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JP4020372B2 - Condensate treatment method and apparatus - Google Patents
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JP4020372B2 - Condensate treatment method and apparatus - Google Patents

Condensate treatment method and apparatus Download PDF

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JP4020372B2
JP4020372B2 JP2002202633A JP2002202633A JP4020372B2 JP 4020372 B2 JP4020372 B2 JP 4020372B2 JP 2002202633 A JP2002202633 A JP 2002202633A JP 2002202633 A JP2002202633 A JP 2002202633A JP 4020372 B2 JP4020372 B2 JP 4020372B2
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condensate
ions
ion
concentration
ammonia
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JP2004045195A (en
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祐輔 永田
伸一 大橋
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Organo Corp
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Organo Corp
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Priority to PCT/JP2003/005888 priority patent/WO2004007375A1/en
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    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/12Processing by absorption; by adsorption; by ion-exchange
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/60Cleaning or rinsing ion-exchange beds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/80Automatic regeneration
    • B01J49/85Controlling or regulating devices therefor
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/12Processing by absorption; by adsorption; by ion-exchange
    • G21F9/125Processing by absorption; by adsorption; by ion-exchange by solvent extraction
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21DNUCLEAR POWER PLANT
    • G21D1/00Details of nuclear power plant
    • G21D1/02Arrangements of auxiliary equipment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、火力発電所や加圧水型原子力発電所(以下、PWR型原子力発電所と言う。)におけるアンモニア型復水脱塩装置での復水処理方法および装置に関するものである。
【0002】
【従来の技術】
