WO2013011901A1 - Procédé pour séparer/collecter un élément des terres rares et appareil pour séparer/collecter un élément des terres rares - Google Patents

Procédé pour séparer/collecter un élément des terres rares et appareil pour séparer/collecter un élément des terres rares Download PDF

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WO2013011901A1
WO2013011901A1 PCT/JP2012/067736 JP2012067736W WO2013011901A1 WO 2013011901 A1 WO2013011901 A1 WO 2013011901A1 JP 2012067736 W JP2012067736 W JP 2012067736W WO 2013011901 A1 WO2013011901 A1 WO 2013011901A1
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rare earth
water
earth element
soluble polymer
aqueous solution
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PCT/JP2012/067736
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English (en)
Japanese (ja)
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佐々木　洋
小林　金也
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株式会社日立製作所
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Priority to CN201280035250.8A priority Critical patent/CN103827328B/zh
Priority to JP2013524683A priority patent/JP5683705B2/ja
Publication of WO2013011901A1 publication Critical patent/WO2013011901A1/fr

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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
    • C22B59/00—Obtaining rare earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/16—Magnetic separation acting directly on the substance being separated with material carriers in the form of belts
    • B03C1/18—Magnetic separation acting directly on the substance being separated with material carriers in the form of belts with magnets moving during operation
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • 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
    • 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 method and apparatus for separating and recovering rare earth elements contained in a magnet alloy or the like.
  • Magnetic alloys used in motors of magnetic recording devices and hybrid vehicles etc. are added to iron as the main component, and small amounts of neodymium (Nd), dysprosium (Dy), etc. to increase the coercive force.
  • Rare earth elements are added. In recent years, separation, recovery, and reuse of these rare earth elements from discarded magnetic alloys have been studied from the viewpoint of effective utilization of resources.
  • phosphors containing rare earth elements used in cathode ray tubes, plasma display panels (PDPs), etc. are also enormous amounts on a global scale, so separation of rare earth elements from these phosphors Recovery is also required.
  • rare earth elements are difficult to separate as a single substance because various physical properties and chemical properties are similar to each other.
  • the electronegativity of rare earth elements is in the range of 0.86 to 1.14, in particular the electronegativity of Nd in the magnet alloy is 1.07 and that of Dy is very close to 1.10.
  • the ion radius of the rare earth element is also in the range of 0.0745 to 0.117 nm, and in particular, the ion radius of Nd in the magnet alloy is 0.099 nm, and that of Dy is close to 0.091 nm (both trivalent ions).
  • Non-Patent Document 1 scientific article
  • a phosphoric acid-based extractant and a hydrocarbon-based organic solvent are added and stirred, and left standing
  • different types of rare earth elements are distributed to water and an organic solvent depending on the type of extractant.
  • Patent Document 1 discloses a water-soluble polymer having an acidic group by adding a water-soluble polymer having an acidic group and a water-soluble polymer having an amino group to waste water in which a metal salt is dissolved. It is described that a water-soluble polymer having an amino group is crosslinked to trap metal ions in waste water and precipitate as an aggregate.
  • Non Patent Literature 1 uses a hydrocarbon-based organic solvent, recovery and processing of the solvent in consideration of the load on the environment and health are required, which causes an increase in cost.
  • the distribution ratio of different types of rare earth elements is small in the solvent extraction method, it is necessary to repeat the solvent extraction process several dozen times to increase the purity of the separated rare earth elements (for example, to 99% or more). is there.
  • the metal recovery method by aggregate precipitation of the above-mentioned Patent Document 1 is originally intended to efficiently recover (remove) metal ions from a large amount of industrial wastewater, and it is aggressive to separate for each metal species. Not for the purpose. That is, separation of different types of rare earth elements by element type is not sufficiently considered.
  • an object of the present invention is a separation and recovery method capable of increasing the distribution ratio of different types of rare earth elements to solve the above problems and achieving cost reduction in separation and recovery of rare earth elements, and a separation and recovery apparatus for realizing the same. To provide.
  • a rare earth element separation and recovery method comprising the steps of:
  • the present invention can add the following improvement or change in the rare earth element separation and recovery method (I) according to the present invention described above.
  • (I) When the total number of rare earth element ions having the smallest ion radius among the plurality of rare earth elements is “R”, and the total number of acid groups of the water-soluble polymer having the acid group is “C” The water-soluble polymer having the acid group is added to the aqueous solution so as to satisfy the inequality “R ⁇ C ⁇ 3R”.
  • the water-soluble polymer having an acidic group has an average molecular weight of 126 to 25,000, and the water-soluble polymer having an amino group has an average molecular weight of 60 to 25,000.
  • a water-soluble polymer having an amino group is added such that the total number of amino groups is larger than the total number of acidic groups of the polymer, and the method further comprises the additional aggregation step of additionally forming an aggregate.
  • the hydrogen ion exponent pH of the aqueous solution is 1 or more and 5 or less.
  • the water-soluble polymer having an amino group is added such that the pH of the aqueous solution is 6 or more and 9 or less.
  • a strong base is added such that the pH of the solution in which the aggregate is dissolved is 1 or more and 3 or less.
  • the water-soluble polymer having an amino group has a primary amino group and a tertiary amino group.
  • a cation exchange resin having an acid group is added in place of the water-soluble polymer having an acid group in the aggregation step.
  • the cation exchange resin contains magnetic powder.
  • an apparatus for separating and recovering a specific rare earth element from an aqueous solution having ions of a plurality of types of rare earth elements wherein a mixing tank and a mechanism for charging the aqueous solution into the mixing tank , A mechanism for adding a water-soluble polymer having an acidic group to the mixing tank, a mechanism for adding a water-soluble polymer having an amino group to the mixing tank, a mechanism for stirring the aqueous solution, and aggregation from the aqueous solution
  • the rare earth element separation and recovery device is provided with a mechanism for separating and recovering a substance, and a mechanism for dissolving the aggregates and adding an acid for producing a solution to the mixing tank.
  • the present invention can add the following improvements and changes in the rare earth element separation and recovery apparatus (II) according to the present invention described above.
  • the apparatus further comprises a mechanism for washing the aggregate separated and recovered from the aqueous solution.
  • the mechanism for adding the water-soluble polymer having an acidic group to the mixing tank and the mechanism for adding the water-soluble polymer having an amino group to the mixing tank each have a plurality of discharge nozzles. .
  • (Xii) further comprising a mechanism for suctioning the aqueous solution after the aggregates are separated and collected.
  • (Xiii) A mechanism for adding a cation exchange resin to the mixing vessel instead of the mechanism for adding the water-soluble polymer having the acidic group to the mixing vessel, or further comprising a cation exchange resin in the mixing vessel It is housed.
  • the cation exchange resin has a magnetic powder, and is further provided with a mechanism for separating and collecting the cation exchange resin from the mixing tank by a magnetic separation method.
  • a filter is provided at the bottom of the mixing tank to filter the aggregates.
  • the apparatus further includes a mechanism for disposing the upper surface of the filter at a position the same as or higher than the upper end of the inner wall of the mixing tank.
  • the filter comprises a mechanism for heating the aggregates.
