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WO2012011770A2 - Procédé de récupération sélective de métaux rares - Google Patents

Procédé de récupération sélective de métaux rares Download PDF

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Publication number
WO2012011770A2
WO2012011770A2 PCT/KR2011/005418 KR2011005418W WO2012011770A2 WO 2012011770 A2 WO2012011770 A2 WO 2012011770A2 KR 2011005418 W KR2011005418 W KR 2011005418W WO 2012011770 A2 WO2012011770 A2 WO 2012011770A2
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metal
rare
metal component
aqueous solution
hydroxide
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Korean (ko)
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WO2012011770A3 (fr
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야부타니토모키
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University of Tokushima NUC
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University of Tokushima NUC
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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
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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

  • This invention relates to the selective collection method of the rare metal component which consists of molybdenum, tungsten, and vanadium.
  • molybdenum is an important metal widely used in the manufacture of special steels, lubricants, spark plugs, electronic materials, color pigments, filaments such as fluorescent lamps, etc., but it is an item that requires monitoring for which water is regulated.
  • Vanadium is a desulfurization catalyst; clothing material; Additives for titanium, aluminum, zirconium, steel and the like; Heat-resistant materials such as jets and guided missiles; Sputtering target; Materials for vacuum tube deposition; Alloy superconducting materials; It is used for various uses, such as a hydrogen storage alloy. Moreover, tungsten is used abundantly for uses, such as a cemented carbide and a catalyst.
  • strong acid nitric acid, hydrochloric acid, sulfuric acid
  • This is achieved by exchanging cations of metals with protons in strong acids, elution of surface-adsorbed metal salts, dissolution by precipitation acids, and the like.
  • strong acids it is expensive to construct treatment systems with acid resistance specifications.
  • the thing with low selectivity of the metal to elute is mentioned.
  • nitric acid is a very good solvent for dissolving metal ions
  • nitrogen is regulated by the law for the prevention of eutrophication.
  • hydrogen sulfide and ammonia are used to recover heavy metals and form precipitates, but they have problems such as odor.
  • Non-Patent Document 1 Bulletin of Chemical Society of Japan, 74 (1), 31-38 (2001).
  • Non-Patent Document 2 Modern Methods for Trace Element Determination, John Wiley and Sons Ltd (1993).
  • This invention is made
  • the main objective is the collection
  • the metal component containing a rare metal is adsorbed or occluded in a solid phase, and then the solid phase is contacted with an aqueous solution containing peroxy compounds such as sodium percarbonate, hydrogen peroxide, and ozone.
  • peroxy compounds such as sodium percarbonate, hydrogen peroxide, and ozone.
  • specific rare metal components such as molybdenum, vanadium and tungsten can be eluted with good selectivity.
  • This method is inexpensive, easy to handle, and has a high economic efficiency in that a specific rare metal can be recovered selectively using a peroxy compound having a low environmental load, which is advantageous for high purity of the rare metal. found.
  • the recovery liquid containing the rare metal component contains almost no nitrogen, other heavy metals, etc., it is possible to cope with the regulation of the total amount of nitrogen in the wastewater, and the chelating resin and the adsorbent after the recovery can be reused. Found out how. This invention is completed based on this knowledge.
  • this invention provides the selective recovery method of the following rare metals.
  • Item 1 A selective recovery method of a rare metal, comprising the following steps (1) and (2):
  • Item 2 The selective recovery method of the rare metal according to the item 1, wherein the chelate resin used in the step (1) is a resin containing an imino diacetic acid group or a salt thereof.
  • the precipitate formed in step (1) is a precipitate containing at least one component selected from the group consisting of aluminum hydroxide, magnesium hydroxide, gallium hydroxide, iron hydroxide, manganese hydroxide, manganese oxide, indium hydroxide, and a rare earth element hydroxide.
  • the selective recovery method of the rare metal according to the above item 1 or 2.
  • Item 4 The selective recovery method for rare metal according to any one of items 1 to 3, wherein the peroxy compound used in step (2) is at least one component selected from the group consisting of sodium percarbonate, hydrogen peroxide, and ozone.
