Ion exchange resin and method for adsorbing and separating metal

Abstract

Provided is a system for efficiently recovering trace metal from a large amount of a raw material, such as when trace metal is recovered from nickel oxide ore. This ion exchange resin has, on a carrier, an amide derivative represented by the following general formula. In the formula, R1 and R2 represent the same or different alkyl groups, R3 represents a hydrogen atom or an alkyl group, and R4 represents a hydrogen atom or an arbitrary group, other than an amino group, bonded to carbon as an amino acid. The amide derivative is preferably a glycinamide derivative. The carrier preferably includes a primary amine and/or a secondary amine.

Claims

1. A method for adsorbing and separating a metal, the method comprising: applying an acid solution containing one or more metals selected from cobalt, nickel, scandium and rare earth elements to an ion exchange resin to adsorb the metal on the ion exchange resin, and recovering the metal adsorbed on the ion exchange resin, wherein the ion exchange resin has an amide derivative represented by the following general formula (I) on a carrier, and the carrier includes 3-aminopropyl silica gel and/or 3-(ethylenediamino)propyl silica gel: ##STR00003## (wherein, R.sup.1 and R.sup.2 each represent the same or different alkyl groups, the alkyl group is optionally a straight chain or a branched chain, R.sup.3 represents a hydrogen atom or an alkyl group, and R.sup.4 represents a hydrogen atom or an arbitrary group other than an amino group bonded to carbon as an amino acid).

2. The method for adsorbing and separating a metal according to claim 1, wherein the amide derivative is a glycinamide derivative.

3. The method for adsorbing and separating a metal according to claim 2, the method comprising adsorbing a metal contained in an acid leaching solution obtained by high pressure acid leaching of nickel oxide ore on the ion exchange resin and recovering the metal adsorbed on the ion exchange resin.

4. The method for adsorbing and separating a metal according to claim 1, the method comprising adsorbing a metal contained in an acid leaching solution obtained by high pressure acid leaching of nickel oxide ore on the ion exchange resin and recovering the metal adsorbed on the ion exchange resin.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph showing the relationship between the pH of the post-extraction liquid and the adsorption rate on the resin when using the ion exchange resin according to Example 1.

(2) FIG. 2 is a graph showing the relationship between the pH of the post-extraction liquid and the adsorption rate on the resin when using the ion exchange resin according to Example 2.

PREFERRED MODE FOR CARRYING OUT THE INVENTION

(3) The specific embodiments of the present invention will now be described in detail. It should be noted however that the present invention is not limited to the following embodiments, and can be carried out with modifications within the scope of the object of the present invention.

(4) <Ion Exchange Resin>

(5) The ion exchange resin of the present invention has, on a carrier, an amide derivative represented by the following general formula (I). In the present invention, lipophilicity is increased by introducing an alkyl group into the skeleton of amide, and it can be used as a functional group when adsorbing one or more metals selected from cobalt, nickel, scandium and other rare earth elements.

(6) ##STR00002##

(7) As long as the ion exchange resin can suitably adsorb a trace metal (one or more trace metals selected from cobalt, nickel, scandium and other rare earth elements) contained in an acid leaching solution of, for example, nickel oxide ore, and the metal adsorbed on the resin can be suitably recovered by later treatment, the type of ion exchange resin is not particularly limited.

(8) Solid extractants such as ion exchange resins have advantages including physically stable handling being possible, it being possible to carry out operations using simple equipment, and separation can be comparatively stably carried out even when operating conditions change. In addition, the reaction by ion exchange does not have many physical movements, for example mixing an extractant and a solution in the solvent extraction method, and the contact of the ion exchange resin and the solution is generally carried out in a sealed column in many cases. Therefore, there are also features in which catching e.g. air is prevented, the production of CRUD is thus suppressed, and operations are stably carried out.

(9) [Amide Derivative]

(10) In the formula, substituents R1 and R2 each represent the same or different alkyl groups. In R1 and R2, the alkyl group may be a straight chain or a branched chain. In R1 and R2, the number of carbons in an alkyl group is not particularly limited, and is preferably 5 or more and 11 or less.

(11) R3 represents a hydrogen atom or an alkyl group. R4 represents a hydrogen atom or an arbitrary group other than an amino group bonded to carbon as an amino acid.

(12) As long as the amide derivative can adsorb one or more metals selected from cobalt, nickel, scandium and other rare earth elements, the type of the above amide derivative is not particularly limited, and the amide derivative is preferably a glycinamide derivative from the viewpoint that the derivative can be easily produced. When the amide derivative is a glycinamide derivative, the above glycinamide derivative can be synthesized by the following method. First, a 2-halogenated acetyl halide is added to an alkylamine having a structure represented by NHR1R2 (R1 and R2 are the same as the above substituents R1 and R2), and the hydrogen atom of amine is substituted with 2-halogenated acetyl by the nucleophilic substitution reaction to obtain 2-halogenated(N,N-di)alkylacetamide.