火力発電所あるいはPWR型原子力発電所では、発電タービンを駆動させた後の蒸気を冷却して復水とし、この復水を加熱して再び蒸気とし発電するサイクルをくり返している。このため、復水は、ボイラーや蒸気発生器、原子炉等の腐食防止の観点から高度に浄化する必要があり、混床式復水脱塩装置、粉末イオン交換樹脂フィルター、中空糸フィルター等の浄化装置が単独あるいは組み合わされて採用されている。
【0003】
上記復水脱塩装置は、通常、複数の復水脱塩塔(以下、単に脱塩塔と言うこともある。)からなる通水系統と、脱塩塔にて使用したイオン交換樹脂を再生する再生系統とからなり、このような脱塩塔では、一定水量を処理した段階で再生工程に入るようにしている。再生工程では例えば、充填されていたイオン交換樹脂をカチオン交換樹脂とアニオン交換樹脂に分離し、カチオン交換樹脂には塩酸もしくは硫酸を、アニオン交換樹脂には水酸化ナトリウムを通薬し、それぞれ不純物を脱着する。不純物を脱着した樹脂を脱塩塔に移送し、再び復水を通水して処理するようにしている。
【0004】
また、火力発電所やPWR型原子力発電所では、通常、脱塩塔の後段より、腐食発生を制御するためにpH調整剤として通常アンモニアイオンを、また脱酸素剤としてヒドラジニウムイオンを注入している。これら復水脱塩塔は、上記アンモニアおよびヒドラジンが復水脱塩塔から漏洩しない条件で採水する、いわゆるH−OH形運転が行われている。また、一部の火力発電所では、運転コスト削減の観点から、これらのイオンが脱塩塔出口から漏洩した状態でも復水の通水を継続する、いわゆるアンモニア形運用を行っている。アンモニア形運用においては、復水脱塩装置のイオン交換樹脂がアンモニアでブレークした後の通水期間が長いほど運転コストが低減できる。
【0005】
【発明が解決しようとする課題】
しかしながら、上記のようなアンモニア形運用において、アンモニアでブレーク後の運転状態を長期間追跡調査した結果、以下のような問題があることが判明した。すなわち、上記のようなアンモニア型運用において、アンモニアブレーク後にある一定期間以上通水を継続すると、CLイオンの漏洩ピークが現れる現象のあることが判明した。この現象は、これまではこのようなピークが現れる以前に再生工程に入っていたので、今まで把握されていなかった現象である。本現象は、復水中のイオン濃度が十分に低く、復水脱塩装置のイオン負荷がほとんどない状態でも発生することから、このピークの発生は、通水当初よりイオン交換樹脂中に含まれるCLイオンが、徐々に脱塩塔出口近傍の樹脂層中へと押し出されながら濃縮され、それが急激に漏洩して、ピーク形状が現れるものと推察される。イオン交換樹脂中の含有量にもよるが、現状の樹脂中のCLイオン含有レベルでは、上記ピークの最大値は1ppb程度にまで達する場合もあるので、ボイラー、蒸気発生器および配管などの腐食防止の観点からは、そのまま通水を継続できる水質レベルではない。従来はアンモニアブレーク直後の水質の変動に着目して運用されており、その変動を勘案して例えば再生を早目のタイミングにて行う検討はなされていたが、前述の如くアンモニアブレーク後の運転をより長期間にわたって継続しようとすると、上記のようなCLイオンのピークが現れる現象をさらに考慮しなければならないことが判明し、従来考慮されていなかった対策を講じることが必要であることが判明した。
【0006】
そこで本発明の課題は、上記のような新たな知見に基づき、復水脱塩装置をアンモニア形で運用する場合、CLイオンのピークが現れる現象を適切に防止して、従来の運転に比べより長期間にわたってアンモニアブレーク後の運転を継続でき、再生の頻度を大幅に低減して安定処理継続時間を延長できるとともに、再生剤の使用量低減等による復水処理の大幅なコスト低減が可能な、復水処理方法および装置を提供することにある。
【0007】
【課題を解決するための手段】
上記課題を解決するために、本発明に係る復水処理方法は、イオン交換樹脂を充填したアンモニア型復水脱塩装置の出口におけるCLイオンを監視し、CLイオン濃度または/および濃度上昇傾向が予め定めた基準値以上に達した段階で採水を中止し、薬品再生することなく樹脂層を混合して再度通水を開始することを特徴とする方法からなる。
【0008】
上記混合の実施の判断基準となるCLイオン濃度の基準値については、たとえば、復水脱塩装置出口CLイオン濃度にて5ng/Lとすることができる。また、CLイオンの濃度上昇傾向の基準値については、たとえば、所定測定時間間隔での測定値の上昇幅で3ng/Lとすることができる。所定測定時間間隔としては、たとえばある測定時刻から次の測定時刻までの間隔を3時間とし、その間の上昇幅で上記CLイオンの濃度上昇傾向を判断することができる。すなわち、CLイオン濃度の検出値の絶対値を基準値と比較し判断することに加え、アンモニアブレーク後の一定期間後に検出されるCLイオンの上昇傾向を基準値と比較、判断することができる。
