Adsorbent for rare earth element and method for recovering rare earth element

Abstract

An adsorbent for rare earth element and a method for recovering a rare earth element, in which a rare earth element contained in an aqueous solution can be simply and inexpensively adsorbed and recovered, and a rare earth element present in an aqueous solution in combination with a base metal can be selectively adsorbed and recovered. The adsorbent includes a base material and diglycolamic acid introduced into the base material. The method for recovering a rare earth element includes steps of: bringing an aqueous solution containing a rare earth element into contact with the adsorbent for rare earth element to allow the rare earth element to be adsorbed on the adsorbent for rare earth element; and desorbing the rare earth element adsorbed on the adsorbent for rare earth element with an acid of 1 N or less.

Claims

1. An adsorbent for rare earth element which is brought into contact with an aqueous solution containing a rare earth element to adsorb and recover the rare earth element, the adsorbent comprising: a base material; and diglycolamic acid introduced into the base material, wherein the base material is polyethylene or polypropylene.

2. The adsorbent for rare earth element according to claim 1, wherein the diglycolamic acid has been introduced into the base material by reacting diglycolic acid or diglycolic anhydride with a carrier having a primary amine and/or a secondary amine on the base material.

3. The adsorbent for rare earth element according to claim 2, wherein the carrier is selected from the group consisting of poly(allylamine), polyethyleneimine, and chitosan.

4. A method for recovering a rare earth element comprising: bringing an aqueous solution containing a rare earth element into contact with an adsorbent for rare earth element to adsorb the rare earth element on the adsorbent, the adsorbent comprising a base material and diglycolamic acid introduced into the base material; and desorbing the rare earth element with an acid of 1 N or less.

5. The method for recovering a rare earth element according to claim 4, wherein the acid is hydrochloric acid.

6. The method for recovering a rare earth element according to claim 5, wherein the aqueous solution containing a rare earth element is a mixed aqueous solution containing a rare earth element and a base metal in which pH is not adjusted, and the rare earth element is selectively adsorbed and recovered from the mixed aqueous solution.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1(1) is a view showing a method for preparing an adsorbent for rare earth element. FIG. 1(2) is an explanatory view of a carrier other than (1). FIG. 1(3) is a view showing the structural formula of diglycolic acid.

(2) FIG. 2 is a graph showing the adsorption percentage of each rare earth element when an adsorbent for rare earth element B was used.

(3) FIG. 3 shows the results of investigation on the pH dependency of the adsorption percentage of each rare earth element when an adsorbent for rare earth element C was used in a mixed system of a rare earth element and a base metal.

(4) FIG. 4 shows the results of investigation on the pH dependency of the adsorption percentage of each rare earth element when an adsorbent for rare earth element D was used in a mixed system of a rare earth element and a base metal.

(5) FIG. 5 shows the results of investigation on the pH dependency of the adsorption percentage of each rare earth element when an adsorbent for rare earth element E was used in a mixed system of a rare earth element and a base metal.

(6) FIG. 6 shows the results of investigation on the pH dependency of the adsorption percentage of each rare earth element when an adsorbent for rare earth element F was used in a mixed system of a rare earth element and a base metal.

(7) FIG. 7 shows the results of investigation on the adsorption percentage of each rare earth element when the adsorbent for rare earth element D was used at a pH of 1.0.

(8) FIG. 8 shows a dysprosium adsorption isotherm when the adsorbent for rare earth element D was used at each initial pH.

(9) FIG. 9 shows the results of investigation on the desorption ratio from the adsorbent for rare earth element D on which Dy is adsorbed.

(10) FIG. 10 shows the results of investigation on the adsorption percentage of each rare earth element when the adsorbent for rare earth element D was used.

(11) FIG. 11 shows the results of investigation on the specific surface area, the average pore size, and the whole pore volume of amino-silica gel and an adsorbent D.

(12) FIG. 12 shows the results of investigation on the change of the dysprosium adsorption percentage with time when an adsorbent D was used.

(13) FIG. 13 shows the column test results of rare earth elements and base metals when an adsorbent D was used.

(14) FIG. 14 is the results of investigation on the integrated adsorption amount of dysprosium and neodymium when an adsorbent D was used.

