JPH01167202A - Purification of heavy water - Google Patents
Purification of heavy waterInfo
- Publication number
- JPH01167202A JPH01167202A JP62326243A JP32624387A JPH01167202A JP H01167202 A JPH01167202 A JP H01167202A JP 62326243 A JP62326243 A JP 62326243A JP 32624387 A JP32624387 A JP 32624387A JP H01167202 A JPH01167202 A JP H01167202A
- Authority
- JP
- Japan
- Prior art keywords
- heavy water
- exchange resin
- resin
- weakly basic
- basic anion
- 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 title claims abstract description 78
- 238000000746 purification Methods 0.000 title claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 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 abstract description 17
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005115 demineralization Methods 0.000 claims abstract description 4
- 230000002328 demineralizing effect Effects 0.000 claims abstract description 4
- -1 nitric acid ions Chemical class 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 101100149536 Caenorhabditis elegans skn-1 gene Proteins 0.000 abstract 1
- 101100083855 Rattus norvegicus Pou2f3 