【0009】
また、上記CLイオンを監視する場合のCLイオン濃度の基準値および上昇傾向の基準値は、たとえば以下のように決定される。すなわち、通常PWR型原子力発電所の管理基準としては、概ね5g/Lで運用されている。よって本発明におけるCLイオン濃度の管理基準値も現状のPWR型原子力発電所における管理および実運用値に合せ、復水脱塩塔出口で5g/Lを基準値とすることが好ましい。
【0010】
さらに、実際の復水脱塩塔出口CLイオンの測定に関しては、測定が微量におよぶことから、種々の誤差を考慮して、一つの測定値だけではなく、CLイオンの上昇傾向を把握することによりCLイオンのピークをより的確に捕らえ、回避することが可能となる。したがって、上記CLイオン5ng/L以下での管理および、CLイオン測定の精度と測定検体数(1検体:たとえば30分以上)を考慮して、一定測定時間間隔での上昇分の管理基準値を3ng/L以上とすることにより、CLイオンのピーク発生をより的確に監視、管理することができる。
【0011】
また、上記方法においては、アンモニア型復水脱塩装置の出口におけるCLイオン濃度または/および濃度上昇傾向が予め定めた基準値以上に達したことを検出して、採水の中止、樹脂層の混合を行うようにしたが、基準値に達するまでの時間が大略予想できる場合には、これらの値が基準値に達する前に、樹脂層の混合を行うようにすることも可能であり、これを繰り返し定期的に行うことが可能である。
【0012】
すなわち、本発明に係るもう一つの復水処理方法は、所定復水処理時間以上経過した後、イオン交換樹脂を充填したアンモニア型復水脱塩装置の出口からCLイオンが漏洩する前に、たとえば、前記基準値に達するようなCLイオンが漏洩する前に、樹脂層の混合を定期的に行うことを特徴とする方法からなる。上記所定復水処理時間は、たとえば30日程度に設定することができる。
【0013】
上記のような復水処理方法においては、樹脂層の混合は復水脱塩塔で実施してもよく、また再生系統に樹脂を移送して実施してもよい。そのまま復水脱塩塔で行う方が、簡単に実施できる。
【0014】
本発明に係る復水処理装置は、イオン交換樹脂を充填したアンモニア型復水脱塩装置の出口におけるCLイオンを監視する手段と、該監視手段により監視されたCLイオン濃度または/および濃度上昇傾向が予め定めた基準値以上に達したときに、採水を中止し、薬品再生することなく樹脂層を混合するための信号を発する手段を有することを特徴とするものからなる。この信号により、自動的に、あるいは手動操作で、採水の中止、樹脂層の混合を行うことができる。
【0015】
上記のような本発明に係る復水処理方法および装置においては、これまで管理対象とされてこなかった、アンモニア型運用におけるアンモニアブレーク後、ある長時間経過後の、CLイオンの漏洩、とくにCLイオン濃度のピークの発生が監視、検出対象とされる。そして、望ましくない大きさのピークが発生する前に、脱塩塔における樹脂層が、薬品再生されることなく単に混合される。樹脂層を混合することにより、樹脂層中を移動して濃縮局在化されていた樹脂層中のCLイオンが再び全樹脂層中に均一に分散化される。復水脱塩装置出口水のCLイオン濃度は復水脱塩装置最下層のイオン交換樹脂のCL含有量に依存するため、このように単に樹脂層を混合し、局在化されていたCLイオンを全樹脂層中に均一に分散させることにより、復水脱塩装置出口水のCLイオン濃度を大幅に低減することが可能となる。
【0016】
復水中のCLイオン濃度は通常十分に低いため、復水脱塩装置出口のCL濃度がある程度上昇した段階においても、樹脂層中のCLイオンの全体量としては、ほぼ通水初期とはぼ同等に保たれている。したがって、上記混合により、樹脂層中に局在化されていたCLイオンを全樹脂層中に均一に分散させるだけで、復水脱塩装置出口水のCLイオン濃度を実質的に初期のレベルにまで低下、あるいは、上昇しそうになったCLイオン濃度レベルを、それ以降もそのまま低いレベルに維持することが可能になる。つまり、単に復水脱塩塔の樹脂混合を繰り返すことで、出口CLイオン濃度を通水開始初期の値まで低減しながら、アンモニア型運用を継続できるようになり、樹脂再生の頻度は大幅に低減される。従って本発明によれば、海水漏洩などの不慮の事態が発生しない限り、薬品再生を行わずに長期間通水することが可能となり、再生に伴う運転コストおよび再生時間を大幅に低減することが可能となる。
【0017】
【発明の実施の形態】
