US20020070171A1 - Method for separating metal ions - Google Patents

Method for separating metal ions Download PDF

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Publication number
US20020070171A1
US20020070171A1 US09/795,481 US79548101A US2002070171A1 US 20020070171 A1 US20020070171 A1 US 20020070171A1 US 79548101 A US79548101 A US 79548101A US 2002070171 A1 US2002070171 A1 US 2002070171A1
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Prior art keywords
metal ions
aqueous solution
capturing agent
separating
selective capturing
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Abandoned
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US09/795,481
Inventor
Yu Komatsu
Shigekazu Tsurubou
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National Institute for Research in Inorganic Material
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National Institute for Research in Inorganic Material
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Assigned to NATIONAL INSTITUTE FOR RESEARCH IN INORGANIC MATERIALS reassignment NATIONAL INSTITUTE FOR RESEARCH IN INORGANIC MATERIALS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KOMATSU, YU, TSURUBOU, SHIGEKAZU
Publication of US20020070171A1 publication Critical patent/US20020070171A1/en
Priority to US10/316,923 priority Critical patent/US7041262B2/en
Abandoned legal-status Critical Current

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Classifications

    • 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
    • B01J39/04—Processes using organic exchangers
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/302—Ethers or epoxides
    • C22B3/304—Crown ethers
    • 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 for separating metal ions. More particularly, the present invention relates to a method for separating metal ions by separating a specific type of metal ions while preventing inclusion of impurities to obtain metal ions with a high purity.
  • the ion exchange method is a separation method utilizing a reaction wherein metal ions in an aqueous solution replace ions in an ion exchanger and undergo phase transition.
  • the reaction amount is determined by the ratio of the amount of the ion exchanger to the amount of the aqueous solution, and the separative power shows a constant value depending upon the ion exchanger.
  • the solvent extraction method is a separation method utilizing a reaction wherein metal ions in an aqueous solution react with an extracting agent or a synergistic extracting agent dissolved in an organic solvent and undergo phase transition into an organic phase.
  • the amount of the metal ions to be extracted depends on the type of the extracting agent or the synergistic extracting agent, and the separative power shows a constant value characteristic to the extracting agent or the synergistic extracting agent.
  • the separative power is determined by the type of the extracting agent or the synergistic extracting agent, depending upon the type of the extracting agent or the synergistic extracting agent, inclusion of at least 1% of impurities may be inevitable in separation of Ca and Sr.
  • the present invention has been made to overcome the above drawbacks of conventional methods for separating metal ions, and it is an object of the present invention to provide a method for separating metal ions, which comprises separating a specific type of metal ions while preventing inclusion of impurities to obtain metal ions with a high purity.
  • the present invention provides a method for separating metal ions, which comprises adding a selective capturing agent to an aqueous solution containing plural types of metal ions, said selective capturing agent being a cyclic compound and forming a complex with metal ions having ion radii suitable for the size of the ring alone, so that unnecessary metal ions are held by the selective capturing agent in the aqueous solution, and bringing said aqueous solution into contact with an ion exchange solid phase so as to transport desired metal ions alone to the solid phase.
  • the present invention further provides the above method wherein the plural types of metal ions are in the same Group.
  • the present invention further provides the above method wherein the plural types of metal ions are at least two types belonging to alkaline earth metal ions.
  • the present invention still further provides the above method wherein the selective capturing agent is a cryptand or a crown ether.
  • a selective capturing agent which selectively captures specific types of metal ions is used.
  • This selective capturing agent is a cyclic compound, and forms a complex with metal ions having ion radii suitable for the size of the ring alone.
  • the above selective capturing agent is added to an aqueous solution containing plural types of metal ions, and the aqueous solution is brought into contact with an ion exchange solid phase.
  • the selective capturing agent forms a metal complex with specific metal ions alone in the aqueous solution. This reaction takes place in accordance with a theoretical equilibrium value, and the metal ions forming a metal complex are held in the aqueous solution even after the reaction. Accordingly, in the aqueous solution, metal ion species forming a metal complex with the selective capturing agent and metal ion species not forming a metal complex are present, and there is a significant difference in the ion radius between them.
  • Metal ions capable of being held in the aqueous solution are determined by the type of the selective capturing agent and the size of the metal ions, and the amount of metal ions held shows a characteristic value depending on the type of the selective capturing agent and the type of the metal ions.
  • a specific type of metal ions can be completely or substantially completely separated while preventing inclusion of impurities, and metal ions with a high purity can be obtained. Further, the separation efficiency of metal ions will improve.
  • metal ions in the same Group have the same reaction mechanism in an ion exchange reaction, and are likely to move to the ion exchange solid phase.
  • metal ions other than desired ones are held by the selective capturing agent in the aqueous solution, whereby inclusion of impurities into the solid phase will be inhibited.
  • the selective capturing agent may optionally be determined depending upon the ion radii of metal ions to be held, and a cryptand or a crown ether may, for example, be mentioned.
  • a water-soluble organic solvent such as propanol may be added to the aqueous solution.
  • titania hydrate was used as the ion exchanger, and in the solvent extraction method, TTA (thenoyltrifluoroacetone) was used as an extracting agent, and TOPO (trioctylphosphineoxide) was used as a synergistic extracting agent.
  • TTA thenoyltrifluoroacetone
  • TOPO trioctylphosphineoxide
  • Cryptand [2.2.2] has Sr capturing properties in a pH of the aqueous solution of from 4 to 9, and particularly in a pH of from 6.3 to 7.8, it can capture 100% of Sr. Accordingly, when the aqueous solution is neutral or has a pH in the vicinity thereof, separation of Ca and Sr can be carried out completely or substantially completely.
  • metal ions with a high purity can be obtained by separating a specific type of metal ions while preventing inclusion of impurities.

