JPH0512997B2 - - Google Patents
Info
- Publication number
- JPH0512997B2 JPH0512997B2 JP1318958A JP31895889A JPH0512997B2 JP H0512997 B2 JPH0512997 B2 JP H0512997B2 JP 1318958 A JP1318958 A JP 1318958A JP 31895889 A JP31895889 A JP 31895889A JP H0512997 B2 JPH0512997 B2 JP H0512997B2
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- present
- anion exchange
- ion exchange
- surface potential
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003957 anion exchange resin Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 14
- 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 claims description 13
- 239000012535 impurity Substances 0.000 claims description 10
- 239000003729 cation exchange resin Substances 0.000 claims description 9
- 238000010248 power generation Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 238000010612 desalination reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 238000011033 desalting Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036449 good health Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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
- Treatment Of Water By Ion Exchange (AREA)
Description
〔産業上の利用分野〕
本発明は、混床式濾過脱塩による懸濁性不純物
の除去方法に関し、特に従来品よりもイオン交換
容量および／または表面電位を低下させた陰イオ
ン交換樹脂と、陽イオン交換樹脂を混合してなる
混床式濾過脱塩方法を用いた懸濁性不純物の除去
方法方法に関するものである。
〔従来の技術〕
汽力発電設備では、ボイラーの内部を常に清浄
な状態に保たなければならないので、タービン復
水器からボイラー内へ環流する復水を復水脱塩器
にて浄化処理し、高度に浄化した後、ボイラー内
への冷却水として給水している。
この復水脱塩器は、陽イオン交換樹脂と陰イオ
ン交換樹脂とが混合充填された、いわゆる混床式
脱塩塔であつて、復水中のイオン成分と懸濁性不
純物（クラツドと通称される。）とをイオン交換
及び吸着によつて分離し、復水を浄化するもので
ある。そして、陽イオン交換樹脂と陰イオン交換
樹脂とを混合して混床を形成する方法としては、
ゲル型樹脂とポーラス型樹脂を使用する方法が提
案され採用されてきた。
この粒状イオン交換樹脂を用いる方法にあつて
は、イオン交換樹脂に吸着されたイオン成分やク
ラツドは、定期的に化学的薬品再生や物理的逆洗
再生を施すことによつて、イオン交換樹脂から不
純物を除去し、常に復水脱塩塔の清浄度の維持に
務めている。
〔発明が解決しようとする課題〕
最近、汽力発電設備においては、復水からイオ
ン成分やクラツドの除去効果のうち、クラツドの
除去効果を強化することにより、復水からボイラ
ーへ持ち込まれるクラツドを低減し、ボイラーの
健全性を維持する傾向があり、前述のイオン交換
樹脂を用いる方法ではクラツドの除去効果が小さ
く、装置の高度化要求に対応できないことが判つ
た。
本発明者はこのような現状に鑑み鋭意研究を重
ね本発明に想到したものであつて、本発明は復水
の処理操作において、クラツドの分離能力の大き
い混床式濾過脱塩方法を提供することを目的とす
る。
〔課題を解決するための手段〕
本発明は、汽力発電設備の復水浄化装置の被処
理水中に微量存在する懸濁性不純物を、陽イオン
交換樹脂及び陰イオン交換樹脂から成る混床によ
つて濾過脱塩する懸濁性不純物の除去方法におい
て、イオン交換量が0.9〜1.1meq／ml・Ｒ−Cl及
び／又は表面電位が20〜35ｍＶである該陰イオン
交換樹脂を用いることを特徴とする懸濁性不純物
の除去方法であり、これにより上記課題を解決す
ることができる。
本発明において、汽力発電設備とは、火力、原
子力発電等の設備を、復水浄化装置の被処理水中
に微量存在する懸濁性不純物とは、主に金属酸化
物、例えば、酸化鉄、酸化銅等のコロイド物質で
クラツドと通称されるものを意味する。
本発明に用いられる陽イオン交換樹脂及び陰イ
オン交換樹脂は上記条件を満足するならば特に限
定されず、業界公知のものが使用できるが、好ま
しくは、ゲル型樹脂、具体的には、スチレン・ジ
ビニルベンゼン共重合を基体とした、強酸性ゲル
型陽イオン交換樹脂及び強塩基性陰イオン交換樹
脂等が挙げられる。また、該両樹脂の形状も任意
であるが、乾燥時の平均粒径が粒状の場合、350
〜1200μｍ、粉末状の場合、30〜200μｍの範囲の
粒状または粉末状のものが好ましい。
本発明に用いられる陰イオン交換樹脂のイオン
交換容量の単位、meq／ml・Ｒ−Clは樹脂基準型
体積基準単位当たりの当量数を意味し、本発明で
は、この値を従来のゲル型樹脂の標準値（1.2〜
1.4meq／ml・Ｒ−Cl）よりも低下させた範囲
（0.9〜1.1meq／ml・Ｒ−Cl）とする。
又は、該陰イオン交換樹脂の表面電位を従来品
のゲル型樹脂の標準値（35〜45ｍＶ）よりも低下
させた範囲（20〜35ｍＶ）とするか、前記0.9〜
1.1meq／ml・Ｒ−Clのイオン交換容量の樹脂と
この20〜35ｍＶの範囲の樹脂とを併用する。即
ち、カラムに充填された陰イオン交換樹脂のイオ
ン交換容量と表面電位とがともに上記本発明の範
囲にあらなければならないとは限らない。該表面
電位は、具体的には、電気泳動法により測定でき
る。
又、本発明における陰イオン交換樹脂を該イオ
ン交換容量、表面電位に調整するための具体的手
段としては、製造段階では、ジビニルベンゼンの
含有量を調整することにより可能であり、また、
人為的には高分子電解質処理等により調整でき
る。
〔作用〕
本発明においては、従来の混床式濾過脱塩方法
に比較し、陰イオン交換樹脂のイオン交換容量及
び／又は表面電位が低いため、クラツドとの間に
働く相互作用が小さく陽イオン交換樹脂がクラツ
ドを捕捉し易い環境となることにより、濾過脱塩
操作に際し、よりクラツド濃度の低い高純度の復
水を得ることができる。
以下、本発明を従来技術と対比して述べれば、
表−１は従来の陰イオン交換樹脂の物性を比較し
たものであるが、本発明の陰イオン交換樹脂は従
来品よりイオン交換容量が小さく、また表面電位
が小さいことがわかる。