以下に、本発明の実施の形態について、カラム試験による実施例とともに、図面を参照しながら詳細に説明する。
まず、火力発電所およびPWR型原子力発電所での復水脱塩装置アンモニア型運用に関して、装置例を図面に基づいて説明する。図1は、本発明を説明するための、復水脱塩装置についての概略構成図である。まず、復水脱塩装置において、各復水脱塩塔1に所定のイオン交換樹脂Rが所定の充填率で充填されており、脱塩塔1の上流側よりアンモニア、ヒドラジンを所定濃度で含んだ復水が所定の流量で移行して採水状態となる。ここで、脱塩塔出口水のCLイオンをサンプリングライン5を介して各塔別にCLイオンモニター2で検出し、CLイオン濃度の値が復水脱塩装置出口で予め設定した基準値を超える点、または、CLイオンモニター2である時刻における測定値から次の時刻における測定値の上昇幅(つまり、所定の測定時間間隔での測定値の上昇幅)に予め設定した基準値を超える増加傾向がみられる時点を終点とし、採水を中止する。次に、採水が中止した樹脂は、脱塩塔1または再生塔3にて空気ライン7および逆洗水ライン6より空気および逆洗水を供給して樹脂層を一定時間混合する。脱塩塔1での混合の場合には、樹脂は移送されることなく十分に混合された後に再度採水を再開する。また、再生塔3での混合の場合は、採水を中止した後、樹脂移送配管4にて再生塔3に移送され、再生塔3にて十分に混合した後再度脱塩塔1に移送されて再度採水を開始する。脱塩塔1または再生塔3での樹脂混合は、樹脂層が十分に混合されていればよく、特に空気および逆洗水の流量流速、時間を規定する必要はない。
【0018】
【実施例】
実験室にて、カラムを使用して、以下の通水条件にてモデル試験を行った。

Figure 0004020372
【0019】
実施例として、樹脂の混合を実施した場合の通水結果を図2に示す(通水試験1)。また比較例として、混合を実施しない場合の通水結果を図3に示す(通水試験2)。図3に示した比較例では、通水開始から約1100時間(45.8日)後にCLイオンの上昇が生じるが、混合を実施した図2に示した実施例では、CLイオン濃度は充分に低く保たれている。
【0020】
上記試験結果からも分かるように、本発明における混合を適切なタイミングで行うことにより、CLイオン濃度の望ましくないピークの発生を防止することができ、樹脂再生を行うことなく、そのまま安定してアンモニア型運用を継続することができる。この混合により、前述の如く、CLイオンの樹脂層中における局在が解消され、全樹脂層中のCLイオンの実質的な変化なしに、初期状態に戻されると考えられるから、定期的な混合、あるいは、上記の如く混合すべき状態に達したことを検知した後の混合をくり返すことにより、複数回、このようなCLイオンの分散化を実現できる。したがって、極めて長期間にわたって、CLイオン濃度の望ましくないピークの発生を防止することが可能になり、安定したアンモニア型運用を低コストで継続することが可能になる。
【0021】
【発明の効果】
以上説明したように、本発明に係る復水処理方法および装置によれば、アンモニア型復水脱塩装置の出口水におけるCLイオン濃度の望ましくないピークが発生する前に、イオン交換樹脂を薬品再生することなく樹脂層を単に混合するだけの簡単な操作で、所望のアンモニア型運用を長期間にわたって確実に継続できるようになり、イオン交換樹脂の再生に要する時間、コストを削減して、全体としての運転コストを大幅に低減することができる。
【図面の簡単な説明】
【図1】本発明を適用した復水脱塩装置の概略構成図である。
【図2】本発明に係る混合を実施した実施例の結果を示す、復水脱塩装置出口水に相当するカラム出口水のCLイオン濃度推移特性図である。
【図3】混合を実施しない比較例の結果を示す、復水脱塩装置出口水に相当するカラム出口水のCLイオン濃度推移特性図である。
【符号の説明】
1 復水脱塩塔
2 CLイオンモニター
3 再生塔
4 樹脂移送配管
5 サンプリングライン
6 逆洗水ライン
7 空気ライン
R イオン交換樹脂[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a condensate treatment method and apparatus in an ammonia type condensate demineralizer in a thermal power plant or a pressurized water nuclear power plant (hereinafter referred to as a PWR nuclear power plant).
