite, and other accessory minerals. Rare Earths are not very soluble and are not mobile in aqueous solutions (eg during metamorphic events).

    On the other hand, yttrium (Y 39) closely resembles the elements of Rare Earths. The stable isotope 45 89Y constitutes 100% of the natural element, which is almost always associated with the Rare Earths and is often classified as one of them. Chemically resembles the lanthanides.

    The primary obtaining of metallic resources in general and of rare earths and yttrium in particular, 50 occurs exclusively from extractive mining processes. Well, the need for these metallic resources by the current technological society is increased
    Over time, and in particular the demand for rare earths and yttrium has an extraordinary growth in the last two decades, with the demand that the demand continues to grow over time.

    Due to this increase in the need for metal resources in general and rare earths 5 in particular, there is a boom in mining exploration and exploitation, which inevitably implies the opening of new mines to meet these needs, so that this situation It entails a deterioration of the environment.

    A clear example of this deterioration is the generation of acid mine waters during and after the cessation of mining activity.

    As is known, acid mine waters are solutions that are characterized by having a low pH, as well as high acidity and a very high concentration of metals and metalloids in solution. fifteen

    When these metal-rich waters interact with natural rain systems, they cause chemical and ecological deterioration. In addition, this type of water carries significant amounts of global metal flow to the oceans. For example, it has been estimated that approximately 37% of the global Zn flow to the oceans comes from the 20 rivers contaminated by acid mine waters in Spain (Tinto and Odiel rivers). (Nieto et al., 2007, Environment International, 33 (4), 445-455).

    It has been known in the prior art for the recovery of metallic species from an acidic aqueous solution that contains them, by means of liquid-liquid extractions, generally resorting to cationic extraction agents, more frequently dissolved in a inert organic diluent.

    By doing this, the metallic species are more or less selectively extracted from the aqueous phase in the organic phase according to the chosen extraction agent, the starting aqueous phase and the working conditions, after which the organic phase enriched in metallic species , it is treated according to physical-chemical procedures (precipitation, aqueous regeneration or second extraction cycle, etc.) to recover valuable metals from it.

    The necessary and industrially indispensable condition for a recovery procedure 35 of these metals by a liquid-liquid extraction procedure, taking into account the weak concentrations of these species in the aqueous solutions of attack of the minerals and consequently of the important volumes put at stake for an industrial production, it is to be able to recover them simultaneously through a single extraction stage with a high depletion rate of the aqueous phase in the different species. 40 That is to say, it is convenient to have a powerful and non-selective species extraction agent.

    EP 2537813 discloses a process for the treatment of mine waters comprising the addition, at least in one step, of a hard-free alkaline reagent to the water to be treated to precipitate metals in the form of hydroxides, a precipitation of the Metal hydroxides formed, the addition of a hardness forming precipitation reagent, after separating the precipitated metal hydroxides and finally adding a curing lime reagent to mine water to precipitate sulfate as gypsum.
    For its part, the Spanish patent ES 495,176 discloses a procedure for the global recovery of yttrium and rare earths contained in an acidic aqueous phase, consists in putting
    contacting the aqueous · acidic solution with a homogeneous organic phase comprising a di- (alcoholphenyl) -phosphoric acid and an inert organic solvent chosen from aliphatic or aromatic hydrocarbons, used alone or in admixture, whereby, as a result, after phase separation, a substantially depleted aqueous phase and an organic phase loaded with yttrium and rare earths are collected. 5

    Industrially, rare earths can be extracted by means of solvents or from ion exchange methods. For the separation and purification of rare earths, the use of solvent extraction techniques (liquid-liquid extraction) is often more frequent because they facilitate the processing of larger volumes in consecutive stages. In the industrially used solvent extraction techniques, an aqueous phase, in the form of an aqueous solution containing metallic elements, is contacted, with an organic phase containing an extracting agent for a specific metallic element and an organic solvent to dilute the extracting agent, to thereby extract the specific metallic element with the extracting agent. In this way, the specific metallic element 15 is separated. A variety of extracting agents are used in the art, for example tributyl phosphate (TBP), carboxylic acid (Versatile acid 10), esters of phosphoric acid, phosphonic acid and phosphic acid. All these industrial processes are complex and expensive.