[Industrial Application Field] The present invention relates to a method for removing suspended impurities by mixed bed filtration and desalination, and in particular, an anion exchange resin with lower ion exchange capacity and/or surface potential than conventional products; The present invention relates to a method for removing suspended impurities using a mixed bed filtration and desalting method in which a cation exchange resin is mixed. [Conventional technology] In steam power generation equipment, the inside of the boiler must be kept clean at all times, so the condensate that flows back into the boiler from the turbine condenser is purified using a condensate demineralizer. After being highly purified, water is supplied to the boiler as cooling water. This condensate demineralizer is a so-called mixed bed demineralizer that is packed with a mixture of cation exchange resin and anion exchange resin, and contains ionic components and suspended impurities (commonly known as crud) in the condensate. ) by ion exchange and adsorption to purify condensate. The method of mixing a cation exchange resin and an anion exchange resin to form a mixed bed is as follows:
Methods using gel-type resins and porous-type resins have been proposed and adopted. In the method using this granular ion exchange resin, the ionic components and crud adsorbed on the ion exchange resin can be removed from the ion exchange resin by periodically performing chemical regeneration and physical backwashing regeneration. It removes impurities and constantly maintains the cleanliness of the condensate demineralization tower. [Problem to be solved by the invention] Recently, in steam power generation equipment, the amount of crud brought into the boiler from condensate has been reduced by strengthening the crud removal effect among the effects of removing ionic components and crud from condensate. However, there is a tendency to maintain the integrity of the boiler, and it was found that the method using the above-mentioned ion exchange resin had a small crud removal effect and could not meet the demand for more sophisticated equipment. In view of the current situation, the present inventor has conducted extensive research and has come up with the present invention, and the present invention provides a mixed bed filtration desalination method that has a large crud separation capacity in a condensate treatment operation. The purpose is to [Means for Solving the Problems] The present invention removes suspended impurities present in trace amounts in the water to be treated in a condensate purification system for steam power generation equipment by using a mixed bed consisting of a cation exchange resin and an anion exchange resin. The method for removing suspended impurities by filtration and desalination is characterized by using the anion exchange resin having an ion exchange amount of 0.9 to 1.1 meq/ml R-Cl and/or a surface potential of 20 to 35 mV. This is a method for removing suspended impurities, which can solve the above problems. In the present invention, steam power generation equipment refers to thermal power generation, nuclear power generation, etc. It refers to colloidal substances such as copper, commonly known as clades. The cation exchange resin and anion exchange resin used in the present invention are not particularly limited as long as they satisfy the above conditions, and those known in the industry can be used. Preferably, gel-type resins, specifically styrene, Examples include strongly acidic gel-type cation exchange resins and strong basic anion exchange resins based on divinylbenzene copolymerization. In addition, the shape of both resins can be arbitrary, but if the average particle size when dry is granular, 350
~1200 μm, and in the case of powder, granules or powders with a size of 30 to 200 μm are preferred. The unit of ion exchange capacity of the anion exchange resin used in the present invention, meq/ml・R-Cl, means the number of equivalents per resin standard volume basis, and in the present invention, this value is compared to that of the conventional gel type resin. Standard value (1.2~