[0002]
[Prior art]
In a thermal power plant or a PWR nuclear power plant, the steam after driving the power generation turbine is cooled to condensate, and this condensate is heated to generate steam again to generate power. For this reason, condensate needs to be highly purified from the viewpoint of preventing corrosion of boilers, steam generators, nuclear reactors, etc., such as mixed bed condensate demineralizers, powder ion exchange resin filters, hollow fiber filters, etc. A purification device is used alone or in combination.
[0003]
The condensate demineralizer usually regenerates a water flow system composed of a plurality of condensate demineralization towers (hereinafter sometimes simply referred to as a demineralization tower) and an ion exchange resin used in the demineralization tower. In such a desalting tower, the regeneration process is started when a certain amount of water is treated. In the regeneration step, for example, the packed ion exchange resin is separated into a cation exchange resin and an anion exchange resin, hydrochloric acid or sulfuric acid is poured into the cation exchange resin, and sodium hydroxide is poured into the anion exchange resin. Detach. The resin from which the impurities have been desorbed is transferred to a desalting tower and treated again by passing through condensate.
[0004]
In thermal power plants and PWR nuclear power plants, ammonia ions are usually injected as pH adjusters and hydrazinium ions as deoxidizers in order to control the occurrence of corrosion from the latter stage of the desalting tower. Yes. In these condensate demineralization towers, so-called H—OH type operation is performed in which water is collected under the condition that the ammonia and hydrazine do not leak from the condensate demineralization tower. In addition, some thermal power plants have a so-called ammonia-type operation in which the condensate continues to flow even when these ions leak from the desalting tower outlet from the viewpoint of reducing operating costs. In the ammonia type operation, the operation cost can be reduced as the water flow period after the ion exchange resin of the condensate demineralizer breaks with ammonia is longer.
[0005]
[Problems to be solved by the invention]
However, as a result of long-term follow-up investigation of the operating state after a break with ammonia in the above ammonia type operation, it has been found that there are the following problems. That is, in the ammonia type operation as described above, it has been found that there is a phenomenon in which a leakage peak of CL ions appears when water continues to flow for a certain period after the ammonia break. This phenomenon has not been grasped so far because the regeneration process was entered before such a peak appeared. This phenomenon occurs even when the concentration of ions in the condensate is sufficiently low and there is almost no ion load in the condensate demineralizer, so the occurrence of this peak has occurred since the beginning of water flow. It is presumed that ions are concentrated while being gradually pushed out into the resin layer near the exit of the demineralization tower, and that the ions leak suddenly and a peak shape appears. Depending on the content of ion-exchange resin, the peak value of the above-mentioned peak may reach up to about 1 ppb at the current level of CL ion content in the resin, preventing corrosion of boilers, steam generators, piping, etc. From this point of view, it is not the water quality level that allows continuous water flow. Conventionally, it has been operated paying attention to fluctuations in water quality immediately after the ammonia break, and considering such fluctuations, for example, studies have been made to perform regeneration at an early timing. When trying to continue for a longer period of time, it turned out that it was necessary to take into account the phenomenon of the appearance of the CL ion peak as described above, and it was found that it was necessary to take measures that were not taken into account in the past .
[0006]
Therefore, the problem of the present invention is that, based on the new knowledge as described above, when the condensate demineralizer is operated in the ammonia form, the phenomenon in which the peak of the CL ion appears is appropriately prevented, compared with the conventional operation. The operation after an ammonia break can be continued for a long period of time, the frequency of regeneration can be greatly reduced and the stable treatment duration can be extended, and the cost of condensate treatment can be significantly reduced by reducing the amount of regenerant used. It is to provide a condensate treatment method and apparatus.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, the condensate treatment method according to the present invention monitors CL ions at the outlet of an ammonia type condensate demineralizer filled with an ion exchange resin, and the CL ion concentration or / and the concentration increasing tendency Water sampling is stopped when it reaches a predetermined reference value or more, and the resin layer is mixed without starting chemical regeneration and water flow is started again.