    We can conclude therefore that there is an important problem worldwide due to the shortage of yttrium and Rare Earths, a problem that grows in the face of a demand that does not stop growing, it is expected that in the not too distant future the demand will far exceed to production Traditional systems based on mining extraction (in the few producing countries) and further industrial treatment by the aforementioned techniques, are expensive and complex processes. This situation has given rise to the search for solutions based on the recycling of these metals, mainly from urban or industrial waste.

    The present invention is framed precisely in this field of the search for cost-effective alternatives in the recovery of yttrium and Rare Earths, allowing to obtain a renewable resource in solid state of metals, and in particular rare earths and yttrium, from acidic waters of 30 mine. The ultimate goal is to revalue the metals in dissolved state that are present in the acidic waters of the mine.
    DESCRIPTION OF THE INVENTION
    The process of the invention allows to obtain a renewable resource in solid state of metals, and in particular rare earths and yttrium, from acidic mine waters.

    More specifically, the process of the invention comprises the following operational phases:
    - Neutralization of the acid solution rich in metals to a pH value of 4, by adding a precise amount of alkaline reagent (NaOH, CaOH, etc.) that allows reaching the pH of 4.
    - Mass precipitation under the new hydrochemical conditions of iron, arsenic, chromium, molybdenum and vanadium. Four. Five
    - Neutralization of the above solution to a pH value of 5.5 by adding a precise amount of alkaline reagent to reach said pH of 5.5.
    - Mass precipitation under the new hydrochemical conditions of aluminum, copper, rare earths and yttrium.
    The first stage of neutralization of the acid solution rich in metals takes place in a first mixing tank by adding an alkaline reagent in an amount dependent on the
    flow rate and acidity of acidic water, so that it must be dosed in the precise amount to raise the pH of the solution to a value close to 4.
    The stage of massive precipitation of iron, arsenic, chromium, molybdenum and vanadium, takes place in a decanter raft with a time of hydraulic residence of the water in the decanter raft between 20 and 28 hours. 5
    The second stage of neutralization of the acid solution rich in metals takes place in a second mixing tank, by adding an alkaline reagent in an amount depending on the flow rate and acidity of the effluent water of the decanter tank, so that it must be dosed in the precise amount to raise the pH of the solution to a value close to 5.5. 10
    The stage of massive precipitation of aluminum, copper, rare earths and yttrium, takes place in a second decantering raft with a time of hydraulic residence of the water in the decantering raft between 20 and 28 hours.
    In a preferred embodiment of the invention, an inorganic or organic adjuvant is added in the first mixing tank and / or in the second mixing tank An example of the adjuvant is a cationic polyelectrolyte.
    In another preferred embodiment of the invention, the alkaline reagent to be added in the neutralization steps is preferably selected from those most soluble alkaline reagents under acidic conditions, more preferably from CaCO3, Ca (OH) 2, CaO, Na2CO3, NaOH and MgO in a proportion between 0.4 and 1 ton of alkali per ton of acidity.

