JP4356987B2 - Condensate demineralization treatment method and apparatus and method for forming packed bed thereof - Google Patents

Description

  The present invention relates to demineralization treatment of condensate, and more particularly, a mixed-bed type condensate demineralization treatment method capable of improving the quality of condensate used in a BWR plant, an apparatus therefor, and a packed bed forming method used therefor Technology.

In BWR plant, in order to maintain the reactor water at a high purity, H, a mixed bed demineralizer using a OH type ion exchange resin, removal of the condensate water of the ionic impurities (Na, Cl, SO _4, etc.) It is carried out. In particular, recently, non-regeneration operation in which drug regeneration is not performed has become mainstream in order to prevent water quality deterioration due to reverse regeneration during drug regeneration of ion exchange resin.
In general, a mixed bed type desalination apparatus using H, OH type ion exchange resin is a method that can theoretically easily ensure high-purity water quality, but in order to maintain this operation, it is trapped in a resin layer. In order to suppress an increase in the operating differential pressure of the apparatus due to suspended impurities, it is necessary to periodically back-wash the ion exchange resin. The back washing operation is performed by transferring the ion exchange resin from the desalting tower to the regenerator, and after the back washing is completed, the ion exchange resin is returned to the desalting tower. The transfer of the ion exchange resin is carried out using water and air, but when the ion exchange resin settles in the water, the cationic resin is at the bottom of the resin layer of the desalting tower due to the difference in terminal velocity between the cationic resin and the anion resin. However, there is a tendency that the anionic resin concentrates on the upper part of the resin layer, and the water quality improvement effect by the mixed bed cannot be expected sufficiently.

In particular, the concentration of the cation resin at the bottom of the resin layer causes a problem that organic impurities are directly eluted from the cation resin into the condensate, resulting in deterioration of the quality of the treated water.
As a countermeasure, an anion resin underlay method, in which the anion resin is packed in the lower part of the desalting tower, has been developed. However, elution of amines from the lower anion resin layer occurs and the water quality deteriorates. The problem has not been solved.
As a method for solving these problems, as disclosed in JP-A-11-352283, a method of applying a 12-16% strongly acidic gel-type cation resin having a degree of crosslinking higher than the commonly used 8-10%, A method of adsorbing TOC eluted from a cation resin by disposing an anion resin in the lower layer of the resin layer as disclosed in JP-A-2001-314855, and a strongly acidic gel-type cation as described in JP-A-8-224579 A method of forming a mixed bed with a resin and a porous anion resin having a particle size distribution of Gaussian distribution has been proposed.

However, even if a strongly acidic gel type cation resin having a high degree of crosslinking is used, the deterioration of water quality is unavoidable because the oxidative degradation proceeds and the elution of organic impurities gradually increases with long-term use. In addition, in the method in which the anion resin is arranged in the lower layer part of the resin layer, the elution of organic impurities eluted from the cationic resin can be reduced, but conversely, the organic impurities eluted from the anion resin leak and the decomposition causes nitrate ions and the like. As a result, water quality is lowered. Porous anion resins have macropores and thus have a high adsorption capacity for organic impurities, but commercially available porous anion resins usually used in condensate demineralizers of nuclear power plants have a particle size distribution of 420. The so-called Gaussian distribution of ˜1180 μm has an average particle size of about 800 μm, and the porous ion exchange resin has macropores, so that the resin matrix portion has a very dense structure, and the reaction It will be inferior to gel type resin in terms of speed.
Japanese Patent Laid-Open No. 11-352283 JP 2001-314855 A JP-A-8-224579

  The present invention has been made in view of the above-described circumstances, and when returning the resin to the condensate demineralizer, it is possible to form a sound mixed bed in which the cationic resin does not concentrate on the resin layer bottom of the demineralizer. It is an object of the present invention to provide a condensate demineralization treatment method and apparatus and a method for forming a packed bed used therein.

In order to solve the above problems, in the present invention, in the method of desalinating condensate using an ion exchange resin, the condensate has a particle size used for demineralization of the condensate at the bottom. When backwashing and separating an anionic resin and a cationic resin having a Gaussian distribution, the anionic resin and the cationic resin whose end velocities are overlapped or close to each other are filled with a difficult-to-separate portion that is selectively concentrated. The desalination treatment method is characterized in that the anion resin and the cation resin excluding the portion filled in the bottom portion are passed through a resin layer filled in a mixed bed in a downward flow.
In the desalination process, the separated portion difficult to fill the resin layer bottom, part of the mixed layer together resin particles that suits Ri mixed to focus on the separation surface near the time of backwashing separate the A anion resin and cation resin It can be.

