Purification method for purifying water in a spent fuel pool in a nuclear power plant

Abstract

A method for purifying water in a spent fuel pool in a nuclear power plant, the method including passing the water at a linear flow velocity of 50 m/h or less through a purification apparatus. The apparatus includes an ion exchange resin layer and a metal-doped resin layer laid at a bed height of 2 cm or more on a surface layer of the ion exchange resin layer. The method includes contacting the water with the metal-doped resin layer to decompose a pro-oxidant contained in the water and subsequently contacting the water with the ion exchange resin to produce purified water.

Claims

1. A method for purifying water in a spent fuel pool in a nuclear power plant, the method comprising: passing the water at a linear flow velocity of from 30 m/h or more to about 50 m/h or less through a purification apparatus, wherein the apparatus comprises an ion exchange resin layer and a metal-doped resin layer laid at a bed height of from about 2 cm or more to about 10 cm or less on a surface layer of the ion exchange resin layer; contacting the water with the metal-doped resin layer to decompose a pro-oxidant contained in the water, wherein the pro-oxidant comprises hydrogen peroxide; and subsequently contacting the water with the ion exchange resins to produce purified water, wherein a decomposition rate of hydrogen peroxide in the purified water is 90% or more.

2. The method according to claim 1, wherein the metal in the metal-doped resin layer is selected from the group consisting of fine particles of palladium, platinum, manganese, iron, and titanium.

3. The method according to claim 1 or 2, wherein the pro-oxidant further comprises a hydroperoxyl radical, a hydroxyl radical, or combination thereof.

4. The method according to claim 1 or 2 further comprising recycling the purified water to the spent fuel pool to cool the spent fuel.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic flow diagram of a water treatment apparatus of the present invention for treating spent fuel pool water from a nuclear power plant.

(2) FIG. 2 is a graph showing treatment results of Example 1.

(3) FIG. 3 is a graph showing treatment results of Example 2.

(4) FIG. 4 is a graph showing treatment results of Example 3.

PREFERRED EMBODIMENTS

(5) The present invention is described below with reference to the attached drawings, but they are not intended to limit the scope of the invention.

(6) FIG. 1 outlines a flow in a water treatment apparatus of the present invention for treating spent fuel pool water that is obtained from a nuclear power plant. A spent fuel pool 1 is filled with cooling water for cooling storage of a spent fuel rod that is removed from a nuclear reactor (This cooling water is also referred to as spent fuel pool water). Since the spent fuel rod that is removed from a nuclear reactor continues emitting radiation even while being stored in fuel pool water, the spent fuel pool water is decomposed by the radiation to generate hydrogen peroxide, hydroxyl radicals or hydroperoxyl radicals. The spent fuel pool water (water to be treated) that is removed from the spent fuel pool 1 (a storage tank for the water to be treated) is transferred via a transfer pump 2 to a fuel pool purification device 3. The fuel pool purification device 3 comprises an ion exchange resin layer 3a in which ion exchange resins are filled and a metal-doped resin layer 3b in which metal-doped resins are filled at a bed height of about 2 cm or more, preferably 5 cm or more, on a surface layer of the ion exchange resin layer 3a. When the bed height is less than about 2 cm, pro-oxidants are not well decomposed. The upper limit of the bed height of the metal-doped resin layer 3b is not particularly limited; however, since a bed height exceeding about 10 cm results in the decreases of the flow velocity and the volume of the treated water, an appropriate bed height should be determined. The pro-oxidants contained in the spent fuel pool water are decomposed when passing through the metal-doped resin layer 3b. Subsequently, impurity ions are removed through the ion exchange resin layer 3a. The demineralized water is recycled to the spent fuel pool 1 as cooling water. The flow volume of water to be treated through the demineralizer 3 is based on a linear flow velocity of about 10 to about 50 m/h. When the linear flow velocity is less than about 10 m/h, the volume of the circulated water is decreased and its cooling effect on the spent fuel rod is diminished. When the linear flow velocity exceeds about 50 m/h, the efficiency of contact of the pro-oxidants with the metal-doped resin is reduced and its capability to decompose the pro-oxidants is diminished.

(7) The ion exchange resin used in the present invention may be a common ion exchange resin that is used in purification apparatuses for spent fuel pool water from nuclear power plants, and is preferably a mixed bed anion and cation exchange resin. For example, a mixed bed ion exchange resin (SNM1, a product of Mitsubishi Chemical Corp.) is suitable.

(8) The metal-doped resin used in the present invention is preferably a strongly basic gel-type spherical resin formed of a polymer resin on which metal particles selected from palladium, platinum, manganese, iron and titanium fine particles are doped.

EXAMPLES

(9) The present invention is described below in more detail by means of examples.