  • the surface of the member in contact with the aggregates is treated to have a contact angle with water of 90 ° or more.
  • the present invention it is possible to provide a separation and recovery method in which distribution ratios of different types of rare earth elements are enhanced, and a separation and recovery apparatus for realizing the same.
  • an aqueous solution in which Nd and Dy are mixed is described as an example of an aqueous solution in which a plurality of types of rare earth elements are mixed. This is because these two types of rare earth elements are widely used as magnet alloys in many types of motors.
  • the ion radius of Nd is slightly larger than that of Dy.
  • lanthanum (La), cerium (Ce), europium (Eu), terbium (Tb) or the like used in phosphors can be separated and recovered according to the same principle.
  • FIG. 1 is a schematic view illustrating the aggregation process in the separation and recovery method according to the present invention.
  • a water-soluble polymer 4 having an acidic group is added to an aqueous solution in which Nd ions 1 and Dy ions 2 are mixed.
  • the Nd ion 1 and the Dy ion 2 form an ionic bond with the acidic group 3 of the water-soluble polymer 4.
  • a water-soluble polymer 6 having an amino group is added.
  • the Nd ion 1 having a larger ion radius than the Dy ion 2 preferentially coordinates with the amino group 5 of the water-soluble polymer 6 having an amino group to form a water-soluble aggregate 7 (hereinafter referred to as an aggregate)
  • 7 is referred to as solution 7).
  • the ionic bond between the acid group 3 of the water-soluble polymer 4 having an acid group and the amino group 5 of the water-soluble polymer 6 having an amino group results in intermolecular crosslinking to form an aggregate 8 insoluble in water. Do.
  • the aggregate 8 is formed, the Nd ion 1 and the Dy ion 2 not forming the water-soluble aggregate 7 are taken into the aggregate 8.
  • one amino group 5 is ionically bonded to one acidic group 3. Therefore, considering the amount of amino group 5 necessary to form aggregate 7, the amino acid of water-soluble polymer 6 having an amino group is more than the total number of acidic groups 3 of water-soluble polymer 4 having an acidic group. The total number of groups 5 needs to be large.
  • the water-soluble polymer 4 having an acid group is added after the water-soluble polymer 6 having an amino group is added, it is immediately associated with the water-soluble polymer 6 from the region to which the water-soluble polymer 4 is added. Because of aggregation, most of the Dy ions 2 dispersed throughout the aqueous solution are not taken into the aggregate and remain in the aqueous solution. Therefore, the water-soluble polymer 4 having an acid group is first added to capture the Dy ion 2, and then the water-soluble polymer 6 having an amino group is added. Thereby, the Dy ions 2 in the entire aqueous solution region in the reaction vessel can be taken into the aggregate 8.
  • the dissolved component separated from the aggregate 8 also contains Dy. Therefore, after the water-soluble polymer 4 having an acidic group is added to the aqueous solution from which the aggregate 8 is separated, the water-soluble polymer 6 having an amino group is further added to form an aggregate additionally. Thereby, Dy can be recovered from the solution. In other words, it is possible to efficiently recover Dy without discarding it as much as possible.
  • the rare earth element having the smaller ion radius is preferentially taken into the aggregate 8, and the dissolved portion has the ion radius.
  • the larger rare earth element will be predominantly present.
  • FIG. 2 is a schematic view illustrating a dissolution step and a reaggregation step in the separation and recovery method according to the present invention.
  • the aggregate 8 is dissolved even if a base is added instead of the acid.
  • a base stronger in basicity than the amino group 5 of the water-soluble polymer 6 is brought into contact with the aggregate 8, a state in which the amino group 5 of the water-soluble polymer 6 having an amino group is not dissociated from the dissociated ionic state Change to As a result, the ionic bond bridging the two polymers (water-soluble polymers 4 and 6) disappears, and the aggregate 8 dissolves.
  • the hydrogen ion index pH is 8 or more
  • the Nd ion 1 and the Dy ion 2 change to hydroxides that are poorly soluble in water.
  • the aggregate 8 dissolves, hydroxides of Nd and Dy precipitate, causing problems in the next step. From this, it is preferable to carry out the dissolution process of dissolving the aggregate 8 by adding an acid.
  • (1-6) Reaggregation step After adding the base to the solution in which the aggregate 8 is dissolved in the dissolution step and adjusting the pH to about 2, the water-soluble polymer 6 having an amino group has a pH of about 5 to 5 When it is added until it reaches 6, reaggregates 8 'precipitate.
  • a water-soluble polymer 6 having an amino group may be added as a base for pH adjustment.
  • the liquid of Aggregate 8 is strongly acidic, it is necessary to add water-soluble polymer 6 having a vast amount of amino groups before adjusting pH to about 2, so adjust pH As a base, it is more preferable to use a strong base (base dissociation constant pKb ⁇ 0, for example, sodium hydroxide etc.).
  • the trivalent Nd ion 1 Since the trivalent Nd ion 1 has 3 electrons in the 4f orbit, 11 electrons are required to fill the orbit with electrons. On the other hand, since the number of electrons on the 4f orbital is nine, the trivalent Dy ion 2 requires five electrons to fill the orbital with electrons. Since the Nd ion 1 requires more electrons than the Dy ion 2 to satisfy the 4f orbital, it is presumed that the attractive force with the amino group 5 functioning as an electron donating group is larger. In other words, since the amino group 5 is more easily coordinated by the Nd ion 1, the Nd ion 1 is preferentially distributed in the solution 7, and the Nd ion 1 in a dissociated state in the solution decreases. As a result, the Dy ions 2 in the aggregate 8 and the recoagulate 8 'become relatively large.
  • Yb 3+ is most easily taken into aggregate 8.
  • the order of Tm 3+ , Er 3+ ,... Is as follows, and the more electrons on the 4f orbital, the easier it is to be taken into aggregate 8.
  • Ce 3+ is the largest to be distributed to the dissolved component 7, and in the order of Pr 3+ , Nd 3+,.
  • the present invention aims to increase the distribution ratio of different types of rare earth elements.
  • “raising the distribution ratio of rare earth elements” in the present invention will be briefly described.
  • the purpose is usually to separate and recover as much of the rare earth element as possible from the raw material containing the rare earth element (for example, the discarded rare earth magnet alloy).
  • "to increase the distribution ratio of the rare earth elements” in the present invention means to increase the purity of the rare earth elements to be separated and collected (to separate and collect the rare earth elements having high purity).
  • the present invention differs from the prior art in basic concept.
  • Polymeric material used (3-1) Water-soluble polymer having an acidic group
  • polyacrylic acid is preferable from the viewpoint of being inexpensive and being easy to form an ionic bond with an amino group.
  • polyaspartic acid and polyglutamic acid derived from amino acids are also suitable.
  • Alginic acid is a type of main component of seaweed such as kelp, and has a feature that environmental load is small in that raw materials are derived from organisms.
  • water-soluble polymer having a sulfonic acid group examples include polyvinyl sulfonic acid and polystyrene sulfonic acid. These sulfonic acid groups are preferable in that they have a higher acidity than carboxyl groups, so the proportion of forming ionic bonds with amino groups is high, and stable aggregates can be obtained.
