WO2015155386A1 - Procédé d'obtention d'une ressource renouvelable de métaux à partir d'eaux acides de mine et installation correspondante - Google Patents

Procédé d'obtention d'une ressource renouvelable de métaux à partir d'eaux acides de mine et installation correspondante Download PDF

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Publication number
WO2015155386A1
WO2015155386A1 PCT/ES2015/000045 ES2015000045W WO2015155386A1 WO 2015155386 A1 WO2015155386 A1 WO 2015155386A1 ES 2015000045 W ES2015000045 W ES 2015000045W WO 2015155386 A1 WO2015155386 A1 WO 2015155386A1
Authority
WO
WIPO (PCT)
Prior art keywords
metals
obtaining
acid mine
renewable resource
decanter
Prior art date
Application number
PCT/ES2015/000045
Other languages
English (en)
Spanish (es)
Inventor
José Miguel Nieto Liñán
Francisco Maclas Suárez
Rafael Pérez López
Manuel A. Carallo Monge
Carlos Tomás Ayora Ibáfiez
Original Assignee
Universidad De Huelva
Consejo Superior De Investigaciones Cientificas (Csic)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universidad De Huelva, Consejo Superior De Investigaciones Cientificas (Csic) filed Critical Universidad De Huelva
Publication of WO2015155386A1 publication Critical patent/WO2015155386A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

Definitions

  • the present invention relates to a process for obtaining a renewable resource of metals, in particular rare earths and yttrium, from acidic mine waters.
  • the object of the 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 activity from the mine and for hundreds to thousands of years once this activity ceases.
  • the lanthanide series is the group of chemical elements that follow lanthanum in the MIB group of the periodic table. Their atomic distinction is that they occupy the electronic sublevel 4f. Initially, 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.
  • the 15 elements of the lanthanide series group are: lanthanum, cerium, praseodymium, neodymium, promised, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, tulio, ytterbium 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 of 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) (CO 3 ) F; Monacita (Ce, La, Nd, Th) PO 4 ; Cerite ((Ca, Mg) 2 (Ce) 8 (SiO 4 ) 7.3H 2 O); Xenotima YPO 4 ; Gadolinite (Ce, La, Nd, Y) 2 FeBe 2 [O
  • yttrium (Y 39) closely resembles the elements of Rare Earths.
  • the stable isotope 89 Y constitutes 100% of the natural element, which is almost always associated with the Rare Earth and is often classified as one of them. Chemically resembles the lanthanides.
  • 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.
  • 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 process 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 in The game for an industrial production 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. 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 hydroxides. Metal formed, the addition of a precipitation precipitation reagent hardness, after separating the precipitated metal hydroxides and finally adding a curing lime reagent to the mine water to precipitate sulfate as gypsum.
  • the Spanish patent ES 495,176 discloses a procedure for the global recovery of yttrium and Rare Earth contained in an acidic aqueous phase, consists in contacting the aqueous-acidic solution with a homogeneous organic phase comprising a di-acid ( alcohol-phenyl) -phosphoric and an inert organic solvent chosen from aliphatic or aromatic hydrocarbons, used alone or in admixture, whereby, as a result, after the phase separation, a substantially depleted aqueous phase and a charged organic phase are collected of yttrium and rare earths.
  • a homogeneous organic phase comprising a di-acid ( alcohol-phenyl) -phosphoric and an inert organic solvent chosen from aliphatic or aromatic hydrocarbons, used alone or in admixture, whereby, as a result, after the phase separation, a substantially depleted aqueous phase and a charged organic phase are collected of yttrium and rare earths.
  • rare earths can be extracted by means of solvents or from ion exchange methods.
  • solvent extraction techniques liquid-liquid extraction
  • 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 is separated.
  • TBP tributyl phosphate
  • carboxylic acid Versatile acid 10
  • esters of phosphoric acid phosphonic acid and phosphic acid. All these industrial processes are complex and expensive.
  • 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.
  • the process of the invention comprises the following operational phases:
  • 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 the 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 second stage of neutralization of the acid solution rich in metals takes place in a second mixing tank, by adding an alkaline reagent in quantity dependent on the flow rate and acidity of the effluent water of the decantering 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.
  • the massive precipitation stage of aluminum, copper, rare earths and yttrium takes place in a second decantering raft with a water residence time in the decantering raft between 20 and 28 hours.
  • an inorganic or organic adjuvant is added in the first mixing tank and / or in the second mixing tank
  • An example of adjuvant is a cationic polyelectrolyte.
  • 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 CaCO 3 , Ca (OH) 2, CaO, Na 2 CO 3, NaOH and MgO in a proportion between 0.4 and 1 ton of alkali per ton of acidity.
  • the invention contemplates the use of an installation comprising:
  • 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 a system of aspiration.
  • 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 commonly 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 , CaCO 3 , Na 2 CO 3 , MgO, etc.
  • the dosage of the alkaline reagent will be carried out by means of the usual technical means known in the current 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.
  • the third column reflects the effectiveness of neutralization, which estimates the performance of the chemical reagent to neutralize a mine acid water.
  • neutralization estimates the performance of the chemical reagent to neutralize a mine acid water.
  • 100 tons of acid is the amount to be neutralized, then 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).
  • some type of inorganic or organic adjuvant for example a cationic polyelectrolyte
  • 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.
  • 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.
  • Metals [M] can form different types of insoluble compounds with anions, such as:
  • the water residence time of the water in the settling tank (4) will vary between 20 and 28 hours, in order to provide sufficient time for the water to occur. 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. For this, 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 several pots or channels from which the valve aspirates, (not shown in the figure)
  • the extraction of these decanted sludges (10) by means of aspiration systems is provided.
  • 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.
  • 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).
  • the water reaches a second decanter 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 settling tank (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).
  • 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, so that this effluent outlet (1 1 ) of the water can be poured into a natural channel, minimizing the environmental impact.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Le procédé est prévu pour obtenir une ressource renouvelable de métaux, en particulier des métaux des terres rares et de l'yttrium, à partir d'eaux acides de mine, lequel procédé comprend une phase de neutralisation de la solution acide riche en métaux jusqu'à une valeur de pH de 4, par addition d'une quantité appropriée de réactif alcalin, une phase de précipitation massive dans les nouvelles conditions hydrochimiques du fer, de l'arsenic, du chrome, du molybdène et du vanadium, une phase de neutralisation de la solution antérieure, jusqu'à une valeur de pH de 5,5 suivie pour terminer d'une précipitation massive dans les nouvelles conditions hydrochimiques de l'aluminium, du cuivre, des métaux des terres rares et de l'yttrium. Ce procédé est mis en oeuvre au moyen d'une installation dans laquelle il existe une cuve (1) qui reçoit l'eau acide et un réactif alcalin (3), un réservoir de décantation (4) dans le fond duquel sont précipitées les boues riches en métaux générés (10) et qui est suivi d'une autre cuve (5) qui reçoit l'eau mélangée avec un réactif alcalin (6) ajouté de sorte que l'eau acide mélangée avec ce réactif alcalin atteigne un second réservoir de décantation (7) où se produit la précipitation des boues riches en métaux (10'), lesdites boues riches en métaux pouvant être récupérées au moyen de systèmes d'extraction (9,9') installés dans les réservoirs de décantation (4, 7).
PCT/ES2015/000045 2014-04-07 2015-03-31 Procédé d'obtention d'une ressource renouvelable de métaux à partir d'eaux acides de mine et installation correspondante WO2015155386A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201430510A ES2550526B1 (es) 2014-04-07 2014-04-07 Procedimiento de obtención de un recurso renovable de metales a partir de aguas ácidas de mina, e instalación correspondiente.
ESP201430510 2014-04-07

