JPS59338A - Method for measuring sodium fraction of strong acidic cation exchange resin - Google Patents
Method for measuring sodium fraction of strong acidic cation exchange resinInfo
- Publication number
- JPS59338A JPS59338A JP57109813A JP10981382A JPS59338A JP S59338 A JPS59338 A JP S59338A JP 57109813 A JP57109813 A JP 57109813A JP 10981382 A JP10981382 A JP 10981382A JP S59338 A JPS59338 A JP S59338A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- cation exchange
- acidic cation
- sodium
- strongly acidic
- 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.)
- Granted
Links
- 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 abstract description 94
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 67
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 58
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000011734 sodium Substances 0.000 title claims description 72
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims description 66
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 45
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 45
- 238000005259 measurement Methods 0.000 claims abstract description 18
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 13
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 238000010612 desalination reaction Methods 0.000 claims description 26
- 239000003480 eluent Substances 0.000 claims description 17
- 238000003795 desorption Methods 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 42
- 239000007788 liquid Substances 0.000 abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010828 elution Methods 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 229910021529 ammonia Inorganic materials 0.000 description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229940023913 cation exchange resins Drugs 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000011001 backwashing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 ammonium ions Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012492 regenerant Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は復水脱塩装置１特にアンモニア形復水脱塩装置
に用いられている強酸性陽イオン交換樹脂のナトリウム
分率の測定方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for measuring the sodium fraction of a strongly acidic cation exchange resin used in a condensate desalination apparatus 1, particularly an ammonia type condensate desalination apparatus.
アンモニア形強酸性陽イオン交換樹脂とＯＨ形強塩基性
陰イオン交換樹脂の混合イオン交換樹脂を用いてボイラ
ー復水を処理する。いわゆるアンモニア形復水脱塩装置
は、復水中のアンモニウムイオンを除去せずに他の不純
物を除去するので、Ｈ形強酸性陽イオン交換樹脂とＯＨ
形強塩基性陰イオン交換樹脂の混合イオン交換樹脂を用
いる。いわゆるＨ−ＯＨ形復水脱塩装置と比較し、ラン
ニングコストが廉価であるために、復水の脱塩処理にア
ンモニア形復水脱塩装置が盛んに用いられるようになっ
て来た。Boiler condensate is treated using a mixed ion exchange resin consisting of an ammonia type strongly acidic cation exchange resin and an OH type strongly basic anion exchange resin. The so-called ammonia type condensate desalination equipment removes other impurities without removing ammonium ions in condensate, so it uses H type strongly acidic cation exchange resin and OH
A mixed ion exchange resin of strongly basic anion exchange resin is used. Ammonia type condensate desalination equipment has come to be widely used for desalination treatment of condensate because its running cost is lower than that of so-called H-OH type condensate desalination equipment.
アンモニア形復水脱塩装置の強酸性陽イオン交換樹脂に
おいては、 ＮＨ４形強酸性陽４オン交換樹脂で圧倒的
にアンモニウムイオンが多量に存在する復水中の微量の
ナトリウノ、イオンをイオン交換除去するものであり、
したがってＮＨ，形からＮａ形へとイオン交換平衡を僅
かにずらすだけであるから、当該イオン交換樹脂のすト
リウム分率、すなわちＲ−Ｎａ／Ｆ −ＮＨ４＋ Ｒ−
Ｎａの値が被処理水のナトリウムリークに直接影響を与
え、 Ｎａ分率が帆００３以−上であるとナトリウムイ
オンがリークし。The strongly acidic cation exchange resin of the ammonia type condensate desalination equipment uses NH4 type strongly acidic cation exchange resin to ion exchange remove trace amounts of sodium ions and ions in the condensate, which contains an overwhelmingly large amount of ammonium ions. It is a thing,
Therefore, since the ion exchange equilibrium is only slightly shifted from the NH, form to the Na form, the thorium fraction of the ion exchange resin, that is, R-Na/F -NH4+ R-
The Na value directly affects the sodium leak in the water to be treated, and if the Na fraction is 003 or higher, sodium ions will leak.
アンモニア形復水脱塩装置として運転が困難となる。It becomes difficult to operate as an ammonia type condensate desalination equipment.
しだがってアンモニア形復水脱塩装置においては当該強
酸性陽イオン交換樹脂のナトリウム分率を測定すること
は運転管理上重要である。Therefore, in ammonia type condensate desalination equipment, it is important for operational management to measure the sodium fraction of the strongly acidic cation exchange resin.