  • the water solubility of the polymer having an acid group is not sufficient, the water solubility (solubility in water) is improved by forming a part of the acid group with an ammonium salt structure, a sodium salt structure, and / or a potassium salt structure. It is possible to By adding a polymer in which some of the acidic groups have an ammonium salt structure, a sodium salt structure, and / or a potassium salt structure, it is possible to efficiently form an ionic bond with a water-soluble polymer having an amino group become.
  • the average molecular weight of the water-soluble polymer 4 having an acidic group 3 is preferably 25,000 or less.
  • the average molecular weight of the water-soluble polymer 4 having the acidic group 3 is more preferably 7,000 or less, and still more preferably 5,000 or less.
  • the shortening of the process time of the dissolution step is particularly advantageous when the aggregation step and the dissolution step are repeated a plurality of times.
  • a water-soluble polymer 6 having an amino group 5 (average molecular weight 25,000) is added to an aqueous solution in which a water-soluble polymer 4 having an acidic group 3 is dissolved to form an aggregate, thereby forming hydrochloric acid (1 N)
  • the aggregate having an average molecular weight of 25,000 of the water-soluble polymer 4 used took about 1 minute to completely dissolve.
  • the aggregate having an average molecular weight of 7,000 of the water-soluble polymer 4 used was completely dissolved in about 40 seconds.
  • the aggregate having an average molecular weight of 5,000 of the water-soluble polymer 4 used was completely dissolved in about 3 seconds.
  • At least two or more acidic groups are required to form the aggregate 8 and the reaggregate 8 '.
  • the organic compounds having two or more acidic groups the one having the lowest molecular weight is oxalic acid, and the molecular weight is 126.
  • Oxalic acid can also be considered as a polymer material having a repeating basic unit of “—COOH”. Therefore, the lower limit of the molecular weight of the water-soluble polymer 4 is 126.
  • the aggregation step As the average molecular weight of the water-soluble polymer 4 used is larger, intermolecular cross-linking with the water-soluble polymer 6 having the amino group 5 is more easily formed, and the poor solubility of the formed aggregate is increased. . That is, since the utilization rate of the added water-soluble polymer 4 is increased, the trapping efficiency of the rare earth element ion to be separated and collected is increased.
  • the ratio of forming the insoluble aggregate among the added water-soluble polymer 4 was about 90% when the average molecular weight of the water-soluble polymer 4 used was less than 1,000, and about 95% when the average molecular weight of the water-soluble polymer 4 used was 1,000 or more and less than 2,000.
  • the average molecular weight of the water-soluble polymer 4 was 2,000 or more, it was about 98%. From these results, the average molecular weight of the water-soluble polymer 4 is required to be at least 126, preferably 1,000 or more, and more preferably 2,000 or more.
  • FIG. 3 is a schematic view illustrating an aggregation step using a cation exchange resin in the separation and recovery method according to the present invention.
  • the cation exchange resin 9 to be used preferably has, for example, a sulfonic acid group or a carboxyl group as the acidic group 3. .
  • Nd ion 1 and Dy ion 2 are the acid groups 3 and ions of cation exchange resin 9 Join. Thereafter, when the water-soluble polymer 6 having the amino group 5 is further added, the Nd ion 1 preferentially forms an aggregate 7 with the water-soluble polymer 6 and dissolves. At the same time, the acidic groups 3 of the cation exchange resin 9 and the amino groups 5 of the water-soluble polymer 6 are ionically bonded while preferentially trapping the Dy ions 2.
  • the relationship between the number of acidic groups 3 of the cation exchange resin 9 and the number of amino groups 5 of the water-soluble polymer 6 is the same as in the above-mentioned “(1-1) aggregation step”.
  • the average particle diameter of the cation exchange resin 9 is preferably about 0.1 mm to 3 mm. In order to improve the trapping rate of the rare earth element ions, it is preferable to increase the surface area by providing asperities on the surface of the cation exchange resin 9 or the like.
  • the cation exchange resin 9 used to trap rare earth element ions (bound to the surface) is separated from non-aggregates (dissolved 7) by filtration etc. It is preferable to be easy to do.
  • the cation exchange resin 9 can also be regarded as an aggregate 8.
  • the specific gravity as the cation exchange resin 9 also becomes large, so that it becomes easy to precipitate.
  • magnetic powder in the inside of the cation exchange resin 9 it can be collected magnetically and it becomes possible to utilize magnetic separation in the separation and recovery step.
  • water-soluble polymer having an amino group As the water-soluble polymer 6 having an amino group 5, polyethyleneimine is preferable in that the ratio of the amino group per unit mass is maximized.
  • linear amino groups such as polyvinylamine and polyallylamine are also preferable because they are relatively inexpensive and easily dissolved in water.
  • chitosan has a slightly lower solubility in water, it is obtained by hydrolyzing chitin, which is the main component of the exoskeleton of organisms (eg, crab, shrimp, beetles, cockroaches, etc.), so the raw material is said to be of biological origin. It has the feature that environmental load is small in point.
  • amino acid-derived polylysine and polyarginine are also suitable.
  • the water-soluble polymer 6 having an amino group 5 it is more efficient for the water-soluble polymer 6 having an amino group 5 to have as many amino groups as possible per unit mass.
  • a structure having a small repeating basic unit or a structure having as many amino groups as possible in the repeating basic unit is preferable.
  • polyethylenimine is efficient among water-soluble polymers 6 having an amino group 5 because the repeating basic unit is “—C 2 H 4 N” and the molecular weight is as small as about 43.
  • some structures of polyallylamine may be mentioned. For example, it is the following compound.
  • Compound A has a molecular weight of the repeating basic unit of about 72.
  • compound B a molecule having a molecular weight of about 72 and a molecule of about 100 are combined to form a repeating basic unit. Since the water-soluble polymer 6 having an amino group 5 other than these has a pyrrole skeleton, a sulfonyl moiety or the like, the molecular weight of the repeating basic unit is around 150 to 300.
  • compounds A and B are preferable among polyethyleneimine and polyallylamine.
  • the amino group 5 of the water-soluble polymer 6 is composed of a primary amino group and a tertiary amino group, it tends to form an aggregate 7 with the Nd ion 1 more easily than the Dy ion 2.
  • Polyethyleneimine has all three types of primary amino group, secondary amino group, and tertiary amino group.
  • the compound B also has two types of primary amino group and tertiary amino group.
  • the viscosity of the water-soluble polymer 6 having an amino group 5 increases as the average molecular weight increases, and thus handling becomes difficult from the viewpoint of input amount control and input operation. Specifically, when the average molecular weight of the water-soluble polymer 6 having an amino group 5 such as polyethylenimine or polyallylamine exceeds 100,000, the viscosity is 1,000 mPa ⁇ s at 20 ° C. even in an aqueous solution of 10 mass%. It becomes more than s.
  • the viscosity is 1,000 mPa ⁇ s or more
  • a device with a small discharge amount per unit time for example, a dispenser, etc.
  • Operation becomes difficult.
  • it is desirable that the viscosity of the water-soluble polymer 6 is low, so that the average molecular weight of the water-soluble polymer 6 having the amino group 5 is preferably at least 100,000 or less.