(13) Next, the above 2-halogenated(N,N-di)alkylacetamide is added to a glycine or N-alkylglycine derivative, and one of the hydrogen atoms of the glycine or N-alkylglycine derivative is substituted with an (N,N-di)alkylacetamide group by the nucleophilic substitution reaction. A glycine alkylamide derivative can be synthesized by the two-step reaction.

(14) A histidinamide derivative, a lysinamide derivative or an aspartic acid amide derivative can be synthesized by substituting glycine with histidine, lysine or aspartic acid.

(15) The extraction behaviors of a glycine alkylamide derivative, a histidinamide derivative, a lysinamide derivative, and an aspartic acid amide derivative are thought to be within the scope of the results obtained by using a glycine derivative from the stability constants of complexes of manganese, cobalt and the like, which are subjects.

(16) [Carrier]

(17) As long as the carrier is a solid material which can bond the above amide derivative, is chemically stable with the acid solution which is adsorbed, not physically affected when put into a column and a solution, and not deteriorated during adsorption operations, the carrier is not particularly limited. From the viewpoint of chemical stability, for example, the carrier preferably includes a primary amine and/or a secondary amine. The carrier more preferably includes a primary amine particularly to be able to selectively adsorb a trace metal which is a subject.

(18) Specific examples of carriers include 3-aminopropyl silica gel, 3-(ethylenediamino)propyl silica gel, and the like.

(19) <Adsorption of Valuable Metals on Resin>

(20) The techniques for adsorbing a valuable metal ion using e.g. the above ion exchange resin include a method called a batch method or a resin-in-pulp method, in which while adjusting the acid solution containing the target valuable metal ion, this acid solution is brought into contact with the above ion exchange resin etc., and further a column method in which the above ion exchange resin etc. is filled in a column and the above acid solution is applied to this column to come into contact therewith, and the like. Using these techniques, a target valuable metal ion can be selectively adsorbed on the substituents R1 and R2 of the above ion exchange resin, etc.

(21) [Adsorption of Cobalt]

(22) When efficiently adsorbing cobalt from an acid solution containing cobalt and manganese, the pH of the acid solution is preferably 3.5 or higher and 5.5 or lower, and more preferably 4.0 or higher and 5.0 or lower. When the pH is lower than 3.5, there is a possibility that cobalt cannot be sufficiently adsorbed. When the pH is above 5.5, there is a possibility that not only cobalt but also manganese is adsorbed.

(23) [Adsorption of Scandium]

(24) When adsorbing scandium from an acid solution containing scandium, the pH of the acid solution is preferably 0.5 or higher and 2.5 or lower, more preferably 1.0 or higher and 2.0 or lower, and even more preferably 1.5 or higher and 2.0 or lower. When the pH is lower than 0.5, there is a possibility that scandium cannot be sufficiently adsorbed. In a case when the acid solution is an acid solution obtained by acid leaching of nickel oxide ore, for example, when the pH is above 2.5, there is a possibility that not only scandium but also aluminum, zinc, nickel, cobalt and the like contained in the acid solution are adsorbed, and thus the amount of work involved may increase, for example purification is required in the following step.

(25) [Adsorption of Europium]

(26) When adsorbing europium from an acid aqueous solution containing several types of rare earth metal such as europium and yttrium, and zinc, the pH of the acid solution is preferably 2.0 or higher and 3.0 or lower. When the pH is lower than 2.0, there is a possibility that europium cannot be sufficiently extracted. When the pH is above 3.0, there is a possibility that not only europium but also other rare earth metals including yttrium are adsorbed.

(27) [Adsorption of Rare Earth Elements (Light Rare Earth Elements)]

(28) The ion exchange resin of the present invention etc. has a feature in that light rare earth elements and middle rare earth elements are more easily adsorbed than heavy rare earth elements. Because of this, particularly while adjusting the pH of a solution containing both heavy rare earth elements and light rare earth elements, the solution is allowed to come into contact with the ion exchange resin of the present invention, thereby being able to selectively adsorb light rare earth elements from the solution. As a result, light rare earth elements and heavy rare earth elements can be separated. In addition, when a solution further contains middle rare earth elements, an eluent recovered from the above ion exchange resin etc. by a technique described in <Recovery of Valuable Metals from Resin> mentioned below is used for solvent extraction, for example using an organic solvent containing an amide derivative represented by the above general formula (I), thereby being able to suitably separate light rare earth elements and middle rare earth elements.

(29) When adsorbing light rare earth elements from an acid solution containing heavy rare earth elements and light rare earth elements, the pH of the acid solution is preferably 1.7 or higher and 2.7 or lower. When the pH is lower than 1.7, there is a possibility that light rare earth elements cannot be sufficiently adsorbed. When the pH is above 2.7, there is a possibility that not only light rare earth elements but also heavy rare earth elements are adsorbed.