[0008]
The reference value of the CL ion concentration, which is a determination criterion for carrying out the mixing, can be set to 5 ng / L, for example, at the condensate demineralizer outlet CL ion concentration. In addition, the reference value of the CL ion concentration increasing tendency can be set to 3 ng / L, for example, by the increase width of the measured value at a predetermined measurement time interval. As the predetermined measurement time interval, for example, the interval from one measurement time to the next measurement time is set to 3 hours, and the concentration increasing tendency of the CL ions can be determined by the increase width during that interval. That is, in addition to determining the absolute value of the detected value of the CL ion concentration by comparing with the reference value, it is possible to compare and determine the upward tendency of CL ions detected after a certain period after the ammonia break with the reference value.
[0009]
Further, the reference value of the CL ion concentration and the reference value of the upward tendency when monitoring the CL ions are determined as follows, for example. That is, as the management criteria of normal PWR type nuclear power plants are operated generally at 5 n g / L. Managed by the reference value of CL ion concentration in the present invention also suit administration and a production value of the PWR type nuclear power plants present, it is preferable that the reference value 5 n g / L in the condensate demineralizer outlet.
[0010]
Furthermore, regarding the actual measurement of CL ions at the condensate demineralization tower outlet, since the measurement amount is very small, taking into account various errors, it is necessary to grasp not only one measured value but also the CL ion rising trend. This makes it possible to more accurately capture and avoid the peak of CL ions. Therefore, taking into account the control of CL ions below 5 ng / L and the accuracy of CL ion measurement and the number of samples to be measured (1 sample: for example, 30 minutes or more), the management reference value for an increase at a fixed measurement time interval is set. By setting it to 3 ng / L or more, peak generation of CL ions can be monitored and managed more accurately.
[0011]
Further, in the above method, it is detected that the CL ion concentration at the outlet of the ammonia-type condensate demineralizer or / and the concentration increasing tendency has reached a predetermined reference value or more, and the sampling is stopped. Mixing is performed, but if the time to reach the reference value can be roughly predicted, it is possible to mix the resin layer before these values reach the reference value. Can be repeated periodically.
[0012]
That is, another condensate treatment method according to the present invention, after a predetermined condensate treatment time has elapsed, before CL ions leak from the outlet of an ammonia-type condensate demineralizer filled with an ion exchange resin, for example, The resin layer is periodically mixed before CL ions that reach the reference value leak. The predetermined condensate treatment time can be set to about 30 days, for example.
[0013]
In the condensate treatment method as described above, mixing of the resin layer may be performed in a condensate demineralization tower, or may be performed by transferring the resin to a regeneration system. It is easier to carry out the process in the condensate demineralizer as it is.
[0014]
The condensate treatment apparatus according to the present invention includes a means for monitoring CL ions at the outlet of an ammonia-type condensate demineralizer filled with an ion exchange resin, and a CL ion concentration or / and a concentration increasing tendency monitored by the monitoring means. When the temperature reaches a predetermined reference value or more, it has means for stopping water sampling and generating a signal for mixing the resin layer without regenerating the chemicals. By this signal, water sampling can be stopped or the resin layer can be mixed automatically or manually.
[0015]
In the condensate treatment method and apparatus according to the present invention as described above, leakage of CL ions, particularly CL ions after a certain long period of time after an ammonia break in an ammonia type operation, which has not been a management target until now. The occurrence of a concentration peak is monitored and detected. The resin layer in the desalting tower is simply mixed without chemical regeneration before an undesirably large peak occurs. By mixing the resin layer, the CL ions in the resin layer that have been moved and concentrated in the resin layer are uniformly dispersed again in the entire resin layer. Since the CL ion concentration of the condensate demineralizer outlet water depends on the CL content of the ion exchange resin in the bottom layer of the condensate demineralizer, the resin layer is simply mixed and localized CL ions. Is uniformly dispersed in the entire resin layer, the CL ion concentration in the condensate demineralizer outlet water can be greatly reduced.