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Publication Number Publication Date
WO2015155386A1 true WO2015155386A1 (fr) 2015-10-15

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ES (1) ES2550526B1 (fr)
WO (1) WO2015155386A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108486371A (zh) * 2018-06-07 2018-09-04 广西壮族自治区环境保护科学研究院 一种大理石废浆皂化p507-p204协同萃取体系的方法
CN108706845A (zh) * 2018-06-11 2018-10-26 惠州金茂源环保科技有限公司 一种污泥处理装置
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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112708780B (zh) * 2020-12-09 2022-09-02 金川集团股份有限公司 一种镍钴溶液除铝的方法

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JP2004202488A (ja) * 2002-12-09 2004-07-22 Nippon Steel Corp 金属鉱山排水の処理方法および有価金属の回収方法
WO2012137495A1 (fr) * 2011-04-06 2012-10-11 三菱マテリアルテクノ株式会社 Procédé de récupération de terres rares
WO2012149642A1 (fr) * 2011-05-04 2012-11-08 Orbite Aluminae Inc. Procédés d'extraction d'éléments de terres rares dans divers minerais

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JP2004202488A (ja) * 2002-12-09 2004-07-22 Nippon Steel Corp 金属鉱山排水の処理方法および有価金属の回収方法
WO2012137495A1 (fr) * 2011-04-06 2012-10-11 三菱マテリアルテクノ株式会社 Procédé de récupération de terres rares
WO2012149642A1 (fr) * 2011-05-04 2012-11-08 Orbite Aluminae Inc. Procédés d'extraction d'éléments de terres rares dans divers minerais

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CARABALLO, M.A. ET AL.: "Field multi-step limestone and MgO passive system to treat acid mine drainage with high metal concentrations.", APPLIED GEOCHEMISTRY. SEP. 2009., vol. 24, no. 12, 17 September 2009 (2009-09-17), pages 2301 - 2311, XP026742432 *
MACÍAS, F. ET AL.: "Natural pretreatment and passive remediation of highly polluted acid mine drainage.", JOURNAL OF ENVIRONMENTAL MANAGEMENT. AUG. 15 2012 ., vol. 104, 12 August 2012 (2012-08-12), pages 93 - 100, XP028486425 *
VERPLANCK,P.L. ET AL.: "Rare earth element partitioning between hydrous ferricoxides and acid mine water during iron oxidation.", APPLIED GEOCHEMISTRY, vol. 19, 16 January 2004 (2004-01-16), pages 1339 - 1354, XP055229038 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108486371A (zh) * 2018-06-07 2018-09-04 广西壮族自治区环境保护科学研究院 一种大理石废浆皂化p507-p204协同萃取体系的方法
CN108486371B (zh) * 2018-06-07 2020-01-10 广西壮族自治区环境保护科学研究院 一种大理石废浆皂化p507-p204协同萃取体系的方法
CN108706845A (zh) * 2018-06-11 2018-10-26 惠州金茂源环保科技有限公司 一种污泥处理装置

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Publication number Publication date
ES2550526A1 (es) 2015-11-10
ES2550526B1 (es) 2016-07-18

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