  • the average molecular weight of the water-soluble polymer 6 having the amino group 5 is excessive, the element species to be distributed to the dissolved component 7 is physically separated by a long molecular chain There is a tendency to be entangled (without association with the linking group) together into aggregate 8 and reaggregate 8 '. This tendency becomes remarkable when the average molecular weight of the water-soluble polymer 6 exceeds 25,000. Therefore, the average molecular weight of the water-soluble polymer 6 having an amino group 5 is more preferably 25,000 or less.
  • the average molecular weight of the water-soluble polymer 6 having an amino group 5 is more preferably 7,000 or less, and most preferably 5,000 or less.
  • a water-soluble polymer 6 having an amino group 5 is added to form an aggregate, and hydrochloric acid (1 N)
  • hydrochloric acid (1 N) When this aggregate was dissolved to use, the aggregate of water-soluble polymer 6 having an average molecular weight of 25,000 required about 1 minute to completely dissolve.
  • the aggregate having an average molecular weight of 7,000 of the water-soluble polymer 6 used was completely dissolved in about 40 seconds.
  • the aggregate having an average molecular weight of 5,000 of the water-soluble polymer 6 used was completely dissolved in about 3 seconds.
  • the shortening of the process time of the dissolution step is particularly advantageous when the aggregation step and the dissolution step are repeated a plurality of times.
  • the organic compound having two or more amino groups and having the lowest molecular weight is ethylenediamine, and the molecular weight is 60.
  • Ethylenediamine can also be considered as a polymer material having a repeating basic unit of “—CH 2 NH 2 ”. Therefore, the lower limit of the molecular weight of the water-soluble polymer 6 is 60.
  • the intermolecularity with the water-soluble polymer 4 having an acidic group 3 is Crosslinks are likely to be formed and the poor solubility of the resulting aggregates is increased. That is, since the utilization rate of the added water-soluble polymer 6 is increased, the trapping efficiency of the rare earth element ions to be separated and recovered is increased.
  • a ratio of forming an insoluble aggregate among the added water-soluble polymer 6 was about 90% when the average molecular weight of the water-soluble polymer 6 used was less than 1,000, and about 95% when the average molecular weight of the water-soluble polymer 6 used was 1,000 or more and less than 2,000.
  • the average molecular weight of the water-soluble polymer 6 was 2,000 or more, it was about 98%. From these results, the average molecular weight of the water-soluble polymer 6 needs to be at least 60, preferably 1,000 or more, and more preferably 2,000 or more.
  • the rare earth element ion having the smallest ion radius among the plural kinds of rare earth element ions present in the aqueous solution is the aggregate 8 and the reaggregates 8 'It is taken in preferentially.
  • the addition ratio of the water-soluble polymer is an important process factor.
  • the addition amount of the water-soluble polymer 4 having the acidic group 3 is the total number (R) of the rare earth element ion having the smallest ion radius (ie, the rare earth element ion to be separated and recovered). Or more) (R C C).
  • R the total number of the rare earth element ion having the smallest ion radius
  • R C C the recovery rate of rare earth element ions to be separated and recovered decreases.
  • the total number R of rare earth element ions can be estimated, for example, by an inductively coupled plasma method.
  • the rare earth ion is trivalent and the acid group 3 is monovalent, a maximum of three ionic bonds are formed per one rare earth ion.
  • the total number C of the acidic groups 3 should be at least 3 times the total number R of the rare earth element ions to be separated and collected. If 3R ⁇ C), the rare earth element ion in the aqueous solution is in principle 100% trapped in the aggregate.
  • the total number C of the acidic groups 3 is more than three times the total number R of the rare earth element ions to be separated and recovered ( If 3R ⁇ C) or more than 3R, it will also trap rare earth element ions other than the rare earth elements to be separated and collected. That is, the separation ability of the rare earth element species (distribution ratio of the rare earth element) is lowered. From this, it is desirable that the total number C of the acidic groups 3 is three times or less (C ⁇ 3R) of the total number R of rare earth element ions (the rare earth element ions having the smallest ion radius) to be separated and collected.
  • the addition amount of the water-soluble polymer 4 having the acidic group 3 desirably satisfies the inequality “R ⁇ C ⁇ 3R”.
  • the total number C of the acidic groups 3 is more preferably 2.5 times or less (C ⁇ 2.5 R) the total number R of rare earth element ions to be separated and recovered from the viewpoint of minimizing the mixing of other types of rare earth elements. It is more desirable that the ratio be 2 times or less (C.ltoreq.2R).
  • the cation exchange resin 9 is acidic because the cation exchange resin 9 itself is solid. It is harder to move than the water-soluble polymer 4 having the group 3 (no fluidity like the water-soluble polymer 4). Therefore, in order to increase the probability of association with the rare earth element ion to be captured, it is necessary to increase the addition amount of the cation exchange resin 9 compared to the water-soluble polymer 4 having the acidic group 3. Specifically, in the case of using the cation exchange resin 9 having an acidic group 3, the total number of acidic groups 3 is about 3 to 10 times the total number of acidic groups 3 of the water-soluble polymer 4. Is preferred.
  • the distribution ratio of the rare earth element can be increased.
  • Acid and Base Used (-1) Acid
  • a common acid can be used as the acid used for dissolving the aggregate 8.
  • the linear water-soluble polymer 6 having the amino group 5 constituting the aggregate 8 forms a salt structure with the amino group 5 and the added acid by addition of an acid, thereby forming the aggregate 8
  • the aggregate 8 dissolves because the ionic bond is eliminated.
  • an acid (weak acid) having a low acidity is used, a large amount of addition is required to dissolve the aggregate 8, so the acid used is a strong acid (pKa ⁇ 1), particularly strong inorganic acid (eg hydrochloric acid, sulfuric acid) , Nitric acid) is preferred.
  • acids water-soluble polymer 4 having these acid groups
  • Acid having the same acid group 3 is not preferred.
  • a common base can be used as a base used to form reaggregate 8 ′ from the solution in which aggregate 8 is dissolved.
  • a strong base pKb ⁇ 0
  • strong inorganic bases for example, sodium hydroxide, potassium hydroxide and the like
  • water-soluble polymer 6 having an amino group 5 is further added to form a reaggregate 8 '.
  • FIG. 4 is a schematic view illustrating the flow of steps of the separation and recovery method according to the present invention.
  • the formation of the aggregate 8 inhibits the flow of the water-soluble polymer 6 having an amino group, and if the aggregate that should be originally formed in the mixing tank 12 remains unformed, the recovery rate of separation of Dy may be reduced. There is sex. Therefore, in order to cause aggregation to occur in the entire mixed aqueous solution 10 in the mixing tank 12, the mechanism for adding the water-soluble polymer 6 having an amino group comprises a plurality of nozzles for releasing the water-soluble polymer 6, It is preferable to make the agglutination reaction occur in the entire region of the mixing tank 12.
  • the shutter 7 of the filter with shutter 11 disposed at the bottom of the mixing tank 12 is opened to discharge the dissolved portion 7 out of the mixing tank 12, and the state as shown in FIG. 4C is obtained.
  • Nd ions are mainly removed from the rare earth element ions trapped in the aggregates 8 and the reaggregates 8 ′, and as a result, the Dy ions are removed.
