JP3794603B2 - Method for analyzing the amount of impurities eluted from ion exchange resin - Google Patents
Method for analyzing the amount of impurities eluted from ion exchange resin Download PDFInfo
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- JP3794603B2 JP3794603B2 JP22753998A JP22753998A JP3794603B2 JP 3794603 B2 JP3794603 B2 JP 3794603B2 JP 22753998 A JP22753998 A JP 22753998A JP 22753998 A JP22753998 A JP 22753998A JP 3794603 B2 JP3794603 B2 JP 3794603B2
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- amount
- ion exchange
- exchange resin
- impurities eluted
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- 239000012535 impurity Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 13
- 239000003456 ion exchange resin Substances 0.000 title claims description 11
- 229920003303 ion-exchange polymer Polymers 0.000 title claims description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims description 10
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000001768 cations Chemical class 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- -1 sulfuric acid ion Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Monitoring And Testing Of Nuclear Reactors (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、イオン交換樹脂の分析方法に係り、特に、ＢＷＲ型原子力発電プラントの復水脱塩装置に使用するカチオン樹脂から溶出する有機性不純物量の分析方法に関するものである。
【０００２】
【従来の技術】
ＢＷＲ型原子力発電プラントでは、原子炉の内部を常に清浄に維持しなければならないので、その浄化設備として、イオン交換樹脂を使用している復水脱塩装置が設置されている。そのイオン交換樹脂としては、カチオン樹脂とアニオン樹脂を混床にて使用している。このイオン交換樹脂より溶出する有機性不純物量を評価する手法としては、通常、使用する環境と同様の純水中に浸漬するバッチ法や、純水を通水するカラム法などが行われていた。
最近のＢＷＲ型原子力発電プラントでは、イオン交換樹脂、特にカチオン樹脂から溶出する有機性不純物が、硫酸濃度を上昇させ、処理水質を低下させる要因となっている。従って、使用しているイオン交換樹脂は、定期的に管理を行い、溶出する有機性不純物量を、純水中に浸漬するパッチ法や、純水を通水するカラム法などにて測定していた。しかし、この方法により求められた有機性不純物溶出速度と、実際の原子炉水質における硫酸濃度には相関性がなく、正しい評価方法の開発が急務であった。
【０００３】
【発明が解決しようとする課題】
本発明は、上記従来技術に鑑み、ＢＷＲ型原子力発電プラントの復水脱塩装置に使用するカチオン樹脂から、実際の原子炉水質における硫酸濃度に相関した溶出する有機性不純物量の分析方法を提供することを課題とする。
【０００４】
【課題を解決するための手段】
上記課題を解決するために、本発明では、ＢＷＲ型原子力発電プラントの復水脱塩装置に使用するカチオン樹脂を、無機酸水溶液に所定の時間浸漬した後、該水溶液中に溶出する有機性不純物量を測定することを特徴とするイオン交換樹脂から溶出する不純物量の分析方法としたものである。
前記分析方法において、無機酸水溶液は、塩酸、硫酸又は炭酸の水溶液、好ましくは塩酸水溶液であり、その濃度は０．１〜２規定、好ましくは１規定程度で用い、また、その浸漬時間は１０〜６０分、好ましくは３０分程度とするのが良い。
【０００５】
【発明の実施の形態】
本発明は、ＢＷＲ型原子力発電プラントの復水脱塩装置に使用するカチオン樹脂の分析方法を提供するものである。
カチオン樹脂から有機性不純物が発生する際の反応は、２段階あり、酸化反応と加水分解反応である。１段階目の酸化反応は、樹脂母体の炭素直鎖が酸素と反応し、パーオキサイドが生成するものであり、それが加水分解により、炭素鎖が切断されるのが２段階目の反応である。
そして、本発明では、塩酸などの水溶液に樹脂を浸漬させることにより、この２段階目の加水分解反応を強制的におこし、カチオン樹脂から溶出する有機性不純物量を定量するものである。これにより溶出可能な有機物量を把握することができ、実際の原子炉水質を定量評価することが可能となった。
【０００６】
本発明の数値の規定は、次の実験結果に基づき規定した。
まず、無機酸濃度は、塩酸を用い、０．０１〜２規定の範囲で、カチオン樹脂を３０分間浸漬して溶出する有機物量を測定した。その結果を図１に示す。図からわかるように、その溶出量は、０．１規定で１００００ｐｐｂであり、１規定、特に２規定以上の濃度では、その溶出量はほとんど変化が無いことが確認された。従って、０．１〜２規定、好ましくは１規定とした。
次に浸漬時間は、１規定の塩酸を用い、５〜６０分の範囲でカチオン樹脂を浸漬して溶出する有機物量を測定した。その結果を図２に示す。図からわかるように、その溶出量は１０分で３００００ｐｐｂであり、３０分以上、特に６０分以上ではその溶出量はほとんど変化が無いことが確認された。従って、１０〜６０分、好ましくは３０分とした。
【０００７】
【実施例】
以下、実施例により本発明を具体的に説明する。
実施例１
実際のＢＷＲ型原子力発電プラントの復水脱塩装置において使用しているカチオン樹脂である強酸性ゲル型カチオン樹脂を、１規定の塩酸に３０分間浸漬し、有機性不純物量を以下の手順で測定した。初めに樹脂を５ｍｌ採取し、これに４０ｍｌの１規定の塩酸を加え、マグネティックスターラにて３０分間攪拌する。その後、上澄水を採取し、全有機炭素計にて有機物濃度を測定した。
【０００８】
一方、前記カチオン樹脂が使用されているＢＷＲ型原子力発電プラントの原子炉水中の硫酸イオン濃度を測定した。その測定は、原子炉には原子炉水を採取するサンプリングラインが設置されており、正確に試料水を採取するため、オンラインにて試料水をイオンクロマトグラフ分析装置に導入し、硫酸濃度の測定を行っており、それを用いた。
ここで述べた原子炉水中における硫酸イオンは、カチオン樹脂から溶出した有機性不純物より生成したものであり、これは官能基としてスルホン基を含んでおり、これが原子炉内で反応し、硫酸イオンとなったものである。
図３に、溶出した有機性不純物量と、原子炉水中の硫酸イオン濃度の関係を示す。