DESCRIPTION OF EMBODIMENTS

(15) In the present invention, in order to solve the above problems, functional groups were first as densely distributed as possible by using a material having a plurality of functional groups in the molecule or by increasing the amount of functional groups to be introduced because a plurality of functional groups relative to one rare earth element ion are necessary for allowing rare earth elements to be adsorbed. Next, in order to increase the adsorption rate, an adsorbent was designed so that an adsorption site might be located on the surface of a base material. Further, the specific surface area was increased by using a porous body as a base material, thus increasing also the adsorption amount. In order to allow repeated use, functional groups were introduced by chemical bonds.

(16) Hereinafter, the embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments. Note that, hereinafter, an adsorbent for rare earth element of the present invention may be referred to only as an adsorbent. First, the structure and preparation method of an adsorbent for rare earth element of the present invention will be described with reference to FIG. 1.

(17) As shown in FIG. 1, an adsorbent for rare earth element 1 of the present invention is an adsorbent to be brought into contact with an aqueous solution containing a rare earth element to adsorb and recover the rare earth element. The adsorbent for rare earth element 1 is prepared by introducing diglycolamic acid 4 into a carrier 2.

(18) FIG. 1(1) is a schematic diagram showing an example of the preparation method of the adsorbent for rare earth element 1. The carrier 2 has a primary amine 2b on a base material 2a. Then, the diglycolamic acid 4 (inside the dashed line) is introduced into (bonded to) the base material 2a through an amide group 4a (inside the dotted line) by mixing diglycolic anhydride 3 with the carrier 2. Further, as shown in FIG. 1(2), a material having both a primary amine 2b and a secondary amine 2c can also be used as another carrier 2d, in which diglycolic acid 3a is bonded to both the primary amine 2b and the secondary amine 2c.

(19) The carrier 2 may be of any material and shape as long as it has the primary amine 2b and/or the secondary amine 2c and has mechanical strength, acid resistance, and insolubility in an aqueous solution. Examples of the shape of the carrier 2 include, but are not particularly limited to, a particulate shape, a plate shape, a bar shape, a tubular shape, a fibrous shape, and a film shape.

(20) Examples of the base material 2a include polymers having a primary amine and/or a secondary amine such as poly(allylamine), polyethyleneimine, and chitosan. Further examples of the base material 2a include particles, films, and the like of a general-purpose polymer such as polyethylene and polypropylene to which a primary amine and/or a secondary amine is added (bonded or the like) and silica to the surface of which is bonded alkylamine.

(21) For introducing diglycolamic acid 4 which is an adsorption site of a rare earth element, diglycolic anhydride 3 was used in FIG. 1(1), but it is also possible to use diglycolic acid 3a shown in FIG. 1(3). Diglycolic acid 3a is preferred since it is less expensive than diglycolic anhydride 3.

(22) Hereinafter, a specific method for preparing an adsorbent according to the present invention, adsorption test, and recovery test will be described.

Example 1

Preparation of Adsorbent A

(23) To a solution in which polyethyleneimine was dissolved in methanol, was added silica gel to impregnate the silica gel with polyethyleneimine, and the resulting reaction product was filtered, sufficiently washed with methanol and water, and dried under reduced pressure.

(24) Next, the polyethyleneimine-impregnated silica gel was added to a glutaraldehyde aqueous solution to crosslink the polyethyleneimine in the silica gel, and the resulting reaction product was filtered, sufficiently washed with water, and dried under reduced pressure.

(25) Next, the polyethyleneimine-impregnated silica gel (carrier) crosslinked with glutaraldehyde was added to a diglycolic anhydride-ethanol solution and allowed to react with each other at 25 C. for 3 days. The resulting reaction product was filtered, sufficiently washed with ethanol and water, and dried under reduced pressure to obtain an adsorbent A.

(26) [Adsorption Test of Adsorbent A]

(27) To 5 ml of an aqueous solution for adsorption test containing 20 ppm each of dysprosium and neodymium as rare earth elements, was added 50 mg of the adsorbent A, and the mixture was subjected to adsorption test at 25 C. with shaking.

(28) After the lapse of a predetermined period of time, the solution was collected, filtered with a 0.20-m membrane filter, and measured for the metal ion concentration in the aqueous solution using an ICP atomic emission spectrometer. The adsorption percentage (5) of metal ions on the adsorbent was calculated from the mass balance. As a result, the adsorption percentage of dysprosium was 96.3%, and the adsorption percentage of neodymium was 65.2%.