Abstract

A method for separating metal ions, which comprises adding a selective capturing agent to an aqueous solution containing plural types of metal ions, said selective capturing agent being a cyclic compound and forming a complex with metal ions having ion radii suitable for the size of the ring alone, so that unnecessary metal ions are held by the selective capturing agent in the aqueous solution, and bringing said aqueous solution into contact with an ion exchange solid phase so as to transport desired metal ions alone to the solid phase.

Description

    METHOD FOR SEPARATING METAL IONS
  • The present invention relates to a method for separating metal ions. More particularly, the present invention relates to a method for separating metal ions by separating a specific type of metal ions while preventing inclusion of impurities to obtain metal ions with a high purity. [0001]
  • As a method for separating metal ions, an ion exchange method and a solvent extraction method are well known as representative examples. [0002]
  • The ion exchange method is a separation method utilizing a reaction wherein metal ions in an aqueous solution replace ions in an ion exchanger and undergo phase transition. The reaction amount is determined by the ratio of the amount of the ion exchanger to the amount of the aqueous solution, and the separative power shows a constant value depending upon the ion exchanger. [0003]
  • The solvent extraction method is a separation method utilizing a reaction wherein metal ions in an aqueous solution react with an extracting agent or a synergistic extracting agent dissolved in an organic solvent and undergo phase transition into an organic phase. The amount of the metal ions to be extracted depends on the type of the extracting agent or the synergistic extracting agent, and the separative power shows a constant value characteristic to the extracting agent or the synergistic extracting agent. [0004]
  • However, by either of the ion exchange method and the solvent extraction method as representative examples of the method for separating metal ions, inclusion of impurities is inevitable, and complete or substantially complete separation of desired metal ions is difficult. [0005]
  • Specifically, separation of alkaline earth metal ions will be explained as an example. In the ion exchange method, when a titania hydrate is employed as an ion exchanger, for example, in separation of Ca and Sr which are alkaline earth metal ions adjacent to each other, so much as 16% of impurities will be mixed. [0006]
  • Further, in the solvent extraction method, as the separative power is determined by the type of the extracting agent or the synergistic extracting agent, depending upon the type of the extracting agent or the synergistic extracting agent, inclusion of at least 1% of impurities may be inevitable in separation of Ca and Sr. [0007]
  • Under these circumstances, the present invention has been made to overcome the above drawbacks of conventional methods for separating metal ions, and it is an object of the present invention to provide a method for separating metal ions, which comprises separating a specific type of metal ions while preventing inclusion of impurities to obtain metal ions with a high purity. [0008]
  • The present invention provides a method for separating metal ions, which comprises adding a selective capturing agent to an aqueous solution containing plural types of metal ions, said selective capturing agent being a cyclic compound and forming a complex with metal ions having ion radii suitable for the size of the ring alone, so that unnecessary metal ions are held by the selective capturing agent in the aqueous solution, and bringing said aqueous solution into contact with an ion exchange solid phase so as to transport desired metal ions alone to the solid phase. [0009]
  • The present invention further provides the above method wherein the plural types of metal ions are in the same Group. The present invention further provides the above method wherein the plural types of metal ions are at least two types belonging to alkaline earth metal ions. The present invention still further provides the above method wherein the selective capturing agent is a cryptand or a crown ether. [0010]
  • Now, preferred embodiments of the method for separating metal ions of the present invention will be explained in further detail below. [0011]
  • In the method for separating metal ions of the present invention, a selective capturing agent which selectively captures specific types of metal ions is used. This selective capturing agent is a cyclic compound, and forms a complex with metal ions having ion radii suitable for the size of the ring alone. [0012]
  • In the method for separating metal ions of the present invention, the above selective capturing agent is added to an aqueous solution containing plural types of metal ions, and the aqueous solution is brought into contact with an ion exchange solid phase. [0013]