たとえば新品の強酸性陽イオン交換樹脂はＮａ形である
から、新品樹脂からアンモニア形復水脱塩装置をスター
トする場合は、１回の再生では前記したナトリウム分率
の値にならず、しだがって数サイクルの間Ｈ−ＯＨ形復
水脱塩装置として運転し、徐々にナトリウム分率の値を
低下させ、ある時期にす） ＩＪウム分率を測定して前
記の値以内に達したことを確認した後、アンモニア形復
水脱塩装置に移行させている。またアンモニア形復水脱
塩装置に新品の強酸性陽イオン交換樹脂を補給した場合
や当該装置の混合イオン交換樹脂を除鉄剤で処理した場
合も、ナトリウム分率が増加するので前述と同じような
措置を実施せねばならない。さらにアンモニア形復水脱
塩装置で運転している際に、復水に海水がリークし復水
中のナトリウムイオン濃度が異常に増加した場合もその
サイクルの再生後においては２強酸性陽イオン交換樹脂
のナトリウム分率が増加するので、前述と同じような措
置を実施せねばならない。For example, a new strongly acidic cation exchange resin is in the Na type, so when starting an ammonia type condensate desalination equipment from a new resin, the sodium content will not reach the above-mentioned value after one regeneration, and the It was operated as a H-OH type condensate desalination equipment for several cycles, and the value of the sodium fraction was gradually lowered until a certain period). After confirming this, the system was transferred to an ammonia-type condensate desalination equipment. Also, when a new strongly acidic cation exchange resin is refilled in an ammonia type condensate desalination equipment, or when the mixed ion exchange resin of the equipment is treated with an iron remover, the sodium fraction increases, so the same problem as mentioned above occurs. Measures must be taken. Furthermore, if seawater leaks into the condensate and the sodium ion concentration in the condensate increases abnormally when an ammonia-type condensate desalination equipment is operated, after the cycle is regenerated, two strongly acidic cation exchange resins will be used. Since the sodium content of
このようにアンモニア形復水脱塩装置においては何らか
のアクシデントが発生する毎に強酸性陽イオン交換樹脂
のナトリウム分率を測定することが処理水のナトリウム
リークを管理する上で必要である。As described above, in the ammonia type condensate desalting apparatus, it is necessary to measure the sodium fraction of the strongly acidic cation exchange resin every time some kind of accident occurs in order to manage sodium leakage of the treated water.
また本発明者等は前述したような新品樹脂の補給、除鉄
剤による処理、あるいは海水リーク時などのようなアク
シデントが起らない。In addition, the inventors of the present invention do not have to deal with accidents such as replenishment of new resin, treatment with iron remover, or leakage of seawater as described above.
通常の復水の処理においても強酸性陽イオン交換樹脂の
ナトリウム分率を測定することによって、再生剤費を大
巾に低下させることができることを知見した。We have discovered that even in ordinary condensate treatment, by measuring the sodium content of strongly acidic cation exchange resins, it is possible to significantly reduce regenerant costs.
すなわちコンデンサーから海水がリークしない通常の復
水の場合、復水脱塩装置の入口の復水は酸化鉄などのク
ラッドが存在するもののナトリウムイオンなどの不純物
イオンは極微量しか含まれていない。したがってこのよ
うな復水を処理する場合の通水の終点は。In other words, in the case of normal condensate where seawater does not leak from the condenser, the condensate at the inlet of the condensate desalination equipment contains crud such as iron oxide, but contains only trace amounts of impurity ions such as sodium ions. Therefore, when treating such condensate, what is the end point of water flow?
あらかじめ決定した充分に余裕がある一定収量に達した
場合か、あるいは前記クラッドが樹脂層中に捕捉される
ことによる圧力損失の増加が主なる要因であり１通水の
終点におけるイオン交換樹脂は不純物イオンがほとんど
吸着していないので、イオン交換的見地からはまだ充分
に復水の通水に供することができるものである。換言す
れば、このような復水の通水の終点に達したアンモニア
形復水脱塩装置の強酸性陽イオン交換樹脂のナトリウム
分率は０．００３以下である。The main cause is an increase in pressure loss when a predetermined yield with sufficient margin is reached, or when the cladding is trapped in the resin layer, and the ion exchange resin at the end of one water flow is free of impurities. Since almost no ions are adsorbed, from the viewpoint of ion exchange, it can still be used for sufficient condensate water flow. In other words, the sodium fraction of the strongly acidic cation exchange resin of the ammonia-type condensate desalination apparatus that has reached the end point of such condensate flow is 0.003 or less.
従来のアンモニア形復水脱塩装置においては前述したよ
うな定収量あるいは圧力損失の増加が要因となって復水
の通水の終点に達した混合イオン交換樹脂でも通常の再
生を行なっていたが、たとえば当該混合イオン交換樹脂
を純水等で逆洗してクラッドを除去し２次いで当該混合
イオン交換樹脂の強酸性陽イオン交換樹脂のナトリウム
分率が０．００３以下の値であることが確認できれば再
生することなく、そのまま通水塔に充填し、再び復水の
通水に供することができる。通常の復水を処理する場合
、このような処理方法を採用すれば゛再生剤費を約１／
３に節約することができる。In conventional ammonia type condensate desalination equipment, normal regeneration was performed even when the mixed ion exchange resin reached the end point of condensate water flow due to the above-mentioned fixed yield or increased pressure loss. For example, the mixed ion exchange resin is backwashed with pure water to remove crud, and then it is confirmed that the sodium fraction of the strongly acidic cation exchange resin in the mixed ion exchange resin is 0.003 or less. If possible, the water can be directly filled into a water tower without being regenerated and used to pass condensate again. When treating ordinary condensate, if this treatment method is adopted, the regenerant cost can be reduced by about 1/2.