(30) The mechanism via which the resin of the present invention exhibits behaviors of adsorption or extraction different from those of conventional ion exchange resins etc. and extractants for solvent extraction is unclear; however, it is thought that the effects which have not been conventionally obtained are displayed due to the structural features of the ion exchange resin of the present invention.

(31) <Recovery of Valuable Metals from Resin>

(32) With respect to an ion exchange resin after adsorption of a valuable metal ion, the ion exchange resin is washed with e.g. pure water to remove a part of the above acid solution attached to the surface, and an eluent adjusted to a pH lower than that of the above acid aqueous solution is then applied thereto as known in conventionally known methods, thereby being able to recover a target valuable metal ion from the ion exchange resin.

(33) The eluent is not particularly limited as long as the pH thereof is adjusted to be lower than that of the above acid aqueous solution, and examples thereof include an aqueous solution in which nitric acid, hydrochloric acid, or sulfuric acid is diluted, and the like. In addition, a target valuable metal ion can be concentrated by appropriately changing the contact time of the ion exchange resin and the eluent, i.e. the time the eluent is in the column, and the like.

(34) Since the equilibrium arrival time varies depending on the types and concentration of valuable metal, the eluent flow rate and eluent temperature can be appropriately set depending on an acid aqueous solution of valuable metal ions and conditions. The pH of an acid aqueous solution containing a metal ion can be also appropriately adjusted depending on the types of valuable metal.

EXAMPLES

(35) The present invention will now be described in more detail by way of examples thereof. It should be noted however that the present invention is not limited to these descriptions.

Preparation of Ion Exchange Resin Having Amide Derivative

Example 1

(36) As an example of amide derivatives forming an ion exchange resin according to the present invention, N[N,N-bis(2-ethylhexyl)aminocarbonylmethyl]glycine (or also referred to as N,N-di(2-ethylhexyl)acetamide-2-glycine, and hereinafter referred to as D2EHAG) into which two 2-ethylhexyl groups were introduced was used. The chemical formula of D2EHAG is described in Patent Document 3 mentioned above.

(37) An ion exchange resin having D2EHAG was prepared as follows.

(38) (1) 4.37 g of chloroacetyl chloride (corresponding to 3 equivalents with respect to the amine of silica gel which is supported) and 1.32 g of triethylamine (TEA) were collected, and these were dissolved by adding 70 ml of dichloromethane (DCM).

(39) (2) 10 g of 3-aminopropyl silica gel was added to the solution obtained in (1), and the obtained mixture was stirred for a day while maintaining room temperature.

(40) (3) After stirring, the product was filtered, and washed by adding methanol.

(41) (4) After washing, the product was dried to obtain about 10 g of pale yellow intermediate silica gel. The recovery rate calculated from the amount of substance was about 92%.

(42) (5) 70 ml of methanol solution is added to 5.85 g of glycine (corresponding to 6 equivalents with respect to the amine of silica gel similarly to the above) and 3.15 g of sodium hydroxide, and the obtained mixture is mixed, and gradually added to 8 g of the intermediate silica gel mentioned in (4) above.

(43) (6) The obtained mixture is allowed to react over 15 hours while maintaining 60 C.

(44) (7) The obtained reaction product is washed by successively adding ethyl acetate, methanol, acetone and water, and then dried.

(45) (8) By undergoing (1) to (7) above, 7.94 g of product (glycine acetaminopropyl silica gel) was obtained. This product is used as the ion exchange resin according to Example 1. The recovery rate of the product was about 96%.

Example 2

(46) The ion exchange resin according to Example 2 (glycine aceto(ethylenediamino)propyl silica gel) was obtained in the same manner as in Example 1 except that 3-aminopropyl silica gel was changed to 3-(ethylenediamino)propyl silica gel.

(47) A glycinamide derivative and further a normal-methylglycine derivative, a histidinamide derivative and the like are also known as an amide derivative, and these can be also supported as a functional group on a carrier to make an ion exchange resin as in the case with the above glycinamide derivative.

(48) <Evaluation>

(49) Eight types of acid solution were prepared, which each contained scandium (Sc), yttrium (Y), neodymium (Nd), europium (Eu), dysprosium (Dy), lanthanum (La), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al) and manganese (Mn) at 110-4 mol/l and were adjusted to pH 0.7, 1.0, 1.5, 2.0, 2.5, 3.0, 3.3 and 3.7. The pH was adjusted using sulfuric acid, ammonium sulfate and ammonia with a concentration of 0.2 mol/l.