  • The selective capturing agent forms a metal complex with specific metal ions alone in the aqueous solution. This reaction takes place in accordance with a theoretical equilibrium value, and the metal ions forming a metal complex are held in the aqueous solution even after the reaction. Accordingly, in the aqueous solution, metal ion species forming a metal complex with the selective capturing agent and metal ion species not forming a metal complex are present, and there is a significant difference in the ion radius between them. Metal ions capable of being held in the aqueous solution are determined by the type of the selective capturing agent and the size of the metal ions, and the amount of metal ions held shows a characteristic value depending on the type of the selective capturing agent and the type of the metal ions. [0014]
  • When the aqueous solution in such a state is brought into contact with an ion exchange solid phase, the metal ion species not forming a metal complex alone transfers to the solid phase. The metal ion species forming a metal complex and having a large ion radius does not transfer. Based on this principle, in the method for separating metal ions of the present invention, unnecessary metal ions are held by the selective capturing agent in the aqueous solution, and desired metal ions alone are transferred to the solid phase. Accordingly, metal ions to be brought in the solid phase as impurities will drastically decrease. Therefore, according to the method for separating metal ions of the present invention, a specific type of metal ions can be completely or substantially completely separated while preventing inclusion of impurities, and metal ions with a high purity can be obtained. Further, the separation efficiency of metal ions will improve. [0015]
  • Here, in the method for separating metal ions of the present invention, it is possible to separate metal ions in the same Group. Metal ions in the same Group have the same reaction mechanism in an ion exchange reaction, and are likely to move to the ion exchange solid phase. However, metal ions other than desired ones are held by the selective capturing agent in the aqueous solution, whereby inclusion of impurities into the solid phase will be inhibited. [0016]
  • The selective capturing agent may optionally be determined depending upon the ion radii of metal ions to be held, and a cryptand or a crown ether may, for example, be mentioned. In order to improve complex-forming ability of the selective capturing agent, in the method for separating metal ions of the present invention, a water-soluble organic solvent such as propanol may be added to the aqueous solution.[0017]
  • Now, the present invention will be described in detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples. Further, the type of metal ions, the type of the selective capturing agent and reaction conditions are not limited thereto. [0018]
    • EXAMPLE
  • Into an aqueous solution containing both ions of Ca and Sr as alkaline earth metals, cryptand [2.2.2] as a selective capturing agent was added and dissolved, and this aqueous solution was brought into contact with Amberlite 200CT as an ion exchange resin. After equilibrium was reached, the amounts of metal ions in the liquid phase and the solid phase were measured, and the results were compared with a case where an aqueous solution containing Ca and Sr ions was brought into contact with Amberlite 200CT without addition of cryptand [2.2.2]. Further, the results were compared with separation of Ca and Sr by conventional ion exchange method and solvent extraction method. In the ion exchange method, titania hydrate was used as the ion exchanger, and in the solvent extraction method, TTA (thenoyltrifluoroacetone) was used as an extracting agent, and TOPO (trioctylphosphineoxide) was used as a synergistic extracting agent. [0019]
  • The results are shown in the following Tables 1 and 2. [0020]
    TABLE 1
    pH of aqueous solution 5 6 6.3-7.8 8 9
    Retention of Sr (%)
    Cryptand [2.2.2]added 27 88 100 88 33
    Cryptand [2.2.2]not 0 0  0 0 0
    added
  • [0021]
    TABLE 2
    Inclusion ratio of Sr (%)
    Present separation method 0.00 (pH 6.3-7.8)
    Ion exchange method 16.00
    Solvent extraction method 1.01
  • As shown in Table 1, Sr ions having a large ion radius undergo a complex-forming reaction with cryptand [2.2.2] and are held in the aqueous solution. On the contrary, Ca ions having a small ion radius do not react with cryptand [2.2.2] and move to the ion exchange resin as the solid phase. Cryptand [2.2.2] has Sr capturing properties in a pH of the aqueous solution of from 4 to 9, and particularly in a pH of from 6.3 to 7.8, it can capture 100% of Sr. Accordingly, when the aqueous solution is neutral or has a pH in the vicinity thereof, separation of Ca and Sr can be carried out completely or substantially completely. [0022]
  • When cryptand [2.2.2] is not added, both Ca ions and Sr ions move to the solid phase, and when the aqueous solution has a pH of from 2 to 12, 100% of both metal ions move to the solid phase. Accordingly, separation of Ca and Sr is impossible. [0023]
  • Further, as shown in Table 2, inclusion of impurities is inevitable in the conventional ion exchange method and solvent extraction method, whereas in the method for separating metal ions of the present invention, metal ions with a high purity, without inclusion of impurities, can be obtained. [0024]
  • As explained above, according to the method of the present invention, metal ions with a high purity can be obtained by separating a specific type of metal ions while preventing inclusion of impurities. [0025]

