JP2810981B2 - Method for producing copper hexacyanoferrate (II) -supported porous resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an improvement in a method for producing a porous resin carrying copper hexacyanoferrate (II). More specifically, the present invention is useful as an ion exchanger for cesium separation, has a high cesium adsorption capacity, and in the cesium adsorption / desorption treatment, there is almost no loss of active components, and copper ions are extremely desorbed. The present invention relates to a method for efficiently producing a small amount of copper hexacyanoferrate (II) -supported porous resin.

[0002]

2. Description of the Related Art Cesium separation and recovery technologies include radioactive cesium separation and recovery in waste liquid containing nitric acid and sodium nitrate as a main component generated from facilities related to the use of nuclear power such as a spent fuel reprocessing facility. It is an extremely important technology that can be applied to the removal of radioactive cesium from beverages such as milk contaminated with radioactive cesium and the recovery of cesium contained in waste geothermal water.

As a cesium separating material, a complex of copper hexacyanoferrate (II) and a porous anion exchange resin has been known [Journal of Nuclear Science and Technology (hereinafter referred to as "Journal of Nuclear Technology"). J. Nuc
l. Sci. Technol. 2), No. 8, pages 321-322 (1965)]. However, this composite had the disadvantage that it could not be regenerated after use and that a new one had to be used each time.

Accordingly, the present inventors have conducted various studies and have previously found a method for producing a composite of copper hexacyanoferrate (II) and a porous anion exchange resin which can be used repeatedly (Japanese Patent Application In the composite obtained by this method, in order to prevent the loss of copper hexacyanoferrate (II) as an active ingredient during the adsorption and desorption treatment of cesium, the composite is subjected to regeneration treatment. It is necessary to add a copper salt, which requires addition of a new chemical, and has drawbacks that are not preferable for industrial practice, such as generation of a waste solution containing copper, which is a harmful heavy metal. Furthermore, in order to add a copper salt during regeneration, not only during the first cesium adsorption,
At the time of adsorption after regeneration, copper ions are desorbed and eluted in the adsorption treatment solution. For example, when used to remove radioactive cesium from milk contaminated with radioactive cesium, etc. Vol. 6, No. 8, 497-50
3 (1968)], insoluble hexacyanoiron (I
I) The exchangeable heavy metal substituted for cesium from the heavy metal salt of acid migrates into milk, and the heavy metal is mixed into waste geothermal water when recovering cesium from waste geothermal water. there were.

By the way, if copper hexacyanoferrate (II) can be supported in the pores of a porous resin having no functional group, many of the problems so far can be solved. By the impregnation method known as a general method of introducing a chemical substance into the pores of a porous material having no
To introduce an insoluble substance such as copper hexacyanoferrate (II), it is necessary to carry out two steps. In the latter impregnation operation, the salt impregnated in the former step is re-eluted, and a large amount is contained in the solution outside the resin. It is extremely difficult to convert this by-produced copper hexacyanoferrate (II) into soluble hexacyanoferrate (II) and copper salt as raw materials and to reuse it.

[0006]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a method for forming a porous resin pore having no functional group,
Copper hexacyanoferrate (II) is efficiently supported without using the impregnation method, and the cesium adsorption capacity is high, and in the cesium adsorption / desorption treatment, there is almost no loss of the active ingredient and the copper ion desorption is extremely small. An object of the present invention is to provide a method for producing a porous resin carrying copper hexacyanoferrate (II) which can be repeatedly used as an ion exchanger for separating cesium.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a porous resin carrying a quaternary ammonium salt has been found to be one type of porous resin that is stable in water. Paying attention to the fact that it behaves as an anion exchange resin, by using this porous resin carrying a quaternary ammonium salt, copper hexacyanoferrate (II) can be easily deposited in the resin pores by a known method. Have been found that the quaternary ammonium salt can be easily separated and recovered from the resin, and based on this finding, the present invention has been completed.

That is, the present invention provides a porous resin in which a quaternary ammonium salt that is soluble in a low-boiling organic solvent and hardly soluble in water is supported, and further treated with an aqueous solution containing hexacyanoferrate (II). After that, the treated product is brought into contact with an aqueous solution containing a copper salt to form hexacyanoiron (II) in the pores of the resin.
An object of the present invention is to provide a method for producing a copper hexacyanoferrate (II) -supported porous resin, comprising depositing copper acid and then extracting a quaternary ammonium salt in the resin with a low-boiling organic solvent.