(50) Next, with respect to the ion exchange resin according to Example 1, 50 ml of the above acid solution and 0.5 dry-g of the ion exchange resin according to Example 1 were put into a beaker, and the obtained mixture was maintained at 25 C. and stirred using a stirrer for an hour. With respect to the ion exchange resin according to Example 2, 50 ml of the above acid solution and 0.3 dry-g of the ion exchange resin according to Example 2 were put into a beaker, and the obtained mixture was maintained at 25 C. and stirred using a stirrer for an hour.

(51) After stirring for an hour, the ion exchange resin and a post-adsorption liquid were obtained by solid-liquid separation using filter paper, and the pH of the post-adsorption liquid was measured. Next, the ion exchange resin was washed by a water pouring treatment using a small amount of pure water, and the post-adsorption liquid and washing water were combined to obtain a new post-adsorption liquid. The volume thereof was measured, and the concentration of the components, which were contained in the starting liquid, in the post-adsorption liquid was measured using an inductively coupled plasma atomic emission spectrometer (ICP-AES). From the measurement results, the adsorption rate (distribution) on the ion exchange resins was defined from changes in the amount of substance in an acid solution before and after adsorption using (1Amount of Substance after Adsorption/Amount of Substance before Adsorption), and found. The results for Example 1 are shown in Table 1 and FIG. 1, and the results for Example 2 are shown in Table 2 and FIG. 2. In FIGS. 1 and 2, the pH of an acid solution is the abscissa, and the extraction rate (Unit: -) of metal elements is the ordinate.

(52) TABLE-US-00001 TABLE 1 Modified 3-aminopropyl silica gel (D2EHAG) A: 0.5 g/50 ml 0.2M SO4 (H2SO4(NH4)2SO4) pH (before) pH (after) Sc Y Nd Eu Dy La Fe Co Ni Zn Al Mn 0.7 0.7 0.24 0.01 0.02 0.01 0.00 0.03 0.18 0.00 0.01 0.02 0.00 0.00 1.0 1.0 0.35 0.00 0.03 0.01 0.00 0.00 0.39 0.00 0.01 0.00 0.00 0.00 1.5 1.5 0.55 0.00 0.03 0.02 0.01 0.01 0.76 0.01 0.04 0.01 0.00 0.00 2.0 2.0 0.75 0.01 0.06 0.06 0.05 0.01 0.95 0.00 0.10 0.01 0.00 0.00 2.5 2.4 0.90 0.06 0.12 0.17 0.15 0.02 0.99 0.03 0.30 0.09 0.04 0.01 3.0 2.8 0.97 0.12 0.21 0.31 0.28 0.03 1.00 0.05 0.52 0.20 0.04 0.05 3.3 3.1 0.99 0.16 0.26 0.39 0.38 0.04 1.00 0.06 0.63 0.19 0.02 0.02 3.7 3.2 1.00 0.23 0.32 0.47 0.45 0.07 1.00 0.10 0.73 0.25 0.06 0.03

(53) TABLE-US-00002 TABLE 2 Modified 3-(ethylenediamino)propyl silica gel (D2EHAG) B: 0.3 g/50 ml 0.2M SO4 (H2SO4(NH4)2SO4) pH (before) pH (after) Sc Y Nd Eu Dy La Fe Co Ni Zn Al Mn 0.7 0.7 0.07 0.00 0.00 0.00 0.00 0.01 0.08 0.02 0.01 0.01 0.00 0.01 1.0 1.0 0.16 0.00 0.03 0.00 0.00 0.01 0.17 0.00 0.01 0.00 0.00 0.00 1.5 1.5 0.36 0.00 0.04 0.02 0.00 0.00 0.42 0.02 0.04 0.01 0.00 0.01 2.0 2.0 0.60 0.01 0.10 0.09 0.06 0.02 0.65 0.02 0.10 0.01 0.00 0.01 2.5 2.6 0.83 0.07 0.19 0.25 0.20 0.05 0.79 0.05 0.28 0.08 0.00 0.03 3.0 3.3 0.96 0.21 0.39 0.50 0.44 0.11 0.82 0.10 0.60 0.19 0.00 0.03 3.3 4.0 1.00 0.42 0.58 0.71 0.68 0.20 0.86 0.20 0.84 0.38 0.08 0.03 3.7 5.1 1.00 0.63 0.72 0.84 0.84 0.31 0.73 0.52 0.98 0.71 0.40 0.06

(54) From Tables 1 and 2 and FIGS. 1 and 2, it was verified that, when the ion exchange resins in Examples were used, one or more metals selected from cobalt, nickel, scandium and rare earth elements could be selectively adsorbed by suitably adjusting the pH of an acid solution. From the results, it can be also said that a metal (one or more metals selected from cobalt, nickel, scandium and rare earth elements) contained in an acid leaching solution obtained by high pressure acid leaching of nickel oxide ore can be selectively adsorbed.