You can save up to 3.
このようにアンモニア形復水脱塩装置においては２強酸
性陽イオン交換樹脂のナトリウム分率を測定することは
前述の装置の管理面から、さらには前述したよう乏処理
方法を採用する場合に重要である。In this way, in ammonia type condensate desalination equipment, it is important to measure the sodium fraction of the strongly acidic cation exchange resin from the viewpoint of equipment management, as well as when adopting the poor treatment method described above. It is.
ところで強酸性陽イオン交換樹脂のすｌ−ＩＪウム分率
を測定することは従来では非常に手数がかかり、即座に
測定結果が得られないという欠点を有している。By the way, measuring the sulfur-IJium fraction of a strongly acidic cation exchange resin has conventionally been very time-consuming and has the disadvantage that measurement results cannot be obtained immediately.
すなわち従来の測定方法は検体である強酸性陽イオン交
換樹脂の小量を装置から採取し。In other words, the conventional measurement method involves collecting a small amount of the sample, a strongly acidic cation exchange resin, from a device.
この検体を分析室に持ち込んで、小型カラムに充填し、
逆洗などしてクラッドを除去した後、当該カラムに大過
剰の塩酸などの酸を通液して５強酸性陽イオン交換樹脂
の吸着イオンを全て脱着し２次いで当該脱着液のナトリ
ウムイオン量を原子吸光法や炎光分析などで測定し、そ
の分析値より前記ナトリウム分率を算出していた。This sample is brought to the analysis laboratory and packed into a small column.
After removing the crud by backwashing, etc., a large excess of acid such as hydrochloric acid is passed through the column to desorb all the adsorbed ions of the 5 strongly acidic cation exchange resin, and then the amount of sodium ions in the desorbed solution is It was measured by atomic absorption spectrometry, flame light analysis, etc., and the sodium fraction was calculated from the analytical value.
しかしながら従来のかかる測定方法では測定に時間がか
かりすぎ、即座にナトリウム分率を知ることができず、
前述したような新品樹脂からアンモニア形復水脱塩装置
に移行させる場合とか、クラッドを逆洗で除去しただけ
で再び復水の通水に供するような処理方法を採用する場
合等に即座に操作を追随させることができない。したが
ってナトリウム分率がｏ、ｏｏ３以下の値になっている
にもがかわらず、その値の確認が遅れるため、アンモニ
ア形復水脱塩装置へ移行させる時期が遅れたり。However, the conventional measuring method takes too long to measure, and the sodium content cannot be determined immediately.
It can be operated immediately when transferring from a new resin to an ammonia type condensate desalination equipment as mentioned above, or when adopting a treatment method in which the crud is simply removed by backwashing and the condensate is passed through again. cannot be followed. Therefore, even though the sodium fraction is below o or oo3, there is a delay in confirming the value, which may delay the transition to the ammonia type condensate desalination equipment.
あるいは無駄な再生をせねばならなかった。Or they had to play it back in vain.
本発明はこの点に鑑みてなされたもので。The present invention has been made in view of this point.
強酸性陽イオン交換樹脂のナトリウム分率を速やかに、
かつ正確に、さらに分析室等に持ち込まずに現地にて簡
単に測定することができる方法を提供するものである。Rapidly adjust the sodium content of strongly acidic cation exchange resin.
The purpose of the present invention is to provide a method that is accurate and can be easily measured on-site without having to bring the sample to an analysis laboratory or the like.
すなわち本発明は強酸性陽イオン交換樹脂と強塩基性陰
イオン交換樹脂の混合イオン交換樹脂を用いる復水脱塩
装置の強酸性陽イオン交換樹脂のナトリウム分率を測定
するにあたり、当該混合イオン交換樹脂または当該混合
樹脂から分離した強酸性陽イオン交換樹脂を取り出し９
次いでそのイオン交換樹脂層にナトリウムおよびカリウ
ムを含まない溶離液を通流し、一定時間当該溶離液を通
流した後に得られる脱着液中のナトリウム濃度をナトリ
ウム電極で測定し、ナトリウム分率が既知の強酸性陽イ
オン交換樹脂を用いた混合イオン交換樹脂または当該強
酸性陽イオン交換樹脂について、前記測定条件と同一条
件下であらかじめ測定した脱着液中のす） ＩＪウム濃
度と比較す乞ことにより１強酸性陽イオン交換樹脂のす
） ＩＪウム分率を測定する方法である。That is, the present invention uses a mixed ion exchange resin of a strongly acidic cation exchange resin and a strongly basic anion exchange resin to measure the sodium fraction of a strongly acidic cation exchange resin in a condensate desalination equipment. Take out the strongly acidic cation exchange resin separated from the resin or the mixed resin 9
Next, an eluent that does not contain sodium and potassium is passed through the ion exchange resin layer, and the sodium concentration in the desorption solution obtained after passing the eluent for a certain period of time is measured using a sodium electrode. By comparing the IJium concentration in the desorption solution measured in advance under the same conditions as the above measurement conditions for the mixed ion exchange resin using a strongly acidic cation exchange resin or the strongly acidic cation exchange resin, 1 This method measures the IJ content of strongly acidic cation exchange resins.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
ナトリウム電極によるナトリウムイオンの測定は液中に
含まれている微量のナトリウムイオンの定量に適してお
り、従来からアンモニア形復水脱塩装置の処理水のす）
ＩＪウム濃度の測定に用いられている。Measuring sodium ions using a sodium electrode is suitable for quantifying trace amounts of sodium ions contained in liquids, and has traditionally been used in the treatment of treated water in ammonia-type condensate desalination equipment.