[0009]

DETAILED DESCRIPTION OF THE INVENTION In the method of the present invention, a porous resin having no functional group is preferably used. As a porous resin without this functional group, acrylic acid, which is more compatible with water and easier to handle in an aqueous solution, than non-polar and highly water-repellent resins such as styrene-divinylbenzene copolymer A micropolar porous resin containing an oxygen atom in a structure such as an ester or methacrylate polymer is particularly preferable.

As the quaternary ammonium salt, a quaternary ammonium salt that is soluble in a low-boiling organic solvent and hardly soluble in water is used. As such a quaternary ammonium salt, trioctylammonium chloride, trioctylethylammonium chloride, trioctylpropylammonium chloride and the like are preferable because they have a sufficiently long alkyl chain and are easily available.

In the present invention, first, it is necessary to support these quaternary ammonium salts on the porous resin. As this loading method, for example, a porous resin is added to a solution obtained by dissolving a quaternary ammonium salt in an appropriate organic solvent, and after the solution is sufficiently penetrated into the pores of the porous resin, the solvent is removed. A method is used in which the quaternary ammonium salt adhering to the outer surface of the resin is distilled off, and then the excess quaternary ammonium salt is washed and removed with a low-boiling organic solvent that does not elute the quaternary ammonium salt carried inside the resin. As the organic solvent for washing, petroleum ether is preferable.

Next, the resin carrying the quaternary ammonium salt is treated with an aqueous solution containing hexacyanoferrate (II) to adsorb hexacyanoferrate (II) ions. The adsorption of hexacyanoferrate (II) ions proceeds relatively quickly, but in order to prevent the quaternary ammonium salt from being eluted, the aqueous solution containing hexacyanoferrate (II) preferably has a sufficiently high concentration. Used. Since the hexacyanoferrate (II) ion is selectively captured by the quaternary ammonium group, the treatment liquid after the solid-liquid separation is treated with hexacyanoferrate (II) equivalent to the consumption amount.
It can be reused simply by adding an acid ion. Excess adhering hexacyanoferrate (II) is removed by washing with water.
It is not preferable that the quaternary ammonium salt be eluted during the washing with water. Therefore, it is advantageous to select a quaternary ammonium salt that has a strong bond with the hydrophobic group on the inner surface of the resin and does not elute during the washing with water. As the hexacyanoferrate (II), for example, potassium hexacyanoferrate (II) (potassium ferrocyanide), sodium hexacyanoferrate (II) (sodium ferrocyanide) and the like are preferable.

Next, the hexacyanoiron (I)
I) Contacting the resin treated with the aqueous solution containing a salt with an aqueous solution containing a copper salt. In this treatment, the permeation of the copper salt with donan is enhanced to prevent hexacyanoferrate (II) ions from being eluted into the external solution, and the reaction formula

Embedded image (Wherein R ¹ , R ² and R ³ are a long-chain alkyl group, R ⁴ is a lower alkyl group, X is a negative atom or atomic group such as a halogen atom, and n is a valence of X) In order to efficiently deposit copper hexacyanoferrate (II) in the resin pores, it is preferable to use a copper salt-containing aqueous solution having a concentration as high as possible.

As can be seen from the above reaction formula (I), the liberated quaternary ammonium salt is an acid radical (X
^{Although a} salt having ^n- ) is obtained, it is preferable to select a copper salt to be used in consideration of its properties. Usually, it is advantageous to use a copper salt having the same acid group as that of the quaternary ammonium salt used, and cupric chloride is particularly preferable.

The resin in which the copper hexacyanoferrate (II) is deposited in the pores is subjected to solid-liquid separation by a known method, and then washed with water until Cu ²⁺ is hardly detected. However, excessive washing is not preferable because the quaternary ammonium salt is easily eluted and the liquid foams. In addition, the copper salt aqueous solution after the solid-liquid separation can be used repeatedly by replenishing the consumed copper salt.

Next, the resin washed with water is treated with a low-boiling organic solvent having high solubility in quaternary ammonium salts to extract the quaternary ammonium salts in the resin. Is distilled off to recover a quaternary ammonium salt.
As the organic solvent, ketones having a low boiling point such as acetone are preferable because they have excellent extraction performance.