1.4 meq/ml・R-Cl) (0.9 to 1.1 meq/ml・R-Cl). Alternatively, the surface potential of the anion exchange resin is set to a range (20 to 35 mV) lower than the standard value (35 to 45 mV) of conventional gel type resins, or the surface potential of the anion exchange resin is set to a range (20 to 35 mV) lower than the standard value (35 to 45 mV) of conventional gel type resins, or
A resin with an ion exchange capacity of 1.1 meq/ml.R-Cl and a resin with an ion exchange capacity of 20 to 35 mV are used together. That is, both the ion exchange capacity and the surface potential of the anion exchange resin packed in the column do not necessarily have to fall within the scope of the present invention. Specifically, the surface potential can be measured by electrophoresis. Further, as a specific means for adjusting the ion exchange capacity and surface potential of the anion exchange resin in the present invention, it is possible to adjust the content of divinylbenzene at the manufacturing stage;
It can be artificially adjusted by polymer electrolyte treatment or the like. [Function] In the present invention, since the ion exchange capacity and/or surface potential of the anion exchange resin is lower than in the conventional mixed bed filtration desalination method, the interaction with the cladding is small and the cation By creating an environment in which the exchange resin can easily trap crud, highly purified condensate with a lower crud concentration can be obtained during the filtration and desalination operation. Below, the present invention will be described in comparison with the prior art.
Table 1 compares the physical properties of conventional anion exchange resins, and it can be seen that the anion exchange resin of the present invention has a lower ion exchange capacity and a lower surface potential than conventional products.
以下、本発明を具体的実施例、比較例に基づ
き、更に詳細に説明するが、本発明は、これに限
定されるものではない。
本発明の濾過脱塩方式におけるクラツド除去効
果を混床実機長カラム試験により、従来の濾過脱
塩操作と比較する。
試験条件
第１図の試験装置を使用し、以下の条件によ
り試験を行つた。
(i) 樹脂仕様：従来の強塩基性ゲル型陰イオン
交換樹脂（OH型；イオン交換容量＝
1.3meq／ml・Ｒ−Cl、表面電位＝35ｍＶ）
及び本発明の強塩基性ゲル型陰イオン交換樹
脂（OH型；イオン交換容量＝1.0meq／ml・
Ｒ−Cl、表面電位＝25ｍＶ）と強酸基性ゲル
型陽イオン交換樹脂を組み合わせて混床状態
で使用。
(ii) 樹脂量：陽イオン／陰イオン交換樹脂比＝
1.6／１で層高90cm相当分（約２）を混合
した充填。
(iii) 通水線流速：LV＝108ｍ／ｈ
(iv) 通水期間：２週間
第１図の試験装置は、カラムユニツトとサン
プリングユニツトからなり、カラムユニツト
は、上記条件で通水される被処理水をカラムに
導入する管、弁及び圧力スイツチPS、圧力ゲ
ージPI、温度計TI、及び上記樹脂が充填され
るカラムから概略構成され、サンプリングユニ
ツトは、該樹脂により濾過脱塩処理された処理
水を処理水出口に導く管、流量計FI、濾紙
MF、イオン交換濾紙IEP、積算流量計FQ、導
電率計CEからなり、第２図に示したクラツド
鉄濃度を有する被処理水１を上記条件にて処理
し、処理水出口の同濃度を経時的に測定した。
試験結果
第２図に試験結果の一例を示す。第２図にお
いて、横軸は通水日数を示し、縦軸はカラム入
口及び出口のクラツド鉄濃度を示す。
これによれば、陰イオン交換樹脂の交換容量
及び表面電位を低下させた組合せの本発明例３
の方が、従来例２よりクラツド除去能力が高い
ことが確認できた。
〔発明の効果〕
本発明のイオン交換樹脂による濾過脱塩方法に
おけるクラツド除去効果は、従来の濾過脱塩方法
よりも大幅に優れていることが確認され、その結
果、汽力発電設備の復水を高度に浄化することが
可能となり、ボイラーを健全に維持でき、実用
上、極めて有利な方法であるといえる。
Hereinafter, the present invention will be explained in more detail based on specific examples and comparative examples, but the present invention is not limited thereto. The crud removal effect of the filtration-desalting system of the present invention will be compared with that of conventional filtration-desalting operations through a mixed-bed actual length column test. Test Conditions The test was conducted under the following conditions using the test apparatus shown in Figure 1. (i) Resin specifications: Conventional strong basic gel type anion exchange resin (OH type; ion exchange capacity =
1.3meq/ml・R-Cl, surface potential=35mV)
and strongly basic gel type anion exchange resin of the present invention (OH type; ion exchange capacity = 1.0meq/ml・
R-Cl, surface potential = 25 mV) and a strong acidic gel type cation exchange resin are used in a mixed bed state. (ii) Resin amount: cation/anion exchange resin ratio =