    For the implementation of the mentioned procedure, the invention contemplates the use of an installation comprising:
    -  a mixing tank (1) 25
    -  a decanter raft (4)
    -  a mixing tank (5)
    -  a decanter raft (7)
    -  a set of pipes (8, 8 ’, 8”) that communicate each part of the installation.
    In successive preferred embodiments of the installation object of the invention:
    -  The mixing tanks (1) and (5) include means for mixing and homogenizing the alkaline reagents with the waters to be treated.
    -  The alkaline reagent that is mixed with the acidic water in the tank (1) and the alkaline reagent that is mixed with the effluent from the decanter tank (4) in the mixing tank (5), are applied by means of corresponding dosers.
    -  the bottom of the decanter rafts (4) and (7) has pronounced inclinations to ensure that the decanted sludge is concentrated in one or several pots or channels.
    -  the extraction of the sludge precipitated at the bottom of the decanter rafts (4) and (7) is carried out by means of a valve opening / closing system or by means of a suction system. 40
    -  the water transfer, when mixed with the alkaline reagent, is carried out by means of corresponding pipes (8, 8 ’, 8”).
    DESCRIPTION OF THE DRAWINGS
    To complement the description that will then be made and in order to help a better understanding of the features of the invention, this descriptive report is attached, forming an integral part of it, a single drawing where illustrative and not limiting , the schematic representation corresponding to the installation based on which the procedure object of the invention is carried out is shown. fifty
    PREFERRED EMBODIMENT OF THE INVENTION

    As can be seen in the aforementioned figure, the installation of the invention comprises a first mixing tank (1) receiving the acidic water from a metal-rich mine (2) and an alkaline reagent (3). The alkaline reagent can be any of the chemicals usually used in neutralization processes. The reagent must be sufficiently soluble and reactive so that the addition of the specific amount raises the pH to the desired value. All reagents that generate sufficient alkalinity to raise the pH to neutral values are valid. Those more soluble alkaline reagents are preferable under the acidic conditions of these metal-rich solutions, the more soluble the reagent is, the faster the pH rise will be. Under these premises, the following reagents can be considered suitable, among others: NaOH, CaO, Ca (OH) 2, CaCO3, Na2CO3, MgO, etc.

    The dosage of the alkaline reagent will be carried out by the usual technical means known in the state of the art, according to the specific product to be dosed and the solid or liquid state thereof. The amount of alkaline reagent (3) to be added will depend on the flow rate and acidity of the acidic water (2), so that it must be dosed in the precise amount in order to raise the pH of the solution to a value close to 4.

    By adding this alkaline reagent, new hydrochemical conditions are generated under which metals cease to be soluble and precipitate, regardless of the reagent used to modify the pH. Depending on the reagent used, some mineral or other species will be formed, there being logically for each possible element-reagent combination a product of different solubility, easily obtainable by one skilled in the art. The idea is to take advantage of the fact that the solubility of many metals with an increasing pH decreases, this pH value being different depending on the metals. Thus, the pH value of 4 set at this stage is the one that guarantees the precipitation of the desired metals detailed below.

    The following table provides approximate indicative figures, relative to the amount of alkaline reagent (3) to be added in the acid mine neutralization processes:

     Alkaline Reagent  Need for Alkali (ton / ton of acidity) Efficacy of neutralization (% of alkali added effective)
     CaCO3  1.00 30 - 50
     Ca (OH) 2  0.74
     CaO  0.56
     Na2CO3  1.06 60 - 80
     NaOH  0.80
     MgO  0.4

    In the second column, the relative need for alkali is indicated using 35 CaCO3 as a reference and indicates the precise amount of alkali per unit of acidity (expressed as CaCO3).

    The third column reflects the effectiveness of neutralization, which estimates the performance of the chemical reagent to neutralize an acid mine water. So for example, if 100 tons of
    acid is the amount to be neutralized, so it can be estimated that 82 tons of Ca (OH) 2 are necessary to neutralize the acidity of the water (100 (0.74) /0.90).

    Although it is not necessary for the proper functioning of the process, the possibility of adding in addition to the alkaline reagent (3) some type of inorganic or organic adjuvant (for example a cationic polyelectrolyte) is provided as is done in the conventional processes of coagulation-flocculation. By adding this adjuvant, it is possible to speed up the process.

    The dosage point may be on the tank itself or before it. It is advisable to provide this tank with the necessary means to achieve a good mixing and homogenization of the reagent with acidic mineral waters rich in metals (2). For this purpose, any of the means known in the state of the art can be used. The volume of the tank will be determined by the volume of flow to be treated. The dissolution of the alkaline reagent (3) in these acidic mine waters is very fast, therefore the contact time is not a relevant parameter to take into account in the sizing of these tanks.