  • the percentage of Moreover, the separation and recovery rate of Dy can be further improved by collecting the dissolved portion 7 and repeating the additional aggregation step, the dissolution step and the re-aggregation step.
  • FIG. 5 is a schematic view showing one configuration of the rare earth element separation and recovery apparatus according to the present invention.
  • the pH of the mixed aqueous solution (an aqueous solution in which Nd ions and Dy ions are mixed) to be introduced into the separation and recovery apparatus shown in FIG. 5 is preferably 1 or more and 5 or less.
  • the pH of the mixed aqueous solution is 3.0. If the pH of the mixed aqueous solution to be added is less than 1, the acidity is too high, and even if a water-soluble polymer having an amino group is added in a later step, it becomes difficult to form aggregates, so the recovery rate of separation of Dy ions decreases. Do.
  • a mixed aqueous solution (an aqueous solution containing Nd ions and Dy ions) is introduced into the mixing tank 17 through the mixed aqueous solution pipe 19 by the mixed aqueous solution supply pump 18. Thereafter, the mixed aqueous solution in the mixing tank 17 is stirred by the overhead stirrer 21 equipped with the stirring blade 20. Stirring of the mixed aqueous solution is continued until aggregates 28 are formed in a later step.
  • an aqueous solution of a water-soluble polymer having an acidic group is introduced into the mixing tank 17 from the first tank 22 through the first pipe 24 by the first pump 23.
  • an aqueous solution of a water-soluble polymer having an amino group is introduced into the mixing tank 17 from the second tank 25 through the second pipe 27 by the second pump 26. Then, the water-soluble polymer having an amino group and the water-soluble polymer having an acidic group are associated in the mixing tank 17 to form an aggregate 28. After the formation of aggregates 28, the stirring is stopped. The amount of the water-soluble polymer having an amino group is adjusted so that the pH of the aqueous solution in the mixing tank 17 is 6 or more and 9 or less.
  • the liquid (dissolution) other than the aggregate 8 is discharged from the mixing tank 17 through the filter 30. Since the aggregate 8 is blocked by the filter 30, it is not discharged from the mixing tank 17. After the liquid component of the mixing tank 17 is discharged, the shutter 29 is closed. The discharged solution passes through a valve 31 and enters a recovery tank 32 disposed below the mixing tank 17.
  • deionized water is dropped by the third pump 34 from the third tank 33 through the third pipe 35 onto the aggregates 28 remaining in the mixing tank 17.
  • This operation is intended to remove the Nd component adhering to the surface of the aggregate 28.
  • the shutter 29 is opened to discharge the deionized water, and then the shutter 29 is closed.
  • an acid for example, a hydrochloric acid aqueous solution
  • a hydrochloric acid aqueous solution is introduced into the mixing tank 17 from the fourth tank 36 through the fourth pipe 38 by the fourth pump 37 to dissolve the aggregates 28.
  • an aqueous solution of hydrochloric acid is added until the aggregate 28 is completely dissolved.
  • the fifth pump 40 feeds the base (for example, aqueous sodium hydroxide solution) into the mixing tank 17 from the fifth tank 39 through the fifth pipe 41.
  • the addition of the sodium hydroxide aqueous solution is continued until the pH of the aqueous solution in the mixing tank 17 becomes 1 to 3.
  • an aqueous solution of a water-soluble polymer having an amino group is introduced into the mixing tank 17 from the second tank 25 through the second pipe 27 by the second pump 26.
  • the input amount of the water-soluble polymer having an amino group is adjusted such that the pH of the aqueous solution in the mixing tank 17 is 6 or more and 9 or less. This step produces reaggregates.
  • the shutter 29 is opened to discharge the liquid (dissolved matter) other than the reagglomerated material from the mixing tank 17. Thereafter, washing the reaggregation with deionized water, adding an aqueous solution of hydrochloric acid to dissolve the reaggregation, adding sodium hydroxide aqueous solution and a water-soluble polymer having an amino group to form a reaggregation Repeat several times.
  • the proportion of Nd ions in the reagglomerate decreases, and as a result, the proportion of Dy ions increases (ie, the purity of the Dy component increases).
  • the reagglomerate After raising the percentage of Dy ions in the reagglomerate to the desired value, the reagglomerate is dried and collected.
  • the filter 30 preferably includes a heating mechanism (not shown).
  • FIG. 6 is a schematic view showing an operation of recovering reaggregated material in the separation and recovery apparatus shown in FIG.
  • the bottom 17 'of the mixing tank is configured to be slidable in the vertical direction in the figure with respect to the inner wall 42 of the mixing tank.
  • the bottom 17 'of the mixing vessel is raised together with the shutter 29 and the filter 30, so that the top of the shutter 29 or filter 30 is at the same or slightly higher than the upper end of the inner wall 42 of the mixing vessel.
  • the reaggregates 28 'on the shutter 29 and / or the filter 30 are collected by a scraper or the like. By doing so, the reaggregated matter 28 'can be recovered easily and without waste.
  • the bottom 17 'of the mixing tank is lowered to return to the original state.
  • the positional relationship between the bottom 17 'of the mixing tank and the inner wall 42 of the mixing tank is relative, and the operation of FIG. 6 is performed by lowering the inner wall 42 of the mixing tank. It is also good.
  • the reaggregated material recovered above is heated in the air.
  • the organic compound component (water-soluble polymer having an acidic group, water-soluble polymer having an amino group) in the reagglomerate is decomposed and removed, and the Dy ion combines with oxygen to form Dy 2 O 3. can get.
  • the aqueous solution (the dissolved component) collected in the collection tank 32 also contains the Dy component
  • the dissolved component collected in the collection tank 32 is put into the mixing tank 17, and the additional aggregation step, the dissolution step, and the reaggregation described above are performed.
  • Dy can be recovered from the solution by repeating the steps. This can further improve the separation and recovery rate of Dy as a whole.
  • Nd 2 O 3 can be recovered by heating the aqueous solution (dissolved matter) to remove water and organic compound components.
  • the suspension in the mixing tank may be transferred to a centrifuge tube and centrifuged to separate the aggregate and the dissolved component.
  • the tip of the pipe to which the water-soluble polymer having an amino group is added has a plurality of discharge nozzles so that the water-soluble polymer to be charged can be easily dispersed in the aqueous solution.
  • the stirring blade 20 of the overhead stirrer 21, the mixing tank 17, the fourth tank 36 containing an aqueous solution of acid, and the fourth pipe 38 may be corroded because they touch strong acids such as hydrochloric acid. . Therefore, it is preferable to form an acid resistant resin film for preventing direct contact of the acid with these members.
  • a paint obtained by dissolving a thermoplastic resin such as a polycarbonate resin or an acrylic resin in an organic solvent such as acetone or 2-butanone is applied to a desired portion of the above-described member, and the organic solvent is evaporated to evaporate the organic solvent. It is possible to form a resin film.
  • a coating obtained by dissolving an epoxy resin or a phenol resin and a curing agent (for example, diamine) in an organic solvent is applied to a desired portion of the above member and then heated to thermally cure resin molecules. It is possible to form an acid resistant resin film.