図３から明らかなように、両者の間には良い相関関係が得られている。
【０００９】
【発明の効果】
本発明によれば、ＢＷＲ型原子力発電プラントの復水脱塩装置に用いるカチオン樹脂から溶出する有機性不純物量を、簡単な処理で正確に分析することが可能である。
【図面の簡単な説明】
【図１】ＨＣｌ濃度と有機物溶出量（ｐｐｂ）の関係を示すグラフ。
【図２】浸漬時間と有機物溶出量（ｐｐｂ）の関係を示すグラフ。
【図３】有機性不純物量（ｐｐｂ）と原子炉水中硫酸イオン濃度（ｐｐｂ）の関係を示すグラフ。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ion exchange resin analysis method, and more particularly, to an analysis method of the amount of organic impurities eluted from a cation resin used in a condensate demineralizer of a BWR nuclear power plant.
[0002]
[Prior art]
In a BWR nuclear power plant, the inside of a nuclear reactor must be kept clean at all times, so a condensate demineralizer using ion exchange resin is installed as a purification facility. As the ion exchange resin, a cation resin and an anion resin are used in a mixed bed. As a method for evaluating the amount of organic impurities eluted from this ion exchange resin, a batch method of immersing in pure water similar to the environment to be used, a column method of passing pure water, etc. were usually performed. .
In recent BWR nuclear power plants, organic impurities eluted from ion exchange resins, particularly cation resins, increase sulfuric acid concentration and reduce the quality of treated water. Therefore, the ion-exchange resin used is regularly controlled, and the amount of organic impurities to be eluted is measured by a patch method in which pure water is immersed or a column method in which pure water is passed. It was. However, there was no correlation between the organic impurity elution rate obtained by this method and the sulfuric acid concentration in the actual reactor water quality, and there was an urgent need to develop a correct evaluation method.
[0003]
[Problems to be solved by the invention]
In view of the above prior art, the present invention provides a method for analyzing the amount of organic impurities eluted from a cationic resin used in a condensate demineralizer of a BWR nuclear power plant in relation to the sulfuric acid concentration in the actual reactor water quality. The task is to do.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, in the present invention, after impregnating a cationic resin used in a condensate demineralization apparatus for a BWR nuclear power plant in an inorganic acid aqueous solution for a predetermined time, an organic impurity eluted in the aqueous solution This is a method for analyzing the amount of impurities eluted from an ion exchange resin, characterized by measuring the amount.
In the analytical method, the aqueous inorganic acid solution is an aqueous solution of hydrochloric acid, sulfuric acid or carbonic acid, preferably an aqueous hydrochloric acid solution, and the concentration is 0.1 to 2 N, preferably about 1 N, and the immersion time is 10 N. -60 minutes, preferably about 30 minutes.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a method for analyzing a cationic resin used in a condensate demineralizer for a BWR nuclear power plant.
There are two stages of reaction when organic impurities are generated from the cationic resin, which are an oxidation reaction and a hydrolysis reaction. In the first stage oxidation reaction, the carbon straight chain of the resin matrix reacts with oxygen to produce peroxide, which is the second stage reaction in which the carbon chain is cleaved by hydrolysis. .