In the present invention, in the condensate demineralization apparatus filled with the ion exchange resin, the packed bed filled with the ion exchange resin has a Gaussian distribution of the particle size used for the demineralization treatment of the condensate at the bottom. When the anion resin and the cation resin are separated by backwashing, a portion where the anion resin and the cation resin in which the terminal velocities of the resin particles overlap or approach each other is selectively concentrated is filled, An anion resin and a cation resin excluding a portion filled in the bottom portion are filled with a mixed bed, and a condensate inlet is provided at the top of the packed bed and a condensate outlet is provided at the bottom. This is a condensate demineralizer.
In the condensate demineralizer, a resin outlet pipe is provided at the bottom of the packed bed, the resin outlet pipe is connected to a resin backwash separation tower, and the resin backwash separation tower includes an anion resin and a cation resin. In the lower part in the vicinity of the surface, there can be provided an extraction pipe for extracting the mixed layer mixed with both, and a flow path for filling the extracted mixed layer to the bottom of the packed layer of the demineralizer, In the resin backwash separation tower, the anion extraction pipe connected to the anion regeneration tower for regenerating the backwash separated anion layer, and the cation layer after the anion layer and the mixed layer in the vicinity of the separation surface are extracted are regenerated. And a reproducing means.

  Furthermore, in the present invention, in the method for forming a packed bed of the condensate demineralizer, the first means for backwashing and separating at the resin separation backwashing tower with a backwashing flow velocity at which the ion exchange resin can be sufficiently developed. The second means for transferring the anion resin to the anion resin regeneration tower, excluding the vicinity of the resin separation surface, the resin in the vicinity of the separation surface is withdrawn about 10 to 20% above and below the total packed bed height, and after mixing, A third means for transferring to the desalting apparatus, a remaining anion and cation resin is regenerated or mixed without regenerating, and then transferred to the upper part of the portion difficult to separate formed by the third means. It is supposed to be constituted by the means described above.

As described above in detail, according to the present invention, the following excellent effects are expected.
The present invention is a technique for fundamentally suppressing the separation of an anion resin and a cation resin, which is one of the main problems of a mixed bed type condensate demineralizer, and creating a sound mixed bed. As a result, TOC eluted from the cation resin and the anion resin during water passage is adsorbed and removed by the respective resins, thereby reducing organic impurities brought into the nuclear reactor and ensuring high-purity water quality. According to the present invention, it is possible to reduce impurity ions such as sulfuric acid, which is one of the causes of stress corrosion cracking (SCC) of in-furnace structures, which is currently a problem in BWR plants. It is a revolutionary technology that leads to improvement, and its economic effect is enormous.
Furthermore, the present invention is an effective technique for water quality deterioration due to deterioration of ion exchange resin used in a mixed bed type condensate desalination apparatus, and can be expected to reduce the replacement frequency by extending the life of the resin. It is an epoch-making technology that leads to cost reduction, and its ripple effect is enormous.

As a result of various investigations, the resin layer lower part of the condensate demineralization tower is filled with a mixed resin layer of anions and cations that are difficult to separate, thereby elution from the cationic resin and anion resin from the lower part of the resin layer. It was made by finding out that the ingredients can be suppressed.
The resin extracted from the condensate demineralization tower is backwashed in the backwashing separation tower of the regeneration facility, and separated into two layers, an anion and a cation. In this case, the separation surface vicinity approaches the terminal velocity of the resin particle element separation hardly resin is concentrated. The first means for extracting this portion of resin and filling the bottom layer of the desalting tower, and then thoroughly mixing the remaining anion resin and cation resin, and then filling the upper portion of the resin layer formed by the first means. With the condensate demineralization apparatus having the resin layer constituted by the second means, it is possible to ensure good water quality with little elution from anion and cation resins.