  • the rare metal including the step of selectively recovering the rare metal by the method according to any one of items 1 to 4 above, followed by washing the used chelating resin or the adsorbent with an acid aqueous solution and reusing it in step (1). Selective recovery method.
  • the selective recovery method of the rare metal of the present invention comprises (i) a method of adsorbing a metal component by contacting an aqueous solution containing a metal component including the rare metal with a chelating resin or an adsorbent, or an aqueous solution containing a metal component including the rare metal.
  • a first step of adsorbing or occluding a metal component including a rare metal in a solid phase by a method of forming a precipitate in the precipitate and adsorbing or occluding a metal component in the formed precipitate, and (ii) a solid phase that adsorbs or occludes the metal component. It is a method which consists of a 2nd process which contacts a aqueous solution containing a peroxy compound, and elutes a specific rare metal.
  • the method of this invention is demonstrated concretely.
  • the treatment target is an aqueous solution containing at least one rare metal component selected from the group consisting of molybdenum, vanadium and tungsten.
  • the aqueous solution which extracted the metal component contained in the incineration fly ash collected by the waste incinerator using nitric acid, etc., the dilution of sewage sludge, etc. are processed. You can do In such incineration fly ash and sewage sludge, there have been reports that molybdenum, tungsten, etc. are highly concentrated (analytical chemistry: 57, 659-666 (2008)), and environmental pollution is concerned, but according to the method of the present invention, The causative component can be separated and recovered for effective use.
  • the amount of molybdenum, vanadium, and tungsten in the liquid to be treated is not particularly limited.
  • the amount of emission limitation (Environmental Protection Act for Human Health) Environmental standard about molybdenum It can be reduced to concentration below 0.07mg / L).
  • the rare metal is recovered at a high recovery rate by appropriately selecting the type and amount of the chelating resin or the adsorbent to be used, the amount of precipitation formed, and the like. It is possible.
  • various metal components may coexist in the process liquid.
  • various metal components may coexist in the process liquid.
  • aluminum, iron, manganese, copper, zinc, nickel, cobalt, cadmium, tin, gallium, lead, rare earth elements and the like may be contained.
  • a peroxy compound is used in the second step after performing an adsorption treatment to a solid phase such as a chelating resin, an adsorbent, or a precipitation in the first step by using an aqueous solution containing such various metal components as the treatment target liquid.
  • a treatment liquid containing specific rare metal components such as molybdenum, vanadium and tungsten can be eluted with good selectivity.
  • group containing at least 2 sort (s) of atom chosen from the group which consists of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom is mentioned, for example.
  • group containing at least 2 sort (s) of atom chosen from the group which consists of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom is mentioned, for example.
  • an imino diacetic acid group, an imino diphosphate group, an aminocarboxylic acid group, an aminophosphate group, a glucamine group, a thiol group, a sulfide group, these salts, etc. are mentioned.
  • an imino diacetic acid group, an imino diphosphate group, an aminocarboxylic acid group, an amino phosphate group, these salts, etc. are preferable, and an imino diacetic acid group and its salt are especially preferable.
  • Alkali metal salts such as a sodium salt and potassium salt
  • Alkaline earth metal salts such as magnesium salts and calcium salts
  • Ammonium salts such as a trimethylammonium salt, a triethylammonium salt, ethanol ammonium salt, and diethanol ammonium salt, etc. are mentioned.
  • chelate resin which has various resin skeletons, such as styrene type, a phenol type, an acryl type, an epoxy type, can be used. have.
  • a chelate resin Although there is no limitation in particular also about the shape of a chelate resin, It is preferable to use the thing of the shape with favorable contact with a process liquid. For example, powdered resin, film
  • the ion exchange capacity of the chelate resin is not particularly limited, but for example, one having an exchange capacity of about 0.1-5.0 meq cm -3 can be used.
  • the kind of the adsorbent is not particularly limited, but may be any adsorbent having adsorption capacity to various metal components including rare metals.