It is used to measure IJium concentration.
ナトリウム電極による方法はｐＨ電極と同じように検水
中に電極を挿入し、電位差によってナトリウム濃度を測
定するものであり。The method using a sodium electrode is similar to a pH electrode, in which the electrode is inserted into the sample water and the sodium concentration is measured based on the potential difference.
操作が簡単で、かつ正確である。Easy to operate and accurate.
したがってナトリウム電極を前記ナトリウム分率の測定
に応用できれば迅速に測定結果が得られる。Therefore, if a sodium electrode can be applied to the measurement of the sodium fraction, measurement results can be obtained quickly.
本発明者等は本課題について種々検討した結果、特に大
部分がＮＨ，形で小量がＮａ形であるようなアンモニア
形復水脱塩装置に用いられる強酸性陽イオン交換樹脂の
場合は、検体である強酸性陽イオン交換樹脂を小型カラ
ムに充填し、たとえばアンモニア水などの溶離液を一定
の流速で通液すると、その脱着液のナトリウム濃度は第
２図に示したような特徴のあるリーク曲線を呈し、かつ
その曲線はナトリウム分率によって秩序正しく変化する
ことを知見した。As a result of various studies on this subject, the present inventors found that, in particular, in the case of strongly acidic cation exchange resins used in ammonia type condensate desalination equipment, where most of the NH type and a small amount of Na type are used, When a strongly acidic cation exchange resin sample is packed into a small column and an eluent such as aqueous ammonia is passed through it at a constant flow rate, the sodium concentration of the desorbed solution has the characteristics shown in Figure 2. It was found that the leakage curve was exhibited and that the curve changed in an orderly manner depending on the sodium content.
なお検体として９強酸性陽イオン交換樹脂と強塩基性陰
イオン交換樹脂の混合イオン交換樹脂を用いても全く同
じように特徴のあるリーク曲線が得られる。何故ならば
強塩基性陰イオン交換樹脂には陰イオンしか吸着してい
ないから、たとえ検体に当該陰イオン交換樹脂が混入し
ても何らの障害とならないからである。また溶離液の濃
度を適当な濃度とすることにより、脱着液を希釈するこ
となく。Note that even if a mixed ion exchange resin consisting of a strongly acidic cation exchange resin and a strongly basic anion exchange resin is used as the specimen, a leak curve with exactly the same characteristics can be obtained. This is because only anions are adsorbed on the strongly basic anion exchange resin, so even if the anion exchange resin is mixed into the sample, it will not cause any trouble. In addition, by adjusting the concentration of the eluent to an appropriate concentration, the desorption solution is not diluted.
直接ナトリウム電極で測定できることも併せて知見した
。We also discovered that it can be measured directly with a sodium electrode.
本発明はこのような知見に基づいてなされたもので２通
水塔内の混合イオン交換樹脂の小量を、あるいは再生塔
に移送された当該混合イオン交換樹脂を逆洗で分離する
ことにより得られる強酸性陽イオン交換樹脂の小量を。The present invention was made based on this knowledge, and can be obtained by separating a small amount of the mixed ion exchange resin in the two water towers or by backwashing the mixed ion exchange resin transferred to the regeneration tower. A small amount of strongly acidic cation exchange resin.
検体として小型カラムに充填し、当該イオン交換樹脂に
適当な溶離液を通流して脱着液中のナトリウム濃度をナ
トリウム電極で測定し。Fill a small column as a sample, pass an appropriate eluent through the ion exchange resin, and measure the sodium concentration in the desorption solution using a sodium electrode.
前記検体に対応してナトリウム分率が既知の強酸性陽イ
オン交換樹脂を用いた混合イオン交換樹脂あるいはナト
リウム分率が既知の強酸性陽イオン交換樹脂について、
前記測定条件と同一条件下であらかじめ測定しだ溶離液
中のナトリウム濃度を比較することにより強酸性陽イオ
ン交換樹脂のナトリウム分率を定量するのである。Regarding a mixed ion exchange resin using a strongly acidic cation exchange resin with a known sodium fraction corresponding to the specimen, or a strongly acidic cation exchange resin with a known sodium fraction,
The sodium fraction of the strongly acidic cation exchange resin is quantified by comparing the sodium concentration in the eluent which is measured in advance under the same conditions as the above measurement conditions.