Example 1

(10) A metal-doped resin was used to examine its capability to decompose hydrogen peroxide in an immersion test.

(11) The metal-doped resin was the Pd-doped resin Lewatit (registered trademark) K7333, a product of Lanxess. To a 200 ml beaker, 100 ml of a solution to be treated (Sample 1) containing H.sub.2O.sub.2 in a concentration of 20 mg/L and boric acid dissolved in a concentration of 2800 mg/L (as B) was added, 1 ml of the Pd-doped resin was added, and the hydrogen peroxide concentration was determined with time. These hydrogen peroxide and boron concentrations were applied to simulate the quality of fuel pool water that is obtained from a pressurized-water reactor (PWR) nuclear power plant. For reference, the same test was conducted with a boric acid-free solution, i.e., water containing only hydrogen peroxide (This solution is referred to as Sample 2). The hydrogen peroxide concentration was calculated based on absorbance measured at a wavelength of 350 nm with a spectrophotometer by iodometry (Atomic Energy Society of Japan: PWR Standard Chemical Analysis 2006). The results are shown in Table 1 and FIG. 2.

(12) TABLE-US-00001 TABLE 1 Immersion Conc. (mg/L) of hydrogen peroxide time (min) Control Sample 2 Sample 1 0 19.4 19.4 19.4 60 19.4 12.1 12.0 120 19.5 10.8 10.5 180 19.6 9.5 9.8 240 19.5 8.8 9.0

(13) FIG. 2 shows that the Pd-doped resin had such a high capability to decompose hydrogen peroxide that about 50% or more of contained hydrogen peroxide was decomposed at about 2 hours after the start of immersion. The influence of contained boric acid on the capability to decompose hydrogen peroxide was not observed.

Example 2

(14) A metal-doped resin was used to examine its capability to decompose hydrogen peroxide in a test in which hydrogen peroxide-containing water was passed through a column.

(15) The metal-doped resin, which was the Pd-doped resin Lewatit (registered trademark) K7333, a product of Lanxess, was filled at a bed height of about 1 to about 10 cm in a glass column with an inside diameter of about 16 mm. An untreated water comprising H.sub.2O.sub.2 adjusted to about 2 mg/L was passed through the column at a linear velocity LV of about 10 to about 70 m/h to examine the hydrogen peroxide removing performance of the metal-doped resin. The results are shown in Table 2 and FIG. 3.

(16) TABLE-US-00002 TABLE 2 Hydrogen peroxide decomposition Linear flow rate (%) by bed height velocity (m/h) 1 cm 2 cm 5 cm 10 cm 1 95 95 95 95 10 80 95 95 95 30 50 95 95 95 50 10 90 93 95 70 2 60 80 90

(17) FIG. 3 shows that about 90% or more of hydrogen peroxide can be decomposed at a bed height of about 2 cm or more and an LV of about 50 m/h or less.

Example 3

(18) The influence of hydrogen peroxide on degradation of ion exchange resin was examined.

(19) Cation resins of the same type were respectively immersed in solutions having various hydrogen peroxide concentrations for 24 hours and the total organic carbon (TOC) concentrations were measured with TOC-V, a product of Shimadzu Corp. As shown in FIG. 4, it was confirmed that hydrogen peroxide contained in a concentration of less than about 1 ppm had little influence on resin degradation. Hence, it is adequate to decompose 90% or more of hydrogen peroxide present in the order of a few or several ppm in fuel pool.

(20) In general, ion exchange resins are replaced by fresh resins in a TOC concentration of more than about 20 ppm. FIG. 4 shows that when the hydrogen peroxide concentration exceeds about 3.5 ppm, the TOC concentration exceeds about 20 ppm and replacement of ion exchange resin is required. FIGS. 2 and 4 show that untreated water (hydrogen peroxide concentration: 20 ppm) has such a high hydrogen peroxide concentration as to require replacement of ion exchange resin after the water is passed through the resin once, whereas the treatment method of the present invention achieves the hydrogen peroxide decomposition rate of about 95%, decreases the hydrogen peroxide concentration of water to be treated through an ion exchange resin to about 1 ppm or less, and considerably lowers the frequency of replacement of the ion exchange resins.

INDUSTRIAL APPLICABILITY

(21) Before an ion exchange resin is used to demineralize water to be treated that contains pro-oxidants (e.g., hydrogen peroxide) generated by radiolysis of spent fuel pool water from nuclear power plants of PWR, it is possible according to the present invention to reduce the pro-oxidants contained in the water to be treated, decrease load placed on a demineralizer and maintain the high purity of the treated water as well as prolong the life of the ion exchange resins and reduce generation of spent ion exchange resins that are radioactive secondary wastes. Accordingly, the present invention is significant.