  • adsorbent used in this method selective adsorption capacity for a specific component is not required, and one having an adsorption capacity for various metal components can be used.
  • Carbon powder such as activated carbon; iron content; Various ceramics (alumina, zirconia, ceria, etc.); Porous polymers; Wood adsorbents; Fibers and the like.
  • the adsorbent mentioned above can be used individually by 1 type or in mixture of 2 or more types.
  • the adsorption mechanism of the metal component to the adsorbent is considered to be surface adsorption, occlusion, mixed crystals, formation of complexes, etc., and is considered to be introduced into the adsorbent as a combination thereof.
  • the method for adsorbing an aqueous solution containing at least one metal component selected from the group consisting of molybdenum, vanadium and tungsten, which is the liquid to be treated, is not particularly limited, and the liquid to be treated and the chelate resin or the adsorbent are not particularly limited. What is necessary is just the method which can fully contact.
  • the amount of the chelate resin and the adsorbent in this case is not particularly limited either, and the amount of the chelate resin or the adsorbent capable of adsorbing a sufficient amount of the metal component is dispersed according to the amount of the metal component contained in the treatment liquid. Just do it.
  • a weight ratio (rare metal / chelate resin or adsorbent) of a rare metal with respect to a chelate or an adsorbent it is good to set it as the range about 0.000001 to 1 time normally.
  • the compound used as a raw material is soluble in the aqueous solution containing the rare metal to be processed, and can form a poorly soluble or insoluble metal compound in the aqueous solution. You just need to be. In particular, it is preferable that the specific surface area of the precipitate formed is large, and a precipitation phenomenon arises quickly.
  • Examples of such precipitation include poorly soluble hydroxides, poorly soluble phosphates, sulfides, and oxides.
  • specific examples of poorly soluble hydroxides include aluminum hydroxide, magnesium hydroxide, gallium hydroxide, iron hydroxide, manganese hydroxide, zirconium hydroxide, indium hydroxide, yttrium hydroxide, titanium hydroxide, bismuth hydroxide, thorium hydroxide, and hydroxides of rare earth elements.
  • Examples of the poorly soluble phosphate include aluminum phosphate, calcium phosphate, zirconium phosphate, lead phosphate, bismuth phosphate, and phosphates of rare earth elements.
  • sulfides include copper sulfide, cadmium sulfide, indium sulfide, barium sulfide, mercury sulfide, lead sulfide and the like.
  • Manganese oxide etc. can be illustrated as an oxide.
  • aluminum hydroxide, magnesium hydroxide, gallium hydroxide, iron hydroxide, manganese hydroxide, manganese oxide, indium hydroxide, rare earth elements and the like are preferred from the viewpoints of ease of precipitation recovery, metal adsorption capacity, and economy of the precipitant.
  • the metal compound which forms the above-mentioned precipitation may be one type, or may be a combination of 2 or more types.
  • the method for forming a precipitate in an aqueous solution containing at least one metal component selected from the group consisting of molybdenum, vanadium and tungsten to be treated is not particularly limited, but for example, precipitation in a treatment target liquid containing rare metal
  • a precipitate can be formed by dissolving a soluble compound (e.g., nitrate, chloride, sulfate, etc.), which is a raw material for forming a precipitate, and adding a component (precipitant) necessary to form a precipitate in the liquid.
  • a soluble compound e.g., nitrate, chloride, sulfate, etc.
  • the kind of precipitant may be determined depending on the kind of precipitation to be formed.
  • Precipitation of hydroxide can be formed by adding an alkali component.
  • precipitation of poorly soluble phosphate can be formed by reaction with a metal component contained in the liquid by adding soluble phosphate.
  • the addition amount of the compound serving as a raw material for forming the precipitate is not particularly limited, but may be appropriately determined depending on the amount of the rare metal contained in the liquid to be treated. Usually, it is preferable to add the raw material for precipitation formation of the quantity of about 10 to 1000 weight times of the quantity of the rare metal to collect, and to add the raw material for precipitation formation about 100 to 1000 weight times. More preferred.