Filled with a mixture of 1.6/1 equivalent to a layer height of 90cm (approximately 2). (iii) Linear water flow velocity: LV = 108 m/h (iv) Water flow period: 2 weeks The test equipment shown in Figure 1 consists of a column unit and a sampling unit. The sampling unit is roughly composed of a pipe for introducing treated water into the column, a valve, a pressure switch PS, a pressure gauge PI, a thermometer TI, and a column filled with the above resin. Pipe leading water to treated water outlet, flow meter FI, filter paper
It consists of MF, ion-exchange filter paper IEP, integrated flow meter FQ, and conductivity meter CE, and treated water 1 having the clad iron concentration shown in Figure 2 is treated under the above conditions, and the same concentration at the treated water outlet is measured over time. was measured. Test Results Figure 2 shows an example of the test results. In FIG. 2, the horizontal axis shows the number of days of water flow, and the vertical axis shows the clad iron concentration at the column inlet and outlet. According to this, Example 3 of the present invention is a combination in which the exchange capacity and surface potential of the anion exchange resin are reduced.
It was confirmed that the crud removal ability was higher than that of Conventional Example 2. [Effects of the Invention] It has been confirmed that the crud removal effect of the filtration desalination method using the ion exchange resin of the present invention is significantly superior to that of the conventional filtration desalination method. This method can be said to be extremely advantageous from a practical point of view, as it makes it possible to purify to a high degree and maintain the boiler in good health.
第１図は、本発明の成果を証明すべく実施した
混床式カラム試験装置の系統図であり、第２図は
混床式カラム試験結果のうち、イオン交換樹脂に
よるクラツド除去に関する破過曲線の一例を示す
グラフである。
符号の説明、１：被処理水入口水中のクラツド
鉄濃度、２：従来法処理水出口のクラツド鉄濃
度、３：本発明法処理水出口のクラツド鉄濃度。
Figure 1 is a system diagram of the mixed bed column test equipment carried out to prove the results of the present invention, and Figure 2 shows the breakthrough curve for crud removal by ion exchange resin among the mixed bed column test results. It is a graph showing an example. Explanation of the symbols: 1: Clad iron concentration in treated water inlet water, 2: Clad iron concentration at conventional method treated water outlet, 3: Clad iron concentration at present method treated water outlet.
Claims (1)
微量存在する懸濁性不純物を、陽イオン交換樹脂
及び陰イオン交換樹脂から成る混床によつて濾過
脱塩する懸濁性不純物の除去方法において、イオ
ン交換量が0.9〜1.1meq／ml・Ｒ−Cl及び／又は
表面電位が20〜35ｍＶである該陰イオン交換樹脂
を用いることを特徴とする懸濁性不純物の除去方
法。1. A method for removing suspended impurities in which trace amounts of suspended impurities present in water to be treated in a condensate purification device of a steam power generation facility are filtered and desalted using a mixed bed consisting of a cation exchange resin and an anion exchange resin. A method for removing suspended impurities, characterized in that the anion exchange resin having an ion exchange amount of 0.9 to 1.1 meq/ml·R-Cl and/or a surface potential of 20 to 35 mV is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318958A JPH03181385A (en) | 1989-12-11 | 1989-12-11 | Removing method for suspendible impurity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318958A JPH03181385A (en) | 1989-12-11 | 1989-12-11 | Removing method for suspendible impurity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03181385A JPH03181385A (en) | 1991-08-07 |
| JPH0512997B2 true JPH0512997B2 (en) | 1993-02-19 |
Family
ID=18104892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1318958A Granted JPH03181385A (en) | 1989-12-11 | 1989-12-11 | Removing method for suspendible impurity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03181385A (en) |
-
1989
- 1989-12-11 JP JP1318958A patent/JPH03181385A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03181385A (en) | 1991-08-07 |
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