本発明は強酸性陽イオン交換樹脂に吸着しているナトリ
ウムイオンを溶離液で脱着して。In the present invention, sodium ions adsorbed on a strongly acidic cation exchange resin are desorbed using an eluent.
その溶離液中のナトリウムイオンを測定するのであるか
ら、溶離液にナトリウムを含んではならないことは云う
までもないが、ナトリウム電極によるナトリウムイオン
の測定においてはカリウムイオンが訪客イオンとなるの
で、カリウムを含まないものが必要である。Since we are measuring sodium ions in the eluent, it goes without saying that the eluent must not contain sodium.However, in the measurement of sodium ions using a sodium electrode, potassium ions become visitor ions. What is not included is required.
したがって、これらの条件を満たす溶離液としては、塩
酸、硫酸等の鉱酸およびアンモニア水が適当である。但
し、ナトリウム電極によるナトリウムイオンの測定は水
素イオンも防害するので、溶離液として鉱酸を用いる場
合はその脱着液をアンモニア等で中和してｐＨをアルカ
リ性にしてから測定せねばならない。一方溶離液として
アンモニア水を用いた場合はこのような中和操作が一切
不用であり、そのままナトリウム電極で測定できるので
１本発明に用いる溶離液としてはアンモニア水が最も適
している。Therefore, mineral acids such as hydrochloric acid and sulfuric acid, and aqueous ammonia are suitable as eluents that satisfy these conditions. However, when measuring sodium ions using a sodium electrode, hydrogen ions are also prevented, so if a mineral acid is used as an eluent, the desorption liquid must be neutralized with ammonia or the like to make the pH alkaline before measurement. On the other hand, when aqueous ammonia is used as an eluent, such a neutralization operation is not necessary at all, and measurement can be performed directly with a sodium electrode, so aqueous ammonia is most suitable as an eluent for use in the present invention.
また本発明に用いるナトリウム電極については、たとえ
ば実用新案公報昭和５２年第１５８３５号に示されてい
るようなもので、ナトリウム電極と比較電極において生
ずる両者の電位差によりナトリウムイオンを測定する公
知のものを用いることができる。The sodium electrode used in the present invention is, for example, the one shown in Utility Model Publication No. 15835 of 1972, which is a known one that measures sodium ions by the potential difference between the sodium electrode and the reference electrode. Can be used.
次に本発明の実施態様を図面に従って説明する。Next, embodiments of the present invention will be described with reference to the drawings.
第１図は本発明の一例を示すフローの説明図であるが、
まずナトリウム分率を測定しようとする強酸性陽イオン
交換樹脂と強塩基性陰イオン交換樹脂の混合イオン交換
樹脂ｌが充填されている通水塔２から弁３および弁４を
開けてイオン交換樹脂層面上約３０ｆｆｉまで水を抜き
９次いで弁３を閉じて弁５を開けて圧縮空気を通水塔２
に送り、混合イオン交換樹脂を充分に混合する。次いで
弁６． ’／、 ８．９．１０を開け、純水配管１１か
ら通水塔２に純水を供給しながら樹脂移送管１２を用い
て混合イオン交換樹脂を通水塔２から再生塔１３に移送
を開始する。次に混合イオン交換樹脂を移送している間
に、弁１４を開けて樹脂移送管 □１２から分岐し
た樹脂採取管１５より計量ホッパー１６に混合イオン交
換樹脂を充填する。FIG. 1 is an explanatory diagram of a flow showing an example of the present invention,
First, valves 3 and 4 are opened from the water tower 2 filled with a mixed ion exchange resin l of a strongly acidic cation exchange resin and a strongly basic anion exchange resin whose sodium content is to be measured. Drain water to about 30ffi (9), then close valve 3, open valve 5, and supply compressed air to water tower 2.
to thoroughly mix the mixed ion exchange resin. Then valve 6. '/, Open 8.9.10 and start transferring the mixed ion exchange resin from the water tower 2 to the regeneration tower 13 using the resin transfer pipe 12 while supplying pure water from the pure water pipe 11 to the water tower 2. . Next, while the mixed ion exchange resin is being transferred, the valve 14 is opened and the mixed ion exchange resin is filled into the weighing hopper 16 from the resin collection pipe 15 branched from the resin transfer pipe □12.
計量ホッパー１６は液は通すが、イオン交換樹脂は通さ
ないサランネットなどのようなスクリーン１７を上部に
付設したもので当該計量ホッパー１６により規定量の混
合イオン交換樹脂を採取することができる。The measuring hopper 16 is equipped with a screen 17 such as Saran net on the top that allows the liquid to pass through but not the ion exchange resin, and allows a specified amount of the mixed ion exchange resin to be collected through the measuring hopper 16.
計量ホッパー１６に規定量の混合イオン交換樹脂を採取
した抜弁１４を閉じ１次いで弁１８および弁１９を開は
小型力、ラム２０に混合イオン交換樹脂を充填する。次
いで弁１８および１９を閉じて弁２１および弁２２を開
けて常法により当該混合イオン交換樹脂を逆洗し。A predetermined amount of mixed ion exchange resin is collected in the weighing hopper 16. The extraction valve 14 is closed, and then the valves 18 and 19 are opened to fill the ram 20 with the mixed ion exchange resin. Next, valves 18 and 19 are closed, valves 21 and 22 are opened, and the mixed ion exchange resin is backwashed in a conventional manner.