In the present invention, by immersing the resin in an aqueous solution such as hydrochloric acid, the second-stage hydrolysis reaction is forcibly performed to quantify the amount of organic impurities eluted from the cationic resin. As a result, it was possible to grasp the amount of organic substances that could be eluted and to quantitatively evaluate the actual reactor water quality.
[0006]
The numerical values of the present invention were specified based on the following experimental results.
First, the inorganic acid concentration was measured by using hydrochloric acid in the range of 0.01 to 2 N, and measuring the amount of organic matter eluted by immersing the cationic resin for 30 minutes. The result is shown in FIG. As can be seen from the figure, the elution amount was 0.1 ppb and 10,000 ppb, and it was confirmed that the elution amount hardly changed at a concentration of 1 N, particularly 2 N or more. Therefore, it was set to 0.1-2 N, preferably 1 N.
Next, the immersion time was determined by measuring the amount of organic substances eluted by immersing the cationic resin in the range of 5 to 60 minutes using 1N hydrochloric acid. The result is shown in FIG. As can be seen from the figure, the elution amount was 30000 ppb in 10 minutes, and it was confirmed that there was almost no change in the elution amount after 30 minutes or more, particularly 60 minutes or more. Therefore, the time is 10 to 60 minutes, preferably 30 minutes.
[0007]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
Example 1
A strongly acidic gel-type cation resin, which is a cation resin used in the condensate demineralizer of an actual BWR nuclear power plant, is immersed in 1N hydrochloric acid for 30 minutes, and the amount of organic impurities is measured by the following procedure. did. First, 5 ml of the resin is collected, 40 ml of 1N hydrochloric acid is added thereto, and the mixture is stirred for 30 minutes with a magnetic stirrer. Thereafter, supernatant water was collected, and the organic matter concentration was measured with a total organic carbon meter.
[0008]
On the other hand, the sulfate ion concentration in the reactor water of the BWR nuclear power plant where the cationic resin is used was measured. For the measurement, the reactor has a sampling line for collecting the reactor water. In order to collect the sample water accurately, the sample water is introduced online into the ion chromatograph analyzer and the sulfuric acid concentration is measured. And used it.
The sulfate ion in the reactor water described here is generated from organic impurities eluted from the cation resin, which contains a sulfone group as a functional group, which reacts with the sulfate ion in the reactor. It has become.
FIG. 3 shows the relationship between the amount of eluted organic impurities and the sulfate ion concentration in the reactor water.
As is clear from FIG. 3, a good correlation is obtained between the two.
[0009]
【The invention's effect】
According to the present invention, it is possible to accurately analyze the amount of organic impurities eluted from a cation resin used in a condensate demineralizer of a BWR nuclear power plant by simple processing.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between HCl concentration and organic substance elution amount (ppb).
FIG. 2 is a graph showing the relationship between immersion time and organic substance elution amount (ppb).
FIG. 3 is a graph showing the relationship between the amount of organic impurities (ppb) and the sulfuric acid ion concentration (ppb) in reactor water.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22753998A JP3794603B2 (en) | 1998-07-29 | 1998-07-29 | Method for analyzing the amount of impurities eluted from ion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22753998A JP3794603B2 (en) | 1998-07-29 | 1998-07-29 | Method for analyzing the amount of impurities eluted from ion exchange resin |
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| Publication Number | Publication Date |
|---|---|
| JP2000046990A JP2000046990A (en) | 2000-02-18 |
| JP3794603B2 true JP3794603B2 (en) | 2006-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP22753998A Expired - Fee Related JP3794603B2 (en) | 1998-07-29 | 1998-07-29 | Method for analyzing the amount of impurities eluted from ion exchange resin |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008281509A (en) * | 2007-05-14 | 2008-11-20 | Ebara Corp | Exchange management method of ion-exchange resin in nuclear power plant condensate demineralizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3075450B1 (en) * | 2017-12-15 | 2019-12-27 | Electricite De France | METHOD FOR IDENTIFYING THE UNIT ORIGIN OF A CRUDE WATER LEAKAGE IN A CONDENSER OF A THERMAL POWER PLANT |
| CN110646318A (en) * | 2019-09-03 | 2020-01-03 | 西安建筑科技大学 | Full life cycle monitoring method for activated carbon adsorption module |
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1998
- 1998-07-29 JP JP22753998A patent/JP3794603B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008281509A (en) * | 2007-05-14 | 2008-11-20 | Ebara Corp | Exchange management method of ion-exchange resin in nuclear power plant condensate demineralizer |
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| JP2000046990A (en) | 2000-02-18 |
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