Example 2

Preparation of Adsorbent B

(29) A commercially available chelating resin, DIAION CR20 (a polyamine type, manufactured by Mitsubishi Chemical Corporation) (carrier) was added to a solution of diglycolic anhydride in ethanol and allowed to react with each other at 25 C. for 3 days. The resulting reaction product was filtered, sufficiently washed with ethanol and water, and dried under reduced pressure to obtain an adsorbent B.

(30) [Adsorption Test of Adsorbent B]

(31) To 5 ml of an aqueous solution for adsorption test containing 100 ppm each of dysprosium (Dy) and neodymium (Nd) as rare earth elements and 100 ppm each of iron, copper, and zinc as base metals, was added 50 mg of the adsorbent B, and the mixture was subjected to adsorption test at 25 C. with shaking.

(32) After the lapse of a predetermined period of time, the solution was collected, and the adsorption percentage (%) of metal ions on the adsorbent was calculated in the same manner as in Example 1. The results are shown in FIG. 2. The axis of ordinates in FIG. 2 shows the adsorption percentage (%) of each element, and the axis of abscissas shows each elemental species.

(33) As shown in FIG. 2, it was found that a rare earth element dysprosium was able to be more selectively recovered than base metals such as iron, copper, and zinc by using the adsorbent B.

Example 3

Preparation of Adsorbent C

(34) A commercially available amino-silica gel, 3-Aminopropyl Silica Gel (manufactured by Tokyo Chemical Industry Co., Ltd.) (carrier) was added to a solution of diglycolic anhydride in dichloromethane and allowed to react with each other at 25 C. for 3 days. The resulting reaction product was filtered, sufficiently washed with dichloromethane, ethanol, and water, and dried under reduced pressure to obtain an adsorbent C.

(35) [Preparation of Adsorbent D, E, and F]

(36) In the same manner as in the adsorbent C, an adsorbent D was obtained using 3-(Ethylenediamino)propyl Silica Gel (manufactured by Tokyo Chemical Industry Co., Ltd.) as a carrier; an adsorbent E was obtained using 3-(Ethylenediamino)propyl-functionalized silica gel (manufactured by Aldrich Chemical Co.) as a carrier; and an adsorbent F was obtained using 3-(Diethylenetriamino)propyl-functionalized silica gel (manufactured by Aldrich Chemical Co.) as a carrier.

(37) [Adsorption Test of Adsorbents C to F]

(38) To 5 ml of an aqueous solution for adsorption test containing 100 ppm each of dysprosium and neodymium as rare earth elements and 100 ppm each of iron, copper, and zinc as base metals, the solution being adjusted to an arbitrary pH, was added 50 mg of each of the adsorbents C to F, and the mixture was subjected to adsorption test at 25 C. with shaking.

(39) After the lapse of a predetermined period of time, the solution was collected, and the adsorption percentage (%) of metal ions on the adsorbent was calculated in the same manner as in Example 1. The results are shown in FIG. 3 (adsorbent C), FIG. 4 (adsorbent D), FIG. 5 (adsorbent E), and FIG. 6 (adsorbent F). The axis of ordinates in each Figure shows the adsorption percentage (%), and the axis of abscissas shows the pH value of an aqueous solution during adsorption equilibrium.

(40) As shown in FIGS. 3 to 6, the adsorption of copper and zinc on the adsorbent for rare earth element of the present invention was not observed in the pH range tested. With respect to other ions, the adsorption percentage increased as the pH increased. The adsorption of iron was observed at a pH.sub.eq of 1.5 or more, and the adsorption of neodymium was observed at a pH.sub.eq of 0.5 or more. Further, it was found that the adsorbent of the present invention showed a high adsorption capacity for dysprosium even at a pH.sub.eq of 1.

Example 4

Adsorption Test of Adsorbent D (Influence of pH)

(41) To 5 ml of an aqueous solution for adsorption test containing 100 ppm each of dysprosium and neodymium as rare earth elements and 100 ppm each of iron, copper, and zinc as base metals, the initial pH of the solution being adjusted to was added 50 mg of the adsorbent D, and the mixture was subjected to adsorption test at 25 C. with shaking.

(42) After the lapse of a predetermined period of time, the solution was collected, and the adsorption percentage (%) of metal ions on the adsorbent was calculated in the same manner as in Example 1. The results are shown in FIG. 7. The axis of ordinates in FIG. 7 shows the adsorption percentage (%) of each element, and the axis of abscissas shows each elemental species.