  • a resin composed of a combination of an epoxy resin or a phenol resin and a curing agent is particularly suitable when the member is made of metal (for example, SUS, aluminum, etc.) because the adhesion to metal is high.
  • the above-mentioned member may be made of a highly acid resistant resin.
  • the contact angle with water be 90 ° or more. This is because the formed aggregate 28 / reaggregate 28 'contains a large amount of water, so that the aggregate 28 / reaggregate 28' is also less likely to adhere to the surface that is likely to repel water.
  • the treatment for lowering the surface energy is not particularly limited as long as the contact angle with water on the surface of the resin film is 90 ° or more, but as one example, the compatibility with the above-mentioned acid resistant resin is high and A resin film is formed by mixing and applying a highly water-repellent material (for example, a silicone compound having a siloxane skeleton in the molecular structure, a fluorine compound having a large number of fluorine atoms in the molecular structure, etc.) to the above-mentioned paint There is a way.
  • a highly water-repellent material for example, a silicone compound having a siloxane skeleton in the molecular structure, a fluorine compound having a large number of fluorine atoms in the molecular structure, etc.
  • the present inventors add various organic compounds to the above-mentioned acid resistant resin film (polycarbonate resin, acrylic resin, epoxy resin cured with curing agent, phenol resin cured with curing agent), and the water repellency effect thereby (Surface energy reduction effect) was investigated.
  • acid-resistant resin films formed by adding 2 to 5% by mass of the following organic compounds C to M with respect to the resin in the paint have high contact angles with water as high as 100 ° or more, and aggregates There was an effect that the adhesion of was hardly found visually. This was a significant difference compared to the case of a resin film whose contact angle with water was less than 90 °.
  • the added organic compounds C to M are as follows.
  • the fluorine-containing chain in the molecular structure of the above compound is called a perfluoropolyether chain, and good results were obtained when the average molecular weight of the perfluoropolyether chain was 1,500 or more and 3,000 or less in any of the compounds.
  • the average molecular weight of the perfluoropolyether chain was less than 1,500, the water repellency was not sufficient.
  • the average molecular weight is more than 3000, the compatibility with the acid resistant resin is low, and it is easily separated in the paint, so that it is difficult to form a homogeneous resin film.
  • FIG. 7 is a schematic view showing another configuration of the rare earth element separation and recovery apparatus according to the present invention. As shown in FIG. 7, in the present embodiment, no shuttered filter is disposed in the lower region of the mixing tank.
  • a mixed aqueous solution (an aqueous solution containing Nd ions and Dy ions) prepared separately is passed through the mixed aqueous solution pipe 19 by the mixed aqueous solution supply pump 18 and a filter with a shutter in the lower region Into a mixing tank 43 not equipped with
  • the aqueous solution of the water-soluble polymer having an acidic group is passed from the first tank 22 through the first pipe 24 by the first pump 23. Charge into mixing vessel 43. Thereafter, an aqueous solution of a water-soluble polymer having an amino group is introduced into the mixing tank 43 from the second tank 25 through the second pipe 27 by the second pump 26 to form the aggregates 28.
  • the dissolved component in the mixing tank 43 is transferred from the mixing tank 43 to the collecting tank 32 by the dissolved liquid recovery pump 44 through the dissolving pipe 45.
  • the filter 46 is provided at the water intake port of the dissolution pipe 45, it is possible to suppress the mixture of the aggregates 28 in the recovery tank 32.
  • the separation and recovery apparatus of the present embodiment is characterized in that since the dissolved component is sucked by a pump, the aggregate and the dissolved component can be separated in a shorter time as compared with the above-described separation and recovery apparatus of the first embodiment.
  • FIG. 8 is a schematic view showing still another configuration of the rare earth element separation and recovery apparatus according to the present invention.
  • the shuttered filter is not disposed in the lower region of the mixing tank, and the mixing tank has a mechanism for causing the solution to flow out from the side wall.
  • a mixed aqueous solution (an aqueous solution containing Nd ions and Dy ions) prepared separately is introduced into the mixing tank 49 through the mixed aqueous solution pipe 19 by the mixed aqueous solution supply pump 18.
  • the mixing tank 49 is not provided with a shuttered filter in the lower region, and is provided with a discharge port 48 having a valve 47 for controlling the flow rate of the solution on the side wall.
  • the aqueous solution in the mixing tank 49 is well stirred by the overhead stirrer 21
  • the aqueous solution of the water-soluble polymer having an acidic group is passed from the first tank 22 through the first pipe 24 by the first pump 23.
  • an aqueous solution of a water-soluble polymer having an amino group is introduced into the mixing tank 49 from the second tank 25 through the second pipe 27 by the second pump 26 to form the aggregates 28.
  • the valve 47 of the discharge port 48 is opened to discharge the dissolved component from the mixing tank 49 to the recovery tank 32.
  • a filter not shown
  • the discharge port 48 preferably includes a mechanism (not shown) capable of moving in the vertical direction of the mixing tank 49. Thereby, it is possible to more efficiently separate the aggregate and the solution.
  • FIG. 9 is a schematic view showing still another configuration of the rare earth element separation and recovery apparatus according to the present invention.
  • this embodiment basically has the same apparatus configuration as that of the above-mentioned embodiment 1, but instead of using a water-soluble polymer having an acidic group, a cation exchange resin is used to form a rare earth element. They differ in that they are separated and recovered.
  • a separately prepared mixed aqueous solution (an aqueous solution containing Nd ions and Dy ions) is introduced into the mixing tank 17 through the mixed aqueous solution pipe 19 by the mixed aqueous solution supply pump 18. Thereafter, the aqueous solution in the mixing tank 17 is stirred by the overhead stirrer 21.
  • an aqueous solution of a water-soluble polymer having an amino group is introduced into the mixing tank 17 from the second tank 25 through the second pipe 27 by the second pump 26. Then, the water-soluble polymer having an amino group and the acid group of the cation exchange resin 50 are ionically bonded in the mixing tank 17 to form an aggregate on the surface of the cation exchange resin 50. Stirring is stopped after the formation of aggregates.
  • the shutter 29 is opened to discharge the solution from the mixing tank 17.
  • the cation exchange resin 50 in which the aggregates are formed on the surface is blocked by the filter 30, so it is not discharged from the mixing tank 17.
  • the shutter 29 is closed.
  • the discharged solution passes through a valve 31 and enters a recovery tank 32 disposed below the mixing tank 17.
  • deionized water is allowed to fall on the cation exchange resin 50 remaining in the mixing tank 17 from the third tank 33 through the third pipe 35 by the third pump 34, and the surface of the cation exchange resin 50 Wash.
  • the fourth pump 37 feeds the hydrochloric acid aqueous solution from the fourth tank 36 through the fourth pipe 38 into the mixing tank 17 to collect the aggregates on the surface of the cation exchange resin 50. Let it dissolve.
  • the aqueous solution of sodium hydroxide is introduced into the mixing tank 17 through the fifth tank 39 through the fifth pipe 41 by the fifth pump 40 to adjust the pH of the solution, and the second pump 26 subsequently
  • an aqueous solution of a water-soluble polymer having an amino group is introduced into the mixing tank 17 from the tank 25 of the No. 2 through the second pipe 27, reaggregates are formed on the surface of the cation exchange resin 50.