[0016]
Since the CL ion concentration in the condensate is usually low enough, even when the CL concentration at the condensate demineralizer outlet has risen to some extent, the total amount of CL ions in the resin layer is almost the same as the initial water flow rate. It is kept in. Therefore, the CL ion concentration in the condensate demineralizer outlet water can be substantially reduced to the initial level simply by uniformly dispersing the CL ions localized in the resin layer in the entire resin layer. It is possible to maintain the CL ion concentration level, which is likely to decrease or increase to the lower level, as it is. In other words, by simply repeating the resin mixing in the condensate demineralization tower, the ammonia type operation can be continued while reducing the outlet CL ion concentration to the initial value of the water start, and the frequency of resin regeneration is greatly reduced. Is done. Therefore, according to the present invention, unless an unexpected situation such as seawater leakage occurs, it is possible to pass water for a long time without performing chemical regeneration, and the operation cost and regeneration time associated with regeneration can be significantly reduced. It becomes possible.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings together with examples of column tests.
First, an example of the apparatus will be described with reference to the drawings regarding the operation of the condensate demineralizer ammonia type in a thermal power plant and a PWR nuclear power plant. FIG. 1 is a schematic configuration diagram of a condensate demineralizer for explaining the present invention. First, in the condensate demineralizer, each condensate demineralizer 1 is filled with a predetermined ion exchange resin R at a predetermined filling rate, and contains ammonia and hydrazine at a predetermined concentration from the upstream side of the demineralizer 1. However, the condensate moves at a predetermined flow rate and enters a sampling state. Here, the CL ion of the desalting tower outlet water is detected by the CL ion monitor 2 for each tower through the sampling line 5, and the CL ion concentration value exceeds the reference value set in advance at the condensate demineralizer outlet. Or, the CL ion monitor 2 has a tendency to increase from a measurement value at a time to an increase width of the measurement value at the next time (that is, an increase width of the measurement value at a predetermined measurement time interval) exceeding a preset reference value. Stop water sampling with the end point being observed. Next, the resin whose sampling has been stopped is supplied with air and backwash water from the air line 7 and the backwash water line 6 in the desalting tower 1 or the regeneration tower 3, and the resin layer is mixed for a certain time. In the case of mixing in the desalting tower 1, the resin is sufficiently mixed without being transferred, and then sampling is resumed. In the case of mixing in the regeneration tower 3, after sampling is stopped, the water is transferred to the regeneration tower 3 through the resin transfer pipe 4, mixed sufficiently in the regeneration tower 3, and then transferred again to the desalting tower 1. And start sampling again. The resin mixing in the desalting tower 1 or the regeneration tower 3 is sufficient if the resin layer is sufficiently mixed, and it is not particularly necessary to define the flow rate and time of air and backwash water.
[0018]
【Example】
In the laboratory, a model test was performed using a column under the following water flow conditions.
Figure 0004020372
[0019]
As an example, the result of water flow when resin mixing is performed is shown in FIG. 2 (water flow test 1). Moreover, as a comparative example, the water flow result when not mixing is shown in FIG. 3 (water flow test 2). In the comparative example shown in FIG. 3, the CL ion rises after about 1100 hours (45.8 days) from the start of water flow, but in the example shown in FIG. 2 where mixing was performed, the CL ion concentration was kept sufficiently low. I'm leaning.
[0020]
As can be seen from the above test results, by performing the mixing in the present invention at an appropriate timing, it is possible to prevent the occurrence of an undesirable peak of the CL ion concentration, and to stabilize ammonia as it is without performing resin regeneration. The mold operation can be continued. As described above, this mixing eliminates the localization of CL ions in the resin layer, and is considered to return to the initial state without substantial change of the CL ions in the entire resin layer. Alternatively, by repeating the mixing after detecting that the state to be mixed has been reached as described above, such dispersion of CL ions can be realized a plurality of times. Therefore, it is possible to prevent an undesirable peak of the CL ion concentration from occurring for an extremely long period of time, and it is possible to continue stable ammonia type operation at a low cost.