One example of specific conditions for carrying out the present invention will be described below.
FIG. 1 is a schematic configuration diagram showing an example of a resin backwash separation tower used in the present invention, and FIG. 2 is a schematic configuration diagram of a mixed bed type desalting tower showing an example of a condensate demineralization apparatus of the present invention. is there.
(1) The ion exchange resin transferred to the resin backwash separation tower from the desalting apparatus is backwashed for about 15 minutes to 30 minutes at a linear flow rate of about 4 m / h to 15 m / h, and anion resin and cation resin 2 Separate into layers.
(2) The anion resin is transferred to the anion resin regeneration tower, leaving about 10 to 20% of the total layer height on the separation surface.
(3) Next, 10 to 20% of the resin in the mutual contamination zone at the top and bottom of the resin separation surface and about the total layer height is returned to the desalting apparatus.
(4) Mutual contamination zone composed of ion-exchange resins in which the terminal velocities of the resin particles that are concentrated near the separation surface overlap or approach each other by backwashing and separating the anion resin and cation resin having a Gaussian particle size When the return of the resin is completed, drain the water from the desalting apparatus.
(5) Next, the anion resin in the anion resin regeneration tower is regenerated or returned to the resin backwash separation tower as it is, regenerated in the resin backwash separation tower, or mixed with the cationic resin as it is and then removed. Return to the salt tower.
(6) Resin return to the desalting tower is performed while draining the desalting tower to prevent separation of the resin as much as possible.

(7) By such a series of operations, a mixed bed having the following characteristics is formed in the desalting tower.
(8) The treated water introduced from the condensate inlet of the mixed bed desalting tower passes through the rectifying mechanism of the inlet header lateral water spray plate, passes through the mixed resin layer, and then passes through the mutual contamination resin layer that is difficult to separate. After being desalted, it passes through a perforated plate fitted with a wedge wire screen and exits the desalting tower as treated water. In this desalting treatment, ionic impurities contained in the water to be treated and organic impurities eluted from the anion resin and the cation resin themselves are removed. In particular, the technology of arranging the mutual contamination resin layer that is difficult to separate at the bottom of the desalting tower of the present invention is an organic property from the cationic resin concentrated on the bottom of the desalting tower, which is generated in the conventional mixed bed desalting tower. This is an excellent technology that can prevent the deterioration of reactor water quality due to the mixing of impurities (polystyrene sulfonic acid) into the treated water, and can easily maintain the high purity of reactor water simply by changing the operation method. is there.

Example 1
A strongly acidic cation exchange resin (HGR-W2H) and a strongly basic anion exchange resin (SPR-PC-OH) manufactured by Dow Chemical Co. were screened with water to determine the particle size distribution.
The obtained particle size distribution is shown in Table 1 for the cation exchange resin and in Table 2 for the anion exchange resin.

FIG. 3 shows the terminal velocity distribution obtained from the particle size distribution and true specific gravity of each ion exchange resin.
As shown in the schematic diagram of FIG. 3, the terminal velocity of the anion resin and the cation resin has an overlapping portion. This portion corresponds to a separation interface portion between the cation resin and the anion resin in a normal backwash operation, and the resins are difficult to separate from each other.
Although this part differs depending on the type of resin and the combination of anion and cation, it is about 10 to 20% above and below the total height of the resin layer on the resin separation surface. It becomes about 200 mm.
By selectively extracting the resin in this part and filling the lowermost part of the resin layer of the desalting tower, a mixed bed that is difficult to separate is formed.

Example 2
A dough chemical strong acid cation exchange resin (HGR-W2H) and a strongly basic anion-replacement resin (SPR-PC-OH) are combined to form a mixed bed and conduct a water flow test. The water ion concentration was measured. The test was conducted under the following conditions.
A column having an inner diameter of 30 mm is packed with 350 mL of cationic resin and anionic resin at a volume ratio of 1/1. The total resin layer height was 1000 mm, and the filling method was as follows.
Case 1 = Desalting tower in which 20% of the total amount of mixed resin (200 mm as the layer height) is disposed in the lower part of the desalting tower and the remaining mixed bed is disposed in the upper part.
Case 2: A cation resin rich layer (cation resin / anion resin volume ratio = 5/1) equivalent to 20% of the total layer height of 200 mm is arranged at the bottom of the desalting tower, and the rest of the resin is mixed bed Desalting tower arranged in