  • the Nd ions are mainly removed from the aggregates and the Dy ions are removed. The proportion will increase.
  • the reagglomerate After raising the percentage of Dy ions in the reagglomerate to the desired value, the reagglomerate is dissolved in aqueous hydrochloric acid.
  • the shutter 29 is opened to discharge the dissolved liquid (other than the cation exchange resin 50) from the mixing tank 17.
  • the discharged liquid portion is recovered through the valve 31 to the second recovery tank 51 disposed below the mixing tank 17.
  • the surface of the cation exchange resin 50 is washed with deionized water, and the washing solution is also transferred to the second recovery tank 51.
  • the sodium hydroxide aqueous solution is introduced into the second recovery tank 51 through the fifth tank 39 through the fifth pipe 41, the mixing tank 17, and the valve 31 by the fifth pump 40, and the second recovery is performed.
  • the pH of the aqueous solution in the tank 51 is adjusted to around 2 (for example, 1 to 3).
  • an aqueous solution of a water-soluble polymer having an amino group is added from the sixth tank 52 through the sixth pipe 54 by the sixth pump 53, reaggregates 55 are formed.
  • the shutter 56 when the shutter 56 is opened, the liquid (dissolved matter) other than the reaggregate 55 is discharged from the second recovery tank 51 through the filter 57. After the liquid component in the second recovery tank 51 is discharged, the shutter 56 is closed, and the reagglomerated material 55 is heated and dried.
  • the dried reaggregates 55 on the filter 57 are collected by a scraper or the like.
  • the bottom of the second recovery tank 51 is raised with respect to the inner wall of the second recovery tank 51 together with the shutter 56 and the filter 57 for recovery, or the second recovery tank 51 is It is preferable to lower the inner wall relative to the bottom of the second recovery tank 51 for recovery.
  • the recovered reaggregation 55 is heated in the air to decompose and remove the organic compound component (water-soluble polymer having an acidic group, water-soluble polymer having an amino group) in the reaggregation 55 , Dy 2 O 3 are obtained.
  • the aggregates in the mixing tank 17 are formed by adhering to the cation exchange resin 50 by using the cation exchange resin 50.
  • the size of the aggregates can be increased more than that. Therefore, when the aggregate and the solution are separated by filtration, the filter 30 is less likely to be clogged, and the filter 30 can be more easily separated (for example, in a short time).
  • an alkali metal hydroxide for example, sodium hydroxide, potassium hydroxide, etc.
  • Dy ion poorly soluble in water. It produces dysprosium.
  • the rare earth element can also be recycled by filtering this compound out and reducing it.
  • FIG. 10 is a schematic view showing still another configuration of the rare earth element separation and recovery apparatus according to the present invention.
  • this embodiment basically has the same apparatus configuration as the above-mentioned embodiment 4, but in that the separation and recovery of the rare earth elements are performed using the magnetic separation method instead of the filtration by the filter. It is different.
  • the cation exchange resin 58 placed in the mixing tank 17 contains magnetic powder inside.
  • illustration of the part which overlaps with FIG. 9 is partially omitted from a viewpoint of simplification of drawing.
  • a separately prepared mixed aqueous solution (an aqueous solution containing Nd ions and Dy ions) is introduced into the mixing tank 17, and then an aqueous solution of a water-soluble polymer having an amino group is mixed.
  • an aqueous solution of a water-soluble polymer having an amino group is mixed.
  • aggregates are formed on the surface of the magnetic powder-containing cation exchange resin 58.
  • the shutter 29 is opened to discharge the dissolved component from the mixing tank 17 and the surface of the magnetic powder-containing cation exchange resin 58 is washed with deionized water, and then a hydrochloric acid aqueous solution is introduced into the mixing tank 17 to contain magnetic powder. The aggregates on the surface of the cation exchange resin 58 are dissolved.
  • a sodium hydroxide aqueous solution is introduced into the mixing tank 17 to adjust the pH of the solution, and subsequently, a water-soluble polymer having an amino group from the second tank 25 through the second pipe 27 by the second pump 26 The aqueous solution is placed in the mixing tank 17 to form reaggregates on the surface of the magnetic powder-containing cation exchange resin 58.
  • the magnetic powder-containing cation exchange resin 58 having reaggregates formed on the surface is separated from the mixing tank 17 by the mechanism of separating and recovering by the magnetic separation method. Separate and collect.
  • a mechanism (magnetic powder-containing aggregate conveyance mechanism) for separating and collecting by the magnetic separation method includes a first roller 59, a second roller 60, a third roller 61, a fourth roller 62, and a conveyance belt 63. ing.
  • the surface of the conveyance belt 63 between the fourth roller 62 and the first roller 59 to the second roller 60 has a magnetic force, whereby the magnetic powder-containing cation exchange resin in the mixing tank 17 is obtained. 58 can be adhered to the surface of the conveyor belt 63 along with the reaggregates.
  • the surface of the conveyance belt 63 between the second roller 60, the third roller 61, and the fourth roller 62 has a structure having no magnetic force, and the reaggregates are formed from the surface of the conveyance belt 63. It falls off and falls into the aggregate collection tank 64.
  • a shutter 65 and a filter 66 are provided at the lower part of the aggregate recovery tank 64.
  • the separation and recovery apparatus of the present embodiment can recover the magnetic powder-containing cation exchange resin 58 to which the reaggregated matter in which the Dy ions are trapped adheres from the mixing tank 17 to the aggregate recovery tank 64.
  • FIG. 11 is a schematic view showing a mechanism for recovering the rare earth element from the aggregate recovery tank in the separation and recovery apparatus shown in FIG.
  • the seventh pump 68 feeds the hydrochloric acid aqueous solution to the aggregate recovery tank 64 from the seventh tank 67 through the seventh pipe 69, and the magnetic powder-containing cation exchange resin 58 Dissolve surface aggregates.
  • the shutter 65 is opened, the liquid in which the aggregates are dissolved and the dissolved magnetic powder pass through the filter 66 and enter the collection tank 70. Meanwhile, the cation exchange resin remains on the filter 66.
  • a shutter 74 and a filter 75 are provided at the lower part of the recovery tank 70.
  • the eighth tank 72 feeds the sodium hydroxide aqueous solution into the recovery tank 70 through the eighth tank 71 and the eighth pipe 73. Then, the dissolved rare earth element precipitates as a poorly soluble hydroxide in water. Thereafter, when the shutter 74 is opened, the liquid (dissolved magnetic powder) passes through the filter 75 and enters the medicine recovery tank 76. On the other hand, the precipitated rare earth element hydroxide 77 remains on the filter 75. The rare earth element can be reused by recovering and reducing the hydroxide 77 of the rare earth element.
  • a mixed aqueous solution was prepared in which neodymium chloride (NdCl 3 ) and dysprosium chloride (DyCl 3 ) were dissolved in water. At that time, both Nd concentration and Dy concentration were adjusted to 5000 ppm. When the specific gravity of the obtained mixed aqueous solution is approximated to 1.0, the molar concentration of Nd and the molar concentration of Dy are 34.66 mmol / L and 30.77 mmol / L, respectively.