  • the precipitate formed can be separated and recovered from the liquid to be treated by filtration, centrifugation, decantation, flotation, or the like.
  • a solid phase obtained by adsorbing or occluding a metal component including a rare metal, that is, a chelating resin, an adsorbent or a precipitate is brought into contact with an aqueous solution containing a peroxy compound to provide molybdenum It is a process of selectively eluting the rare metal component which consists of vanadium and tungsten.
  • At least 1 sort (s) of component especially chosen from the group which consists of sodium percarbonate, hydrogen peroxide, and ozone is preferable to use as a peroxy compound.
  • s sort of component especially chosen from the group which consists of sodium percarbonate, hydrogen peroxide, and ozone.
  • the elution treatment is carried out by a method described below, whereby a rare layer composed of molybdenum, vanadium and tungsten is obtained from a chelate resin, an adsorbent, or a precipitate adsorbed or occluded a metal component in the first step.
  • the metal component can be eluted with high selectivity.
  • peroxy compounds are inexpensive and easy to handle and contain hydrogen, oxygen, and carbon as constituent elements, and do not contain eutrophic and malodorous elements such as nitrogen and sulfur. Less material.
  • sodium percarbonate is a compound which is not subject to regulation such as a mineral, is a reagent outside the regulation subject to handling amount, and is a solid, and is a compound that is easy to handle.
  • ozone it is advantageous in that it is highly reactive with peroxy compound formation and is a gas generated from water and ultraviolet rays, which can be freely generated in the reaction vessel, but does not remain because it is rapidly decomposed after the reaction. Compound.
  • the concentration of the peroxy compound is not particularly limited, but for example, molybdenum, vanadium and tungsten may be selectively selected in a wide concentration range such as about 0.1 to 40% by weight. It can collect
  • the method for selectively recovering molybdenum, vanadium and tungsten from the solid phase obtained by adsorbing or occluding the metal component, that is, the chelate resin, the adsorbent, or the precipitation obtained in the first step is not particularly limited, What is necessary is just the method which can fully contact the aqueous solution containing an oxy compound.
  • distributing a chelating resin, an adsorbent, or precipitation to the aqueous solution containing a peroxy compound, the method of passing through the aqueous solution containing a peroxy compound to the column filled with the chelate resin or an adsorbent, etc. are mentioned. .
  • the liquid temperature at the time of the elution treatment is not particularly limited, and treatment can be performed at a temperature range of about 90 ° C. from room temperature.
  • the amount of the aqueous solution containing the peroxy compound is not particularly limited, but the amount of the aqueous solution that can sufficiently elute the rare metal, depending on the amount of the rare metal and other metals adsorbed or occluded in the chelate resin, the adsorbent or the precipitation.
  • a sufficient amount of the rare metal can usually be eluted in a relatively short time of about 1 to 10 minutes.
  • the rare metal component which consists of molybdenum, vanadium, and tungsten can be eluted with high selectivity from the solid phase which adsorbed or occluded the metal component containing a rare metal.
  • molybdenum, vanadium, and tungsten are all dominated by ionic species (III to VI), which are highly oxidized, belong to oxo acid-based metal elements, and It is assumed that the present form is different from the metal ion, reacts with the peroxy compound to form a felxo complex or heteropoly acid, and elutes with good selectivity.
  • the eluate obtained by eluting the rare metal component composed of molybdenum, vanadium and tungsten by the above-described method is capable of recovering the rare metal component according to conventional methods such as evaporation method, reprecipitation method and various solid phase methods (activated carbon, various adsorbents). Can be. Since the content of the metal component other than the rare metal component mentioned above is very small, the eluate can collect
  • the alkali metal component other than the heavy metal component bonded to the functional group of the chelate resin is cleaned by sufficiently washing the chelate resin after the adsorption treatment. It can be easily removed. For this reason, an alkali metal component etc. are hardly contained in the eluate after the process by a peroxy compound, and the high purity rare metal component can be obtained easily.
  • the kind of acid used for separating and removing the metal component from the chelate resin and the adsorbent is not particularly limited, and for example, hydrochloric acid, sulfuric acid, nitric acid, and the like can be used.