Thus, hexacyanoiron (II)
The copper oxide-carrying porous resin can be obtained efficiently. This one is
Although it can be used as it is as an ion exchanger for cesium separation, the pretreatment as shown below significantly improves the cesium adsorption capacity and reduces the loss of active ingredients during the cesium adsorption / desorption treatment. Almost gone. That is, first, copper hexacyanoferrate (II) in a porous resin is oxidized to copper hexacyanoferrate (III) with an oxidizing agent, for example, an aqueous nitric acid solution containing nitric acid, and then a reducing agent, for example, an aqueous nitric acid solution containing hydrazine nitrate is used. Thus, the reduction treatment is performed without adding a copper salt. Since no copper salt is added, almost all products resulting from the reduction of copper hexacyanoferrate (III) are A ₂ Cu ₃ [Fe (CN)
₆ ] ₂ (A ⁺ : monovalent cation) is a double salt type, and the cesium adsorption ability is remarkably improved. In addition, copper ion, hexacyanoferrate (II) ion, hexacyanoferrate (III) ) The elution of acid ions is extremely low, and there is almost no loss of the active ingredient.

Next, adsorption and desorption of cesium by the porous resin carrying copper hexacyanoferrate (II) obtained by the method of the present invention or a pretreated product thereof (hereinafter referred to as a cesium separating material) and a regeneration treatment after desorption. First, the cesium-containing aqueous solution is brought into sufficient contact with the cesium separating material to cause cesium to be adsorbed on the separating material. Next, the cesium-adsorbed separating material is oxidized with an oxidizing agent, for example, an aqueous nitric acid solution containing nitric acid to desorb cesium. Next, the separation material to which cesium has been desorbed can be regenerated by reducing treatment with a reducing agent, for example, an aqueous nitric acid solution containing hydrazine nitrate without adding a copper salt. As described in the reduction treatment in the pretreatment of the cesium separation material, the separation material thus regenerated has a high adsorption ability, and in the subsequent adsorption / desorption treatment, copper ions and hexacyanoiron ( II) Elution of acid ions and hexacyanoferrate (III) ions is suppressed to a very low level, and there is almost no loss of active ingredients.

[0019]

According to the present invention, copper hexacyanoferrate (II) is efficiently carried in the pores of a porous resin having no functional group, so that the cesium adsorption capacity is high and the cesium absorption capacity is high. In the desorption treatment, it is possible to easily produce a copper hexacyanoferrate (II) -supported porous resin which hardly loses the active ingredient, has very little copper ion desorption, and can be repeatedly used as an ion exchanger for cesium separation. it can.

The copper hexacyanoferrate (II) -supported porous resin obtained by the method of the present invention can be used, for example, to separate cesium from various radioactive waste liquids, remove radioactive cesium from beverages such as milk contaminated with radioactive cesium, It is useful for recovery of cesium from waste geothermal water.

[0021]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Commercially available trioctylmethylammonium chloride 1.016
g _{[[R 3 (CH 3) N} ] Cl (R: C 8 ~C 10), Nacalai Tesque, content: 87.3 wt%] after was dissolved in petroleum ether 20 ml, Amberlite XAD-7
(Rohm and Haas) 2 g (dry weight basis)
Was added and petroleum ether was distilled off while degassing under reduced pressure of a water jet pump. Then, wash with petroleum ether 3
After repeating this process, the product was vacuum-dried at 50 ° C. to completely remove petroleum ether. The supported amount of trioctylmethylammonium chloride after washing was 0.852 g.

Next, 20 ml of an aqueous solution of potassium hexacyanoferrate (II) having a concentration of 0.5 mol / liter was added thereto, and the mixture was degassed under a reduced pressure of a water pump until almost no bubbles were generated. mixed. Next, after the solid-liquid separation, the solid was sufficiently washed with water and shaken for 24 hours in 60 ml of a 1 mol / liter cupric chloride aqueous solution at 25 ° C. The resin turned deep red-purple and no precipitate was found in the solution.

Next, the resultant was filtered using a polytetrafluoroethylene membrane filter attached to a membrane holder, and washed with water until copper ions were hardly detected. Thereafter, about 15 ml of acetone was added, and the mixture was stirred in a holder to extract trioctylmethylammonium chloride, and then the operation of filtering was repeated until almost no extraction was obtained. The amount of trioctylmethyl ammonium chloride recovered by distilling off acetone from the extract was 0.7
53 g (88.4% recovery). When XAD-7 in the membrane holder was transferred to a container together with water, the XAD-7 was easily floated. Almost no precipitation of copper hexacyanoferrate (II) was found in the solution. After removing the supernatant and air-drying, vacuum-dry at 60 ° C to obtain hexacyanoiron (II).
2.178 g of copper acid-supported XAD-7 was obtained.