[0021]
【The invention's effect】
As described above, according to the condensate treatment method and apparatus according to the present invention, before the undesirable peak of the CL ion concentration in the outlet water of the ammonia-type condensate demineralizer occurs, the ion exchange resin is chemically regenerated. The simple operation of simply mixing the resin layers without the need to do so ensures that the desired ammonia-type operation can be continued for a long period of time, reducing the time and cost required to regenerate the ion exchange resin as a whole. The operating cost can be greatly reduced.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a condensate demineralization apparatus to which the present invention is applied.
FIG. 2 is a graph of CL ion concentration transition characteristics of column outlet water corresponding to condensate demineralizer outlet water, showing the results of an example in which mixing according to the present invention was performed.
FIG. 3 is a graph of CL ion concentration transition characteristics of column outlet water corresponding to condensate demineralizer outlet water, showing the results of a comparative example in which mixing is not performed.
[Explanation of symbols]
1 Condensate Demineralization Tower 2 CL Ion Monitor 3 Regeneration Tower 4 Resin Transfer Piping 5 Sampling Line 6 Backwash Water Line 7 Air Line R Ion Exchange Resin

Claims (7)

イオン交換樹脂を充填したアンモニア型復水脱塩装置の出口におけるCLイオンを監視し、CLイオン濃度または/および濃度上昇傾向が予め定めた基準値以上に達した段階で採水を中止し、薬品再生することなく樹脂層を混合して再度通水を開始することを特徴とする復水処理方法。Monitors CL ions at the outlet of the ammonia-type condensate demineralizer filled with ion-exchange resin, and stops sampling when the concentration of CL ions or / and the concentration increasing trend exceeds a predetermined reference value. A condensate treatment method comprising mixing resin layers without regenerating and starting water flow again. 前記混合の実施の判断基準となるCLイオン濃度の基準値を復水脱塩装置出口CLイオン濃度で5ng/Lとする、請求項1の復水処理方法。The condensate treatment method according to claim 1, wherein a reference value of the CL ion concentration that is a criterion for determining the mixing is 5 ng / L in terms of the CL ion concentration at the outlet of the condensate demineralizer. 前記混合の実施の判断基準となるCLイオンの濃度上昇傾向の基準値を、所定測定時間間隔での測定値の上昇幅で3ng/Lとする、請求項1または2の復水処理方法。3. The condensate treatment method according to claim 1, wherein a reference value of the tendency of increasing the concentration of CL ions, which is a criterion for performing the mixing, is set to 3 ng / L in terms of an increase in the measured value at a predetermined measurement time interval. 所定復水処理時間以上経過した後、イオン交換樹脂を充填したアンモニア型復水脱塩装置の出口からCLイオンが漏洩する前に樹脂層の混合を定期的に行うことを特徴とする復水処理方法。A condensate treatment in which the resin layer is periodically mixed after a predetermined condensate treatment time has elapsed and before CL ions leak from the outlet of an ammonia type condensate demineralizer filled with an ion exchange resin. Method. 所定復水処理時間を30日とする、請求項4の復水処理方法。The condensate treatment method according to claim 4, wherein the predetermined condensate treatment time is 30 days. 樹脂層の混合を復水脱塩塔で行う、請求項1〜5のいずれかに記載の復水処理方法。The condensate treatment method according to any one of claims 1 to 5, wherein the resin layer is mixed in a condensate demineralization tower. イオン交換樹脂を充填したアンモニア型復水脱塩装置の出口におけるCLイオンを監視する手段と、該監視手段により監視されたCLイオン濃度または/および濃度上昇傾向が予め定めた基準値以上に達したときに、採水を中止し、薬品再生することなく樹脂層を混合するための信号を発する手段を有することを特徴とする復水処理装置。Means for monitoring CL ions at the outlet of the ammonia-type condensate demineralizer filled with ion exchange resin, and the CL ion concentration monitored by the monitoring means or / and the concentration increasing tendency has reached a predetermined reference value or more. A condensate treatment apparatus characterized by having means for stopping the sampling of water and generating a signal for mixing the resin layer without regenerating the chemicals.
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