(43) As shown in FIG. 7, the adsorption of iron, copper, and zinc which are base metals was not substantially observed. On the other hand, it was found that the adsorbent D showed a high adsorption capacity for dysprosium and neodymium which are rare earth elements even in a low pH region of pH 1, and had high adsorption selectivity to rare earth elements in a system in which base metals are present in combination with rare earth elements.

Example 5

Adsorption Test of Adsorbent D (Measurement of Saturated Adsorption Amount)

(44) To 5 ml of an aqueous solution of dysprosium which is adjusted to arbitrary metal ion concentration and arbitrary pH, was added 50 mg of the adsorbent D, and the mixture was subjected to adsorption test at 25 C. with shaking.

(45) After the lapse of a predetermined period of time, the solution was collected, and the adsorption amount of metal ions on the adsorbent was calculated in the same manner as in Example 1.

(46) Then, as shown in FIG. 8, the adsorption amount of dysprosium was plotted against the concentration of dysprosium during adsorption equilibrium. In FIG. 8, the axis of ordinates indicates the adsorption amount of dysprosium per unit dry weight of an adsorbent (Q [mmol/g]), and the axis of abscissas indicates the concentration of dysprosium in an aqueous solution during equilibrium (Ceq [mmol/L]).

(47) When these results were correlated by the Langmuir equation to calculate the saturated adsorption amount of dysprosium, the saturated adsorption amount of dysprosium was found to be 0.130 mmol/g (21.1 mg/g) and 0.220 mmol/g (35.7 mg/g) at an initial pH of 1 and 3, respectively. Thus, a high adsorption amount was observed even in a low pH region.

Example 6

Preparation of Adsorbent G

(48) To 10 ml of an aqueous solution of dysprosium, the initial pH of the solution being adjusted to 1, was added 100 mg of the adsorbent D, and the mixture was subjected to adsorption test at 25 C. with shaking.

(49) After the lapse of a predetermined period of time, the solution was collected, and the adsorption amount (%) of metal ions on the adsorbent was calculated in the same manner as in Example 1. Then, the adsorbent was filtered, washed with water, and dried under reduced pressure to obtain an adsorbent G.

(50) [Recovery Test from Adsorbent G Prepared by Allowing Rare Earth Element (Dysprosium) to be Adsorbed on Adsorbent D]

(51) To 5 mL of a hydrochloric acid aqueous solution adjusted to an arbitrary pH, was added 10 mg of the adsorbent G, and the mixture was shaken at 25 C.

(52) After the lapse of a predetermined period of time, the solution was collected, filtered with a 0.20-m membrane filter, and measured for the metal ion concentration in the aqueous solution using an ICP atomic emission spectrometer. The desorption ratio of dysprosium ions was calculated from the mass balance. The results are shown in FIG. 9. The axis of ordinates in FIG. 9 shows the desorption ratio (%), and the axis of abscissas shows the arbitrarily adjusted pH values of the hydrochloric acid aqueous solution.

(53) It was observed that the desorption ratio of dysprosium increased as the pH of hydrochloric acid was reduced, and that the adsorbed dysprosium can be easily and almost quantitatively collected with 1 mol/L (1 N) of hydrochloric acid.

Example 7

Separation and Recovery of Rare Earth Element, Application of Extraction

(54) To 5 ml of an aqueous solution for adsorption test containing 20 ppm each of 14 types of lanthanoid ions excluding promethium (lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium), the initial pH of the solution being adjusted to 1, was added the adsorbent D, and the mixture was subjected to adsorption test with shaking.

(55) After the lapse of a predetermined period of time, the aqueous solution was collected, and the adsorption percentage of metal ions on the adsorbent was calculated in the same manner as in Example 1. The results are shown in FIG. 10. The axis of ordinates in FIG. 10 shows the adsorption percentage (%), and the axis of abscissas shows the elements to be inspected.

(56) It was found that, as the tendency of adsorption, the adsorbent D had higher adsorption percentage for light rare earth elements from lanthanum to neodymium as the atomic number increases. On the other hand, the adsorbent D had uniformly high adsorption percentage for medium-to-heavy rare earth elements after samarium.

(57) From these findings, the possibility of mutual separation between rare earth elements was verified in the light rare earth elements from lanthanum to samarium. Particularly, the possibility of separating industrially important praseodymium and neodymium was verified.

Example 8

(58) Next, the specific surface area, the average pore size, and the whole pore volume of the adsorbent D prepared and amino-silica gel, 3-(Ethylenediamino)propyl Silica Gel, (carrier) before introducing diglycolamic acid were investigated with conventional techniques. The results are shown in FIG. 11.