Example 2 Commercially available trioctylpropyl ammonium chloride 0.97
After dissolving 7 g (manufactured by Kodak, content: 97.1% by weight) in 20 ml of acetone, Amberlite XAD-7 was dissolved.
2 g (dry weight basis) was added, and acetone was distilled off while degassing under reduced pressure of a water jet pump. Thereafter, washing with petroleum ether was repeated three times, followed by vacuum drying at 50 ° C. to completely remove petroleum ether. The supported amount of trioctylpropyl ammonium chloride after washing is 0.904.
g.

Next, 20 ml of a 0.5 mol / liter aqueous solution of potassium hexacyanoferrate (II) was added thereto, and the mixture was degassed under a reduced pressure of a water-jet pump until almost no bubbles were generated, followed by shaking at 25 ° C. for 24 hours. mixed. Next, after the solid-liquid separation, the solid was sufficiently washed with water and shaken for 24 hours in 60 ml of a 1 mol / liter cupric chloride aqueous solution at 25 ° C. The resin turned deep red-purple and no precipitate was found in the solution.

Next, the resultant was filtered using a polytetrafluoroethylene membrane filter attached to a membrane holder, and washed with water until copper ions were hardly detected. Thereafter, about 15 ml of acetone was added thereto, and the mixture was stirred in a holder to extract trioctylpropylammonium chloride, and then the operation of filtering was repeated until almost no extraction was performed. The amount of trioctylpropylammonium chloride collected by distilling off acetone from the extract was 0.823 g (recovery rate 91.0%). When XAD-7 in the membrane holder was transferred to a container together with water, the XAD-7 was easily floated. Almost no precipitation of copper hexacyanoferrate (II) was found in the solution. After removing the supernatant and air-drying, vacuum drying at 60 ° C.
I) 2.151 g of copper-acid-supported XAD-7 was obtained.

Application Example 1 X supported on copper hexacyanoferrate (II) prepared in Example 1
0.1078 g of AD-7 is placed in an Erlenmeyer flask, and water 1
0 ml was added, and the mixture was degassed under reduced pressure by a water pump until foaming was not generated. Next, filtration was performed under reduced pressure (hereinafter simply referred to as filtration) using a polytetrafluoroethylene membrane filter attached to a 25 mm diameter membrane holder (capacity: 15 ml) to perform solid-liquid separation. Then 10 ^{-3 in} 1 liter
Aqueous solution 1 containing mol CsNO ₃ and 3 mol NaNO ₃
While washing the membrane holder with 0 ml, all were transferred to an Erlenmeyer flask, shaken for 1 hour to adsorb cesium, and then filtered. After thorough washing, 10 ml of an aqueous solution containing 10 ⁻³ mol of NaNO ₂ and 5 mol of HNO ₃ in 1 liter
All the resin particles were transferred to an Erlenmeyer flask while washing the membrane holder with and shaken for 24 hours to desorb cesium.

As a result of analyzing the filtrate and the washing solution, the cesium adsorption rate was 31.8% (excluding the portion removed by water washing; the same applies hereinafter), and the cesium desorption rate was 85.3% (the portion that migrated to the washing water). The same applies hereinafter.) The amounts of iron and copper in the treatment solution after adsorption were 0.16 ppm and 4.
The concentration of iron and copper in the treatment liquid after desorption was 7.63 ppm and 30.4 ppm, respectively.

Next, an aqueous solution 10 containing 0.015 mol of hydrazine nitrate and 0.1 mol of HNO ₃ in 1 liter
ml was added to the membrane holder to perform a regeneration treatment (the tip of the funnel was plugged in order to prevent the liquid from dropping).
The mixture was stirred occasionally for about 1 hour until almost no air bubbles were generated, left for 30 minutes, filtered and washed with water. The concentrations of iron and copper in the treated solution after the regeneration were 1.24 ppm and 0.0 ppm, respectively.