  • limiting in particular also about an acid concentration For example, the aqueous solution of the acid of the density
  • soluble salts can be formed with respect to many metal components adsorbed on the chelate resin and the adsorbent, so that the regeneration treatment of the chelate resin and the adsorbent can be performed efficiently.
  • a chelating resin or an adsorbent is isolate
  • the method of carrying out, the method of flowing an aqueous solution of an acid, etc. can be applied to the column which filled the chelating resin or the adsorbent.
  • the peroxy compound which is an active ingredient in the eluate is an inexpensive and easy-to-handle substance, and since acid-resistant devices are unnecessary, the cost can be reduced.
  • the peroxy compound contains hydrogen, oxygen, and carbon as constituent elements, and does not contain eutrophic and malodorous elements such as nitrogen and sulfur.
  • sodium percarbonate is a reagent outside the regulation subject to the handling amount and the like, and is a compound that is easy to handle because it is a solid.
  • ozone is a gas that is highly reactive with peroxy compound formation and is a gas generated from water and ultraviolet rays, and is advantageous in that it does not remain because it can be freely generated in the reaction vessel, but is rapidly decomposed after the reaction. Compound.
  • the recovery liquid containing the rare metal component contains almost no nitrogen or other heavy metals, it is possible to cope with the regulation of the total amount of nitrogen in the wastewater, and the chelating resin and the adsorbent after the recovery can be reused. It is an advantageous way.
  • FIG. 2 is a graph showing the relationship between the temperature of hydrogen peroxide water and the recovery rate of metal components in the elution treatment obtained in Example 1.
  • FIG. 2 is a graph showing the relationship between the temperature of hydrogen peroxide water and the recovery rate of metal components in the elution treatment obtained in Example 1.
  • FIG. 3 is a graph showing the relationship between the concentration of hydrogen peroxide water and the recovery rate of metal components in the elution treatment obtained in Example 1.
  • FIG. 4 is a graph showing the recovery rate of metal components in the hydrogen peroxide elution treatment obtained in Example 1.
  • FIG. 5 is a graph showing a recovery rate of a metal component during nitric acid elution treatment obtained in Example 1.
  • FIG. 6 is a graph showing a recovery rate of a metal component during hydrochloric acid elution treatment obtained in Example 1.
  • FIG. 7 is a graph showing a recovery rate of a metal component in the sulfuric acid leaching treatment obtained in Example 1.
  • FIG. 8 is a graph showing the recovery of each metal when using 30 wt% hydrogen peroxide solution obtained in Example 4.
  • FIG. 9 is a graph showing the recovery of each metal when using 1% by weight hydrogen peroxide solution obtained in Example 4.
  • Ammonium molybdate (NH 4 ) 6 Mo 7 O 24 4H 2 O), ammonium vanadate (NH 4 VO 3 ), and ammonium tungstate pentahydrate (5 (NH 4 ) 2 ⁇ 12 WO 3 ⁇ 5H 2 O ),
  • a weakly acidic cation exchange resin (trade name: Muromac B-1, manufactured by Muromachi Technos Co., Ltd.), having a sodium imino diacetate group, as a chelating resin, has a matrix structure: styrene-divinylbenzene air.
  • 0.3 g of coalescing, total exchange capacity: 2.4 eq / L, water content of 50-55%, particle size distribution: 0.3-1.25 mm) was added, and it stirred with the magnetic stirrer for 2 hours.
  • ICP mass spectrometry ICP-MS
  • ICP emission spectrometry ICP-AES
  • the residual rate, adsorption rate and recovery rate of each element were calculated by the following equation.
  • Residual rate (%) elemental amount / amount of additive element in the upper solution
  • the pH of the metal mixed solution was changed between pH 3.23-6.73, the adsorption test with respect to the chelate resin was performed, and the recovery rate and residual rate of Mo, V, and W were computed.
  • As the buffer an acetate-sodium acetate buffer was used in the range of pH 3.23 to 5.32, and sodium hydrogen phosphate, 12-hydrogen-dihydrogen phosphate buffer in the range of pH 5.78 to pH 6.73.