(59) As shown in FIG. 11, it was found that the specific surface area, the average pore size, and the whole pore volume of the amino-silica gel were not substantially changed, and the pores were not blocked even when diglycolamic acid was introduced into the amino-silica gel by chemical bonds. This means that diglycolamic acid is introduced even into the silica gel (base material) surface in the inner part of the carrier. Thereby, the high adsorption rate of rare earth elements can be achieved.

Example 9

(60) Next, the adsorbent D was investigated for the adsorption rate. To an aqueous solution for adsorption test adjusted to a dysprosium concentration of 1 mM and a pH of 1, was added the adsorbent D prepared, and the mixture was subjected to adsorption test at 298K with shaking. The solution was collected after an arbitrary time period, filtered with a 0.20-m membrane filter, and measured for the metal ion concentration in the aqueous solution using an ICP atomic emission spectrometer. The adsorption percentage of metal ions was calculated from the mass balance. The results are shown in FIG. 12.

(61) As apparent from the change of the dysprosium adsorption percentage with time when the adsorbent D was used as shown in FIG. 12, the equilibrium adsorption was almost reached 10 minutes after the start of adsorption. This adsorption rate is sufficiently practical even if it is compared with commercially available ion-exchange resins and the like.

Example 10

(62) Next, the adsorbent D was investigated for adsorption selectivity. A glass column having an inside diameter of 8 mm was filled with 1 g of the adsorbent D prepared (the height of the filled layer: 3.6 cm), and a hydrochloric acid aqueous solution adjusted to a pH of 1 was sufficiently passed through the column. An aqueous solution containing dysprosium and neodymium as rare earth elements and iron, copper, and zinc as base metals (the concentration of each metal ion: 1 mM, and the initial pH: 1) was passed through the column filled with the adsorbent at a constant flow rate (0.25 mL/min), and the effluent was collected. Subsequently, a cleaning liquid (a hydrochloric acid aqueous solution having a pH of 2) and a desorption liquid (a 2 M hydrochloric acid aqueous solution) were successively passed through the column, and the effluent was collected. Each fraction collected was measured for the metal ion concentration in the aqueous solution using an ICP atomic emission spectrometer. The adsorption amount of metal ions was calculated from the mass balance. The results are shown in FIG. 13.

(63) Immediately after the adsorption liquid was passed through the column, copper, iron, and zinc which are base metals flowed out without interacting with the adsorbent D in the column. On the other hand, dysprosium and neodymium which are rare earth elements were held in the column. When the amount of the adsorption liquid reached a certain level, neodymium reached a breakthrough point and started to flow out at a concentration higher than the initial concentration. This is probably because dysprosium has higher adsorptivity to the adsorbent D than neodymium, and adsorbed neodymium was replaced by dysprosium. When the 2 M hydrochloric acid aqueous solution was passed through the column for desorption after dysprosium reached a breakthrough point, copper, iron, and zinc which are base metals were not substantially contained in the desorption liquid, and only rare earth elements was able to be recovered. Dysprosium was concentrated to about 15 times the initial concentration.

Example 11

(64) Next, the adsorbent D was investigated for the resistance to repeated use. In order to check the degradation in the repeated use of the adsorbent D, the same column test as in Example 10 was performed again. The behavior of the adsorption and desorption of each element was almost the same between the first time and the second time. FIG. 14 shows the integrated adsorption amount of dysprosium and neodymium.

(65) As shown in FIG. 14, the integrated adsorption amount when dysprosium reached a breakthrough point was Dy: 15.25 mg/g and Nd: 1.760 mg/g at the first time and Dy: 14.63 mg/g and Nd: 2.080 mg/g at the second time. It was found that the adsorbent D was able to be repeatedly used because there was substantially no difference in the adsorption amount for both dysprosium and neodymium.

INDUSTRIAL APPLICABILITY

(66) According to the present invention, rare earth elements can be selectively, simply, and inexpensively recovered from an aqueous solution, even from a dilute aqueous solution, containing rare earth elements. Therefore, the present invention can further develop the smelting and the recycling industry of rare earth elements.

REFERENCE SIGNS LIST

(67) 1 Rare earth element adsorbent 2 Carrier 2a Base material 2b Primary amine 2c Secondary amine 2d Carrier 3 Diglycolic Anhydride 3a Diglycolic acid 4 Diglycolamic Acid 4a Amide group