    Through the pipe (8) that mixture of acidic water and alkaline reagent from the tank (1), reach the decanter raft (4). twenty

    In the decanter raft (4) the second stage of the process takes place, that is, the massive precipitation of iron, arsenic, chromium, molybdenum and vanadium under the new hydrochemical conditions generated as a result of the addition of the reagent in the previous stage.
    For this, the effluent of water contaminated by metals, is stored in this decanter raft (4) for a period of time ranging from 20 to 28 hours. Metals [M] can form different types of insoluble compounds with anions, such as:

    Hydroxides: Mx + + x OH- → M (OH) x 30
    Carbonates: 2Mx + + x CO32- → M2 (CO3) x
    Sulfides: 2Mx + + x S2- → M2 (S) x

    The hydraulic residence time of the water in the decanter raft (4) will vary between 20 and 28 hours, in order to provide sufficient time for the precipitation of a mud (10) rich in iron, arsenic, chromium, molybdenum. and vanadium.

    The precipitated sludge (10) is periodically removed through an extraction system (9) provided at the bottom of the decanter raft (4). This system can consist of a valve in which case, the purge will be carried out simply by closing / opening and hydrostatic pressure. To this end, it is expected that the bottom of the raft has very steep inclinations to ensure that the decanted sludge (10) is concentrated in one or more pits or channels from which the valve aspires. (not shown in the figure)

    Alternatively, the extraction of these decanted sludges (10) by means of 45 suction systems is envisaged. In this case, the bottom of the decanter tank (4) will be adapted to the suction system used, to guarantee the absence of “dead zones” where the aspiration is not effective.

    Through the pipeline (8 ’) the effluent waters of the decantering raft (4), reach a second 50 mixing tank (5).

    The third stage of the process takes place in the mixing tank (5), that is to say neutralization of the previous solution to a pH value of 5.5 by adding a precise amount of alkaline reagent (6).

    All the considerations set out above regarding the different types of alkaline reagents to be used, and the dosing techniques to be used, are applicable to this process stage.

    The difference with respect to the first stage of the process is that the pH reached is different (5.5 in this second stage) and therefore the metals that are no longer soluble are different. Thus, a selective recovery of Rare Earth and certain metals is achieved through pH regulation.

    Next, the water reaches a second settling raft (7) where the fourth stage of the process takes place, that is, the massive precipitation under the new hydrochemical conditions of aluminum, copper, rare earths and yttrium.

    The water residence time of the water in the settling tank (7) will vary between 20 and 28 hours.
    The precipitated sludge (10 ') is periodically removed through an extraction system (9') provided at the bottom of the decanter raft (7), which may consist of a simple valve or alternatively a suction system. The considerations set out above in relation to the first decanter raft (4) are also valid for this second decanter raft (7). 25

    As a consequence of the described process, the effluent outlet (11) of the installation, that is to say the outlet water of the second decanter raft (7), will have pH conditions around 5-6. That is, it will be a treated water with a lower acidity than the original water (2) that was introduced into the tank (1), and a very lower concentration of metals in solution, 30 so that this effluent outlet (11 ) of the water can be poured into a natural channel, minimizing the environmental impact.

    权利要求:
    Claims (12)
    [1]

    1.- Procedure for obtaining a renewable resource of metals from acid mine waters, particularly to obtain rare earths and yttrium, characterized in that it comprises the following operational phases:
    - neutralization of the acid solution rich in metals to a pH value of 4.5 by adding a precise amount of alkaline reagent to reach said pH of 4;
    - massive precipitation under the new hydrochemical conditions of iron, arsenic, chromium, molybdenum and vanadium;
    - neutralization of the above solution to a pH value of 5.5, by adding a precise amount of alkaline reagent, to reach said pH of 5.5, and
    - massive precipitation under the new hydrochemical conditions of aluminum, copper, rare earths and yttrium.