クラッドを除去し沈整する。次に弁２１および２２を閉
じ弁２３および２４を開けて溶離液管２５から約０．２
％のアンモニア水を小型カラム２０に一定の流速で通液
し混合イオン交換樹脂中の強酸性陽イオン交換樹脂のナ
トリウムイオンを脱着し、その脱着液を脱着液管２６を
介して、ナトリウム電極を用いるナトリウムモニタ・−
２７に通流し、脱着液中のナトリウムイオンを測定する
。Remove crud and settle. Next, valves 21 and 22 are closed, valves 23 and 24 are opened, and approximately 0.2
% of ammonia water is passed through the small column 20 at a constant flow rate to desorb the sodium ions of the strongly acidic cation exchange resin in the mixed ion exchange resin, and the desorption liquid is passed through the desorption liquid pipe 26 to the sodium electrode. Sodium monitor used -
27 to measure sodium ions in the desorption solution.
ナトリウムイオンの測定が終了したら弁２日。After completing the sodium ion measurement, wait 2 days.
弁１９を開けて小型カラム２０に純水を通水してカラム
内のアンモニア水をよく洗浄した後。After opening the valve 19 and passing pure water through the small column 20, the ammonia water in the column was thoroughly washed.
弁１９を閉じて弁８．弁２１．弁２９を開口して小型カ
ラムに純水を圧入し、小型カラム２０内の混合イオン交
換樹脂を返送配管３０．樹脂移送管１２を介して再生塔
１３に返送する。Close valve 19 and close valve 8. Valve 21. Open the valve 29 to pressurize pure water into the small column, and return the mixed ion exchange resin in the small column 20 to the return pipe 30. The resin is returned to the regeneration tower 13 via the resin transfer pipe 12.
本発明のフローの一例は上述したようなものであるが、
前記のナトリウムイオンの測定値から２強酸性陽イオン
交換樹脂のナトリウム分率を以下のようにして定量する
。An example of the flow of the present invention is as described above,
The sodium fraction of the strongly acidic cation exchange resin is determined from the above measured value of sodium ions as follows.
すなわち測定に供した強酸性陽イオン交換樹脂と同じ銘
柄の強酸性陽イオン交換樹脂を。In other words, use a strong acidic cation exchange resin of the same brand as the strongly acidic cation exchange resin used for the measurement.
たとえばナトリウム分率をそれぞれ０．００２ 。For example, the sodium fraction is 0.002.
０．００４． （１，００６に調整し、この３種類の強
酸性陽イオン交換樹脂に、測定に供した強塩基性陰イオ
ン交換樹脂と同じ銘柄のものを同じ混合比で混合し、当
該混合イオン交換樹脂を前述の測定の際と同容量小型カ
ラム２０に充填し、同一の条件下でアンモニア水を通液
し。0.004. (Adjusted to 1,006, and mixed these three types of strongly acidic cation exchange resins with the same brand of strong basic anion exchange resin used for measurement at the same mixing ratio, and mixed the mixed ion exchange resin. A small column 20 with the same capacity as in the measurement described above was packed, and aqueous ammonia was passed through it under the same conditions.
それぞれの溶離液のナトリウムイオン量を測定し、その
測定結果を基に第２図に示したようなグラフを作成して
おく。The amount of sodium ions in each eluent is measured, and a graph as shown in FIG. 2 is created based on the measurement results.
第２図のようなグラフをあらかじめ作成しておけば、た
とえば前述の通水基２から採取した混合イオン交換樹脂
について測定した溶離開始から２０分後の脱着液のナト
リウム濃度が５０ｐｐｂであれば、当該混合イオン交換
樹脂中の強酸性陽イオン交換樹脂のナトリウム分率は０
．００２以下であることが分る。If you create a graph like the one shown in Figure 2 in advance, for example, if the sodium concentration of the desorption solution measured 20 minutes after the start of elution for the mixed ion exchange resin collected from the water-passing group 2 is 50 ppb, The sodium content of the strongly acidic cation exchange resin in the mixed ion exchange resin is 0.
．． It can be seen that it is less than 002.
なお第１図に示したフローは小型カラム２０に混合イオ
ン交換樹脂を充填するものであるが、たとえば通水基２
の混合イオン交換樹脂の全量を再生塔１３に移送し、再
生塔１３−で両イオン交換樹脂を逆洗により分離し、再
生塔１３に付設した採取ノズルなどから（図示せず）。The flow shown in FIG. 1 is for filling a small column 20 with a mixed ion exchange resin.
The entire amount of the mixed ion exchange resin is transferred to the regeneration tower 13, and both ion exchange resins are separated by backwashing in the regeneration tower 13-, and then from a sampling nozzle attached to the regeneration tower 13 (not shown).