  • the hydrogen peroxide water used at the time of an elution process was diluted with ultrapure water, the hydrogen peroxide water of the density
  • concentration of hydrogen peroxide and the recovery rate of the metal component is shown in the graph of FIG. 3.
  • Mo and V had the highest recovery rate when the hydrogen peroxide concentration was 30%, and a recovery rate close to 100% was obtained. In W, the recovery was maintained up to a low concentration range of 0.1% hydrogen peroxide.
  • Metal mixed solutions containing the metal ions shown in Table 2 below at a concentration of 0.67 mg / kg were prepared, respectively. 15 mL of this metal mixture solution was added to the centrifuge tube, and pH was adjusted to 5.1 with the buffer solution. Subsequently, 0.5 g of weakly acidic cation exchange resins having the same sodium imino diacetate group as used in Example 1 was added to the metal mixture, followed by stirring with a magnetic stirrer for 2 hours. Thereafter, centrifugation was performed at 3500 rpm for 12 minutes, and the supernatant solution was subjected to ICP mass spectrometry (ICP-MS) and ICP emission spectrometry (ICP-AES) to calculate the residual and adsorption rates of the metal components.
  • ICP-MS ICP mass spectrometry
  • ICP-AES ICP emission spectrometry
  • Example 1 10 mL of 2 mol / L nitric acid was added to the chelate resin subjected to the elution treatment with hydrogen peroxide water, and the metal remaining in the chelate resin was eluted. Then, 10 mL of 2 mol / L sodium hydroxide aqueous solution was added, and it left for 2 minutes, and wash
  • the metal adsorbed to the chelate resin was eluted in the same manner as in Example 1 using 50 mL of 1 wt% hydrogen peroxide water or 10 mL of 30 wt% hydrogen peroxide water.
  • the ICP-MS measurement and the ICP-AES measurement were performed, and the recovery rate of the metal component was computed.
  • centrifugation was performed at 3500 rpm by the centrifuge, and decantation was performed. After wash
  • the centrifugal separator was centrifuged at 3500 rpm, and the upper part was filtered with the hole diameter 0.45 mm filter. 1 mL of 69% concentrated nitric acid was added to the obtained supernatant to 9 mL with ultrapure water, and then 1 mL of a standard element solution containing each element of In, Re, and Tl was added at a concentration of 100 mg L ⁇ 1 for inductively coupled plasma mass spectrometry analysis. What made it the measurement solution.
  • the sodium percarbonate aqueous solution 10g mentioned above was added to the chelate resin wash
  • the supernatant and the eluate were diluted, and after addition of 1 mL of the same internal standard element liquid used in Example 5, ICP-MS measurement was performed for each solution to calculate the recovery of each metal.
  • the results are shown in Table 7 below.

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Abstract

L'invention concerne un procédé de récupération de métaux rares d'un type nouveau permettant la récupération d'un composant métallique spécifique avec une bonne sélectivité parmi des métaux rares, et imposant peu de contraintes à l'environnement. Selon l'invention, le procédé de récupération sélectif de métaux rares comprend le procédé (1) et le procédé (2) suivants : (1) un procédé au cours duquel un composant métallique comprenant un métal rare est adsorbé ou entreposé dans une phase solide au moyen d'un procédé dans lequel une solution aqueuse qui contient le composant métallique comprenant le métal rare est amenée en contact avec une résine chélatante ou un agent d'adsorption, ou un procédé au cours duquel un précipité d'un composé métallique est formé dans une solution aqueuse qui contient le composant métallique comprenant le métal rare, et (2) un procédé au cours duquel la phase solide résultant de l'adsorption ou de l'entreposage du composant métallique comprenant le métal rare, obtenue dans le procédé (1), est amenée en contact avec une solution aqueuse contenant un composé peroxy.
PCT/KR2011/005418 2010-07-22 2011-07-22 Procédé de récupération sélective de métaux rares Ceased WO2012011770A2 (fr)

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