  • the second time aggregation process (first time of the re-aggregation step), and Dy ions from about 77.4 wt% of the mixed aqueous solution of NdCl 3 and DyCl 3 charged into the mixing tank ( ⁇ 0.88 2), about 4.8 wt% ( ⁇ 0.222 2 ) Nd ions are incorporated into the aggregate. That is, the proportion (that is, the purity) of the Dy ion to the rare earth element ion in the aggregate is 94.2%.
  • Nd ions About 68.15 mass% ( ⁇ 0.88 3 ) of Dy ions and about 1.06 mass% ( ⁇ 0.88 3 ) in the mixed aqueous solution of NdCl 3 and DyCl 3 charged into the mixing tank in the third aggregation step (second reaggregation step) ⁇ 0.223 3 ) Nd ions are incorporated into the aggregate. That is, the ratio (purity) of the Dy ion to the rare earth element ion in the aggregate is 98%.
  • the aggregate was dissolved in 1 N aqueous hydrochloric acid solution, and then 5 N aqueous sodium hydroxide solution was added little by little while stirring. . Then, an aggregate was formed in the vicinity of neutrality, but the aggregate was dissolved by subsequently adding a 5 N aqueous solution of sodium hydroxide.
  • 5 N aqueous sodium hydroxide solution was further added, poorly soluble dysprosium hydroxide (Dy (OH) 3 ) in water was precipitated. The precipitated dysprosium hydroxide was separated by filtration and recovered, and was reduced to obtain dysprosium alone.
  • Example 2 The same steps as in Example 1 were performed until the desired proportion of Dy ions in the aggregate was obtained. After this, the aggregate was recovered in the step shown in FIG. When the recovered aggregate was heated, the organic compounds (water-soluble polymer having an amino group and water-soluble polymer having an acidic group) in the aggregate were thermally decomposed to form dysprosium oxide. When the obtained dysprosium oxide was reduced, dysprosium alone could be obtained.
  • Example 2 100 g of the same mixed aqueous solution as in Example 1 (number of rare earth element ions: 6.54 mmol) was introduced into a mixing tank containing a cation exchange resin, and an aqueous solution of Compound A was added, resulting in the surface of the cation exchange resin. Aggregates were deposited. The aggregate was washed with deionized water, and then the step of dissolving and reaggregating the aggregate was repeated to increase the percentage of Dy ions in the aggregate.
  • Dy ions in the aggregate After the concentration of Dy ions in the aggregate was increased to the desired proportion, the aggregate was dissolved with 1 N hydrochloric acid, and then dysprosium hydroxide was precipitated by adding an aqueous 5 N sodium hydroxide solution. The precipitated dysprosium hydroxide was separated by filtration and recovered, and was reduced to obtain dysprosium alone.
  • Example 3 it was found through Example 3 that about 80% of Dy ions and about 20% of Nd ions are trapped in the aggregate in one aggregation step.
  • the separation and recovery of the rare earth element was performed in the same manner as in Example 3 using the separation and recovery apparatus of FIG. 10 and using a cation exchange resin containing magnetic powder inside the resin instead of a simple cation exchange resin. .
  • the ratio of Dy ions in the aggregates formed on the surface of the magnetic powder-containing cation exchange resin was increased to a desired value.
  • the magnetic powder-containing cation exchange resin to which the aggregates are attached was recovered by a recovery mechanism comprising a roller and a magnetic belt as shown in FIG.
  • the aggregate formed on the surface of the recovered magnetic powder-containing cation exchange resin was dissolved with hydrochloric acid in the same manner as in Example 1. Thereafter, an aqueous solution of sodium hydroxide was added to precipitate dysprosium hydroxide. The precipitated dysprosium hydroxide was separated by filtration and recovered, and was reduced to obtain dysprosium alone.
  • the ratio of Dy ions in the aggregate can be increased even when Compound B is used as a water-soluble polymer having an amino group.
  • the ratio of Dy ions in the aggregate can be increased even if polyethylene imine is used as the water-soluble polymer having an amino group.
  • the ratio of Dy ions in the aggregate can be increased even if polystyrene sulfonic acid is used as the water-soluble polymer having an acidic group.
  • aqueous solution and dysprosium chloride neodymium chloride were dissolved in water, a cerium chloride (CeCl 3) and ytterbium chloride (YbCl 3) using a mixed aqueous solution prepared by dissolving in water.
  • CeCl 3 cerium chloride
  • YbCl 3 ytterbium chloride
  • stirring blade 21 ... overhead stirrer, 22 ... 1st tank, 23 ... 1st pump, 24 ... 1st piping, 25 ... 2nd tank, 26 ... 2nd pump, 27 ... 2nd piping, 28 ... aggregates, 28 '... reaggregates, 29 ... shutters, Reference Signs List 30 filter, 31 valve, 32 recovery tank 33 third tank 34 third pump 35 third piping 36 fourth tank 37 fourth pump 38 ... 4th piping, 39 ... 5th tank, 40 ... 5th pump, 41 ... 5th piping, 42 ... inner wall of mixing tank, 43 ... mixing tank, 44 ... solution recovery pump, 45 ...

Abstract

La présente invention vise à fournir : un procédé de séparation/collecte qui peut augmenter le rapport de distribution entre différents éléments des terres rares dans le but d'atteindre la réduction de coût dans la séparation/collecte d'un élément des terres rares ; et un appareil de séparation/collecte qui peut atteindre le procédé. Un procédé pour séparer/collecter un élément des terres rares selon la présente invention est un procédé pour séparer/collecter un élément spécifique des terres rares à partir d'une solution aqueuse contenant des ions de multiples éléments des terres rares, et comprend : une étape d'agrégation consistant à ajouter un polymère soluble dans l'eau ayant un groupe acide à la solution aqueuse, puis d'ajouter un polymère soluble dans l'eau ayant un groupe amino au mélange résultant d'une manière telle que le nombre total des groupes amino devient supérieur à celui des groupes acides du polymère soluble dans l'eau ayant le groupe acide, permettant ainsi d'obtenir un produit agrégé ; une étape de séparation/collecte consistant à séparer et collecter le produit agrégé à partir de la solution aqueuse ; une étape de dissolution consistant à dissoudre le produit agrégé dans un acide, permettant ainsi d'obtenir une solution ; et une étape de ré-agrégation consistant à ajouter un polymère soluble dans l'eau ayant un groupe amino à la solution, permettant ainsi d'obtenir un produit ré-agrégé.
PCT/JP2012/067736 2011-07-19 2012-07-11 Procédé pour séparer/collecter un élément des terres rares et appareil pour séparer/collecter un élément des terres rares WO2013011901A1 (fr)

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CN201280035250.8A CN103827328B (zh) 2011-07-19 2012-07-11 稀土元素的分离回收方法及稀土元素的分离回收装置
JP2013524683A JP5683705B2 (ja) 2011-07-19 2012-07-11 希土類元素の分離回収方法および希土類元素の分離回収装置

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CN113481375B (zh) * 2021-07-26 2024-01-30 沛县宗赢工程机械制造有限公司 一种节能环保型稀土溶解分离装置

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