強酸性陽イオン交換樹脂のみを採取し、これを小型カラ
ム２０に充填して前述と同じように脱着液のナトリウム
イオンを測定してもさしつ７５へ、えない。なおこの場
合は、第２図を作成するに際しては強酸性陽イオン交換
樹脂のみとすることは云うまでもない。Even if only the strongly acidic cation exchange resin is collected, packed into the small column 20, and the sodium ions in the desorbed liquid are measured in the same manner as described above, it will not be possible to proceed directly to step 75. In this case, it goes without saying that only the strongly acidic cation exchange resin is used when creating FIG.
また前述したごとく本発明に使用する溶離液としてはア
ンモニア水が好ましいが、その濃度は０．１〜０．２％
のものが好ましい。たとえば０．１チ以下であると脱着
されてくるナトリウムイオンの量が少なすぎて測定が困
難であり、また０、 ２％以上としても脱着されるナト
リウムイオンの量はあまり変らない。Furthermore, as mentioned above, aqueous ammonia is preferable as the eluent used in the present invention, and its concentration is 0.1 to 0.2%.
Preferably. For example, if it is less than 0.1%, the amount of desorbed sodium ions will be too small to measure, and even if it is more than 0.2%, the amount of desorbed sodium ions will not change much.
以上説明したように本発明のナトリウム分率の測定方法
は小型カラムに検体を充填し。As explained above, the method for measuring sodium fraction of the present invention involves filling a small column with a sample.
当該充填層に溶離液を通流して、その脱着液のナトリウ
ムイオンをナトリウム電極で測定するだけであるから操
作が簡単で、現場にて測定することができ、かつ即座に
その測定結果が得られるので、ナトリウム分率の値によ
って次の操作を決定せねばならないような復水脱塩装置
においては多大な効果を発揮する。The operation is simple, as all you have to do is pass the eluent through the packed bed and measure the sodium ions in the desorbed liquid using a sodium electrode, and the measurement can be performed on-site, and the measurement results can be obtained immediately. Therefore, it is highly effective in condensate desalination equipment where the next operation must be determined based on the value of the sodium fraction.
また前述の第２図を演算機などに記憶させておき、かつ
それぞれの弁を自動弁としておけば１本測定操作を完全
自動化することができる。Furthermore, if the above-mentioned FIG. 2 is stored in a computer or the like and each valve is set as an automatic valve, the single measurement operation can be completely automated.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
実施例
あらかじめナトリウム分率０．００２ 、０．００４
。Example Sodium fraction 0.002, 0.004
.
ｏ、ｏｏａに調整した強酸性陽イオン交換樹脂アンバー
ライト（登録商標、以下同様） ２０ＯＣＴを４ｏｏｒ
ｎｌｉづつ用意し、この３種類の強酸性陽イオン交換樹
脂にＯＨ形に調整した強塩基性陰イオン交換樹脂アンバ
ーライトエＲＡ−９００を２００ｄづつ混合し１強酸性
陽イオン交換樹脂と強塩基性陰イオン交換樹脂が２：１
の３種類の混合イオン交換樹脂を調整した。Strongly acidic cation exchange resin Amberlite (registered trademark, hereinafter the same) adjusted to o, ooa 20OCT to 4oor
Prepare 3 types of strongly acidic cation exchange resins and mix 200d of each of Amberlite RA-900, a strong basic anion exchange resin adjusted to OH form, to prepare 1 strong acidic cation exchange resin and 1 strong basic anion exchange resin. Anion exchange resin: 2:1
Three types of mixed ion exchange resins were prepared.
次にこの６ｏｏｎ／の３種類の混合イオン交換樹脂につ
いて、それぞれ第１図に示した小型カラムに充填し、０
．２％のアンモニア水を１２ｔ／Ｈ（ＳＶ２０）で通流
したときの脱着液のナトリウムイオンをナトリウム電極
を用いるナトリウムモニターで測定し、横軸に通流時間
縦軸にナトリウムイオン量をとり、第２図に示したよう
なグラフを作成した。Next, each of the three types of mixed ion exchange resins at a concentration of 6 oon/day was packed into the small column shown in Figure 1, and
．． When 2% ammonia water was passed through it at 12t/H (SV20), the sodium ions in the desorption solution were measured using a sodium monitor using a sodium electrode. A graph like the one shown in Figure 2 was created.
次に、アンバーライト２０ＯＣＴが３，０ＯＯｔ。Next, Amberlight 20OCT is 3,0OOt.
アンバーライトＩＲＡ−９００が１，５００を充填され
ているアンモニア形復水脱塩装置において。In an ammonia type condensate desalination equipment filled with 1,500 Amberlite IRA-900.