Using the sample thus regenerated, the second adsorption / desorption operation was performed in the same manner as described above. As a result, the cesium adsorption rate was 84.2%, and the cesium desorption rate was 8%.
It was 9.4%. The concentrations of iron and copper in the treatment liquid after adsorption were 0.19 ppm and 0.0 ppm, respectively, and the concentrations of iron and copper in the treatment liquid after desorption were 0.66 ppm and 3.7 ppm, respectively. there were.

As described above, hexacyanoiron (II) prepared through trioctylmethylammonium chloride
Regarding the copper-acid-supported XAD-7, the first time the cesium adsorption rate is low and the copper concentration in the treatment solution is high, but after regeneration, the adsorption rate is high and the copper concentration is considerably reduced. In addition, even when the regeneration treatment was performed without addition of copper ions, it was confirmed that the elution of iron in the subsequent adsorption / desorption treatment was sufficiently low.

Application Example 2 X supported on copper hexacyanoferrate (II) prepared in Example 2
About 0.1078 g of AD-7, the first adsorption / desorption operation was performed under the same conditions as in Application Example 1. As a result, the cesium adsorption rate was 31.2%, and the cesium desorption rate was 79.1%. In addition, the concentration of iron and copper in the treatment solution after adsorption is
It is 0.36 ppm and 2.9 ppm, respectively, and the concentration of iron and copper in the treatment liquid after desorption is 3.65 p
pm and 18.4 ppm. Next, as a result of performing a regeneration treatment under the same conditions as in Application Example 1, the concentrations of iron and copper in the treated solution after regeneration were 0.28 ppm and 0.3, respectively.
ppm.

Next, a second adsorption / desorption operation was performed using the regenerated sample in the same manner as described above. As a result, the cesium adsorption rate was 68.7% and the cesium desorption rate was 92.0%. . The concentrations of iron and copper in the treatment solution after adsorption were 0.36 ppm and 0.0 ppm, respectively, and the concentrations of iron and copper in the treatment solution after desorption were 0.90 ppm and 2.8 ppm, respectively. .

As described above, hexacyanoiron (I) prepared through the mediation of trioctylpropylammonium chloride
I) Regarding the copper-acid-supporting XAD-7, the first time, the cesium adsorption rate is low and the copper concentration in the treatment liquid is high, but after regeneration, the adsorption rate is high and the copper concentration is considerably reduced. In addition, even when the regeneration treatment was performed without addition of copper ions, it was confirmed that the elution of iron in the subsequent adsorption / desorption treatment was sufficiently low.

Application Example 3 Copper hexacyanoferrate (II) supported on X prepared in Example 1
0.1075 g of AD-7 is placed in an Erlenmeyer flask, and water 1 is added.
0 ml was added, and the mixture was degassed under reduced pressure by a water pump until foaming was not generated. Next, solid-liquid separation was performed by filtration under reduced pressure using a polytetrafluoroethylene membrane filter attached to a membrane holder having a diameter of 25 mm (capacity: 15 ml).

Next, 10 ^-3 mol of NaN per liter was used.
While washing the membrane holder with 10 ml of an aqueous solution containing O ₂ and 5 mol of HNO ₃ , all the resin particles were transferred to an Erlenmeyer flask, shaken for 24 hours, oxidized, filtered, sufficiently washed, and then washed in 1 liter. An aqueous solution 10 containing 0.015 mol of hydrazine nitrate and 0.1 mol of HNO ₃
ml was added to the membrane holder to perform a reduction treatment (a stopper was plugged at the tip of the funnel to prevent the liquid from dropping).
The mixture was stirred occasionally for about 1 hour until almost no air bubbles were generated, left for 30 minutes, filtered and washed with water.

With respect to the sample thus pretreated,
The first adsorption / desorption operation was performed under the same conditions as in Application Example 1.
That is, 10 ^-3 moles of CsNO ₃ and 3
While washing the membrane holder with 10 ml of an aqueous solution containing molar NaNO ₃ ,
After shaking for a time to adsorb cesium, the mixture was filtered.
After thorough washing, 10 ^-3 mol of NaNO ₂ and 5
All resin particles were transferred to an Erlenmeyer flask while washing the membrane holder with 10 ml of an aqueous solution containing molar HNO _3, and shaken for 24 hours to desorb cesium.

As a result of analyzing the filtrate and the washing solution, the cesium adsorption rate was 78.7% and the cesium desorption rate was 96.6%. The amounts of iron and copper in the treatment solution after adsorption were 0.27 ppm and 0.0 ppm, respectively, and the concentrations of iron and copper in the treatment solution after desorption were 0.76 ppm and 4.6 ppm, respectively. there were.