Case 3: An anion resin-rich layer (cation resin / anion resin volume ratio 1/5) equivalent to 20% of the total height of 200 mm is arranged at the bottom of the desalting tower, and the rest of the resin is mixed with the upper part Desalting tower arranged in
Prior art: Mixed bed The flow rate of the water line was 120 m / h simulating an actual apparatus, the temperature of the water to be treated was 45 ° C., and ultrapure water having a conductivity of 0.0055 mS / m was passed. A portion of the treated water was collected, and the concentration of inorganic ions generated by decomposing organic compounds contained in the treated water by irradiating with ultraviolet rays was measured. Table 3 shows the measurement results.

表３からわかるように、従来技術と比較して本発明のケース１はイオン濃度が低く、対比として実施したケース２では硫酸イオン温度が高く、ケース３では硝酸イオン濃度が高い結果となり、本発明が最も低いイオン濃度であることを検証した。

As can be seen from Table 3, Case 1 of the present invention has a lower ion concentration compared to the prior art, Case 2 performed as a comparison has a higher sulfate ion temperature, and Case 3 results in a higher nitrate ion concentration. Has the lowest ion concentration.

The schematic block diagram which shows an example of the resin backwash separation tower used for this invention. BRIEF DESCRIPTION OF THE DRAWINGS The schematic block diagram of the mixed bed-type desalting tower which shows an example of the condensate desalination apparatus of this invention. The graph which shows distribution of the terminal velocity of ion exchange resin.

Claims (6)

In the method of desalinating condensate using an ion exchange resin, the condensate is back-washed with an anion resin and a cation resin having a Gaussian particle size used for the desalting treatment of the condensate at the bottom. When separating, the anion resin and the cation resin whose end velocities overlap or approach each other are filled with a difficult-to-separate portion where the anion resin and the cation resin are selectively concentrated, and the anion excluding the portion filled in the bottom portion is filled in the upper portion A desalinization treatment method comprising passing a resin layer filled with resin and a cationic resin in a mixed bed in a downward flow. Wherein the separated portion difficult to fill the resin layer bottom, together resin particles concentrated in the separation surface near the time of backwashing separate the A anion resins and cation resins are part of the mixed Ri suits mixed layer The method for desalinating condensate according to claim 1. In a condensate demineralization apparatus filled with an ion exchange resin, the packed bed filled with the ion exchange resin has an anion resin and a cation resin having a Gaussian distribution of particle sizes used for demineralization treatment of the condensate at the bottom. In the backwashing separation, an anion resin and a cation resin in which the terminal velocities of the resin particles overlap or approach each other are selectively filled with a portion that is difficult to separate, and a portion filled in the bottom is placed on the top. A condensate demineralization apparatus comprising a mixed bed filled with the removed anion resin and cation resin, having a condensate inlet at the top of the packed bed and a condensate outlet at the bottom.   The condensate demineralizer according to claim 3, wherein a resin outlet pipe is provided at the bottom of the packed bed, the resin outlet pipe is connected to a resin backwash separation tower, and the resin backwash separation tower includes an anion resin and A lower part of the vicinity of the separation surface of the cation resin, having an extraction pipe for extracting the mixed layer of both, and having a flow path for filling the extracted mixed layer at the bottom of the packed layer of the desalting apparatus. Condensate demineralizer characterized by   In the resin backwash separation tower, the anion extraction pipe connected to the anion regeneration tower for regenerating the backwash separated anion layer and the cation layer after extracting the anion layer and the mixed layer near the separation surface are regenerated. The condensate demineralizer according to claim 4, further comprising a regeneration unit.   6. The method for forming a packed bed of a condensate demineralizer according to claim 5, wherein said resin separation backwash tower is a first means for backwashing and separating by a backwash line flow velocity at which ion exchange resin can be sufficiently developed. Second means for transferring the anion resin to the anion resin regeneration tower, excluding the vicinity of the separation surface, withdrawing about 10 to 20% of the resin in the vicinity of the separation surface above and below the total packed bed height and mixing, Third means for transporting to the salt device, fourth means for transporting the rest of the anion and cation resin to the upper part of the hard-to-separate portion formed by the third means after regenerating or mixing without regeneration A method for forming a packed bed of a condensate demineralizer, comprising:

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