復水の通水が終了した通水塔から両樹脂を充分に混合し
た後、第１図のフローに従′つて混合イオン交換樹脂の
ｅｏｏｍｅを小型カラムに充填し、逆洗してクラッドを
除去した後、０．２チのアンモニア水を１２ ｔ／Ｈ（
８Ｖ２０ ）で通流し、その脱着液のナトリウムイオン
量を測定した。その結果通流開始から２０分後のナトリ
ウム濃度は６２ｐｐｂであった。この２０分後のナトリ
ウム濃度から第２図を用いてナトリウム分率を求めたと
ころ０．００２１であることが解った。After thoroughly mixing both resins from the water tower where the condensate had passed, the mixed ion exchange resin eoome was packed into a small column according to the flow shown in Figure 1, and the crud was removed by backwashing. After that, add 0.2 t/h of ammonia water at 12 t/h (
8V20), and the amount of sodium ions in the desorption solution was measured. As a result, the sodium concentration 20 minutes after the start of the flow was 62 ppb. The sodium fraction was determined from the sodium concentration after 20 minutes using FIG. 2 and was found to be 0.0021.
一方通水塔から採取したと同じ混合イオン交換樹脂を分
析室に持ち込み、常法により逆洗して強酸性陽イオン交
換樹脂を分離し、当該強酸性陽イオン交換樹脂に過剰量
の塩酸を通液して、全てのイオンを脱着し、この脱着液
のナトリウムイオンを従来の方法である原子吸光法（フ
レームレス）にて測定し、ナトリウム分率を算出したと
ころ、その値は０．００２０５であり２本発明の測定方
法の精度は優れているものであった。On the other hand, the same mixed ion exchange resin collected from the water tower is brought to the analysis laboratory, backwashed using a conventional method to separate the strongly acidic cation exchange resin, and an excess amount of hydrochloric acid is passed through the strongly acidic cation exchange resin. All the ions were desorbed, and the sodium ions in this desorption solution were measured using the conventional method of atomic absorption spectrometry (flameless), and the sodium fraction was calculated, and the value was 0.00205. 2 The accuracy of the measuring method of the present invention was excellent.
第１図は本発明の測定方法のフローを示す説明図であり
、第２図は実施例におけるナトリウムイオンのリーク曲
線を示したグラフであり、横軸に通流時間、縦軸にナト
リウムイオン量を示す。FIG. 1 is an explanatory diagram showing the flow of the measurement method of the present invention, and FIG. 2 is a graph showing a sodium ion leak curve in an example, where the horizontal axis is the flow time and the vertical axis is the amount of sodium ions. shows.
Claims (1)
混合イオン交換樹脂を用いる復水脱塩装置の強酸性陽イ
オン交換樹脂のナトリウム分率を測定するにあたり、当
該混合イオン交換樹脂または当該混合樹脂から分離した
強酸性陽イオン交換樹脂を取り出し９次いでそのイオン
交換樹脂層にす） ＩＪウムおよびカリウムを含まない
溶離液を通流し、一定時間当該溶離液を通流した後に得
られる脱着液中のナトリウム濃度をナトリウム電極で測
定し、ナトリウム分率が既知の強酸性陽イオン交換樹脂
を用いた混合イオン交換樹脂または当該強酸性陽イオン
交換樹脂について、前記測定条件と同一条件下であらか
じめ測定した脱着液中のナトリウム濃度と比較すること
によ９１強酸性陽イオン交換樹脂のナトリウム分率を測
定する方法When measuring the sodium fraction of a strongly acidic cation exchange resin of a condensate desalination equipment that uses a mixed ion exchange resin of a strongly acidic cation exchange resin and a strongly basic anion exchange resin, the mixed ion exchange resin or the mixture The strongly acidic cation exchange resin separated from the resin is taken out and then applied to the ion exchange resin layer).In the desorption solution obtained after passing an eluent that does not contain IJ and potassium for a certain period of time. The sodium concentration was measured with a sodium electrode, and the sodium content was measured in advance under the same conditions as the above measurement conditions for a mixed ion exchange resin using a strongly acidic cation exchange resin with a known sodium fraction or for the strongly acidic cation exchange resin. Method for measuring the sodium fraction of 91 strongly acidic cation exchange resin by comparing it with the sodium concentration in the desorption solution
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57109813A JPS59338A (en) | 1982-06-28 | 1982-06-28 | Method for measuring sodium fraction of strong acidic cation exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57109813A JPS59338A (en) | 1982-06-28 | 1982-06-28 | Method for measuring sodium fraction of strong acidic cation exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59338A true JPS59338A (en) | 1984-01-05 |
| JPH0310377B2 JPH0310377B2 (en) | 1991-02-13 |
Family
ID=14519853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57109813A Granted JPS59338A (en) | 1982-06-28 | 1982-06-28 | Method for measuring sodium fraction of strong acidic cation exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59338A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4873946A (en) * | 1987-08-25 | 1989-10-17 | Kioritz Corporation | Two-cycle internal combustion engine |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023137014A (en) | 2022-03-17 | 2023-09-29 | シスメックス株式会社 | Reagent container, reagent container kit, reagent container installation method, reagent container frame, reagent container assembling method, and analyzer |
-
1982
- 1982-06-28 JP JP57109813A patent/JPS59338A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4873946A (en) * | 1987-08-25 | 1989-10-17 | Kioritz Corporation | Two-cycle internal combustion engine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0310377B2 (en) | 1991-02-13 |
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