Next, a reproduction process was performed under the same conditions as in the first application example. That is, an aqueous solution containing 0.015 mol of hydrazine nitrate and 0.1 mol of HNO ₃ in 1 liter
1 was added to the membrane holder to perform a regeneration treatment (the tip of the funnel was plugged in order to prevent the liquid from dropping).
The mixture was stirred occasionally for about 1 hour until almost no air bubbles were generated, left for 30 minutes, filtered and washed with water. The concentrations of iron and copper in the treated solution after regeneration were 0.86 ppm and 0.0 ppm, respectively.

Using the sample thus regenerated, the second adsorption / desorption operation was performed in the same manner as described above. As a result, the cesium adsorption rate was 83.1%, and the cesium desorption rate was 9%.
It was 4.8%. The concentrations of iron and copper in the treatment solution after adsorption were 0.20 ppm and 0.0 ppm, respectively, and the concentrations of iron and copper in the treatment solution after desorption were 0.84 ppm and 3.1 ppm, respectively. there were.

Thus, hexacyanoiron (II) prepared through the mediation of trioctylmethylammonium chloride
For the copper-acid-carrying XAD-7, by performing a reduction treatment following the oxidation treatment as a pretreatment, a treatment with a high cesium adsorption rate can be performed from the first time, and the concentration of iron and copper in each treatment liquid is suppressed to a low level. be able to.

Application Example 4 Copper hexacyanoferrate (II) supported on X prepared in Example 2
0.1078 g of AD-7 is placed in an Erlenmeyer flask, and water 1
0 ml was added, and the mixture was degassed under reduced pressure by a water pump until foaming was not generated. Next, filtration was performed under reduced pressure using a polytetrafluoroethylene membrane filter attached to a membrane holder having a diameter of 25 mm (capacity: 15 ml). Next, application example 3
After performing the oxidation treatment and the subsequent reduction treatment under the same conditions as those described above, the first adsorption / desorption operation was performed. As a result, the cesium adsorption rate was 69.0%, and the cesium desorption rate was 90.9%. In addition, the concentration of iron and copper in the treatment solution after adsorption is
0.36 ppm and 0.0 ppm, respectively, and the concentration of iron and copper in the treatment liquid after desorption was 0.88 p
pm and 3.6 ppm. Next, as a result of performing a regeneration process under the same conditions as in Application Example 3, the concentrations of iron and copper in the treated solution after regeneration were 0.25 ppm and 0.0 pp, respectively.
m.

Using the sample thus regenerated, the second adsorption / desorption operation was performed in the same manner as described above. As a result, the cesium adsorption rate was 71.6%, and the cesium desorption rate was 9%.
3.8%. The concentrations of iron and copper in the treatment solution after adsorption were 0.43 ppm and 0.0 ppm, respectively, and the concentrations of iron and copper in the treatment solution after desorption were 0.64 ppm and 2.5 ppm, respectively. there were.

Thus, the hexacyanoiron (I) prepared through the mediation of trioctylpropylammonium chloride
I) Regarding copper-acid-supporting XAD-7, by performing a reduction treatment following an oxidation treatment as a pretreatment, a treatment with a high cesium adsorption rate can be performed from the first time, and the iron and copper concentrations in each treatment solution can be reduced. It can be kept low.

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Claims (4)

(57) [Claims] 1. A quaternary ammonium salt which is soluble in a low boiling point organic solvent and hardly soluble in water is supported on a porous resin,
After further treatment with an aqueous solution containing hexacyanoferrate (II), the treated product is brought into contact with an aqueous solution containing copper salt to deposit copper hexacyanoferrate (II) in pores of the resin,
Next, a method for producing a porous resin carrying copper hexacyanoferrate (II), comprising extracting a quaternary ammonium salt in the resin with an organic solvent having a low boiling point. 2. The method according to claim 1, wherein the porous resin is a slightly polar resin having no functional group. 3. The method according to claim 1, wherein the quaternary ammonium salt is trioctylmethylammonium chloride, trioctylethylammonium chloride or trioctylpropylammonium chloride. 4. The method according to claim 1, wherein the hexacyanoferrate (II) copper-supported porous resin is used as a cesium separating material.