Claims (6)

What is claimed is:
1. A method for separating metal ions, which comprises adding a selective capturing agent to an aqueous solution containing plural types of metal ions, said selective capturing agent being a cyclic compound and forming a complex with metal ions having ion radii suitable for the size of the ring alone, so that unnecessary metal ions are held by the selective capturing agent in the aqueous solution, and bringing said aqueous solution into contact with an ion exchange solid phase so as to transport desired metal ions alone to the solid phase.
2. The method for separating metal ions according to claim 1, wherein the plural types of metal ions are in the same Group.
3. The method for separating metal ions according to claim 2, wherein the plural types of metal ions are at least two types belonging to alkaline earth metal ions.
4. The method for separating metal ions according to claim 1, wherein the selective capturing agent is a cryptand or a crown ether.
5. The method for separating metal ions according to claim 2, wherein the selective capturing agent is a cryptand or a crown ether.
6. The method for separating metal ions according to claim 3, wherein the selective capturing agent is a cryptand or a crown ether.
US09/795,481 2000-10-13 2001-03-01 Method for separating metal ions Abandoned US20020070171A1 (en)

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JP2000312887A JP3890401B2 (en) 2000-10-13 2000-10-13 Separation of metal ions

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* Cited by examiner, † Cited by third party
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JPS6160699A (en) * 1984-08-31 1986-03-28 Agency Of Ind Science & Technol Novel cyclic octapeptide, its preparation, and extracting and separating agent comprising it as component
US4943375A (en) 1987-09-04 1990-07-24 Brigham Young University The process of separating a selected ion from a plurality of other ions in a multiple ion solution by contacting the solution with a macrocyclic ligand bonded to silica which selectively complexes with the desired ion
IL86766A (en) 1987-09-04 1992-02-16 Bradshaw Jerald S Macrocyclic ligands bonded to sand or silica gel and their use in selectively and quantitatively removing and concentrating ions present at low concentrations from mixtures thereof with other ions
JPH0765130B2 (en) 1989-06-27 1995-07-12 科学技術庁長官官房会計課長 Solvent extraction method using crown ether
JP2685081B2 (en) 1990-06-19 1997-12-03 科学技術庁長官官房会計課長 Europium Selective Extraction Method
DE19520354C2 (en) * 1995-06-07 1997-07-10 Bt Magnettechnologie Gmbh Process for case hardening of higher molybdenum alloyed sintered steels
JP3633739B2 (en) 1996-12-19 2005-03-30 株式会社タクマ Ash processing method
EP0851035B1 (en) 1996-12-26 2002-04-03 Cosmo Research Institute Use of a composition for extracting transition metal and method for extracting transition metal using the same
US5863439A (en) * 1997-06-06 1999-01-26 Arch Development Corporation Process for separation and preconcentration of radium from water

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US20030108464A1 (en) 2003-06-12
JP3890401B2 (en) 2007-03-07
US7041262B2 (en) 2006-05-09
AU2326701A (en) 2002-04-18
AU778634B2 (en) 2004-12-16
JP2002121623A (en) 2002-04-26

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