    [2]
    2. Procedure for obtaining a renewable resource of metals from acid mine waters 15, according to claim 1, characterized in that
    - the first stage of neutralization of the acid solution rich in metals takes place in a mixing tank (1) by adding an alkaline reagent (3) in an amount depending on the flow rate and acidity of the acidic water (2), of so that it must be dosed in the precise amount to raise the pH of the solution to a value close to 20 4.
    - the stage of massive precipitation of iron, arsenic, chromium, molybdenum and vanadium takes place in a decanter raft (4) with a time of hydraulic residence of the water in the decanter raft (4) between 20 and 28 hours.
    - the second stage of neutralization of the acid solution rich in metals takes place in a mixing tank (5), by the addition of an alkaline reagent (6) in an amount depending on the flow rate and acidity of the effluent water of the raft Decanter (4), so that it must be dosed in the precise amount to raise the pH of the solution to a value close to 5.5.
    - the stage of massive precipitation of aluminum, copper, rare earths and yttrium, takes place in 30 a decanter raft (7) with a time of hydraulic residence of the water in the decanter raft (7) between 20 and 28 hours.

    [3]
    3. Procedure for obtaining a renewable resource of metals from acid mine waters, according to any one of claims 1 to 2, characterized in that an inorganic or organic adjuvant is added to the mixing tank (1) and / or in the mixing tank (5).

    [4]
    4. Procedure for obtaining a renewable resource of metals from acid mine waters according to claim 3, characterized in that the adjuvant is a cationic polyelectrolyte. 40

    [5]
    5. Procedure for obtaining a renewable resource of metals from acid mine waters according to any one of claims 1 to 2, characterized in that the alkaline reagent (3) to be added in the neutralization steps, is preferably selected from among those more soluble alkaline reagents under acidic conditions. Four. Five

    [6]
    6. Procedure for obtaining a renewable resource of metals from acid mine waters according to claim 5, characterized in that the alkaline reagent (3) is selected from CaCO3, Ca (OH) 2, CaO, Na2CO3, NaOH and MgO in a proportion between 0.4 and 1 ton of alkali per ton of acidity. fifty

    [7]
    7.- Installation for obtaining a renewable resource of metals from acid mine waters, particularly to obtain rare earths and yttrium, characterized in that it comprises:
    -  a mixing tank (1)
    -  a decanter raft (4)
    -  a mixing tank (5) 5
    -  a decanter raft (7)
    -  a set of pipes (8, 8 ’, 8”) that communicate each part of the installation.

    [8]
    8.- Installation for obtaining a renewable resource of metals from acidic mine waters 10, according to claim 7, characterized in that the mixing tanks (1) and (5) include means for mixing and homogenizing the alkaline reagents (3) and (6) with the waters to be treated.

    [9]
    9. Installation for obtaining a renewable resource of metals from acid mine waters 15, according to any one of claims 7 to 8, characterized in that the alkaline reagent (3) that is mixed with the acidic water (2) in the tank (1) and the alkaline reagent (6) that is mixed with the effluent from the decanter tank (4) in the mixing tank (5), they are applied by means of corresponding dosers.
    [10]
    10.- Installation for obtaining a renewable resource of metals from acid mine waters, according to any one of claims 7 to 9, characterized in that the bottom of the settling rafts (4) and (7) has pronounced inclinations for ensure that decanted sludge is concentrated in one or several pots or channels.
    [11]
    11. Installation for obtaining a renewable resource of metals from acid mine waters, according to any one of claims 7 to 10, characterized in that the extraction of the sludge (10) precipitated at the bottom of the settling rafts ( 4) and (7) is performed by a valve opening / closing system or by a suction system.
    [12]
    12.- Installation for obtaining a renewable resource of metals from acid mine waters, according to any one of claims 7 to 11, characterized in that the water transfer, when mixed with the alkaline reagent, is carried out by corresponding pipes (8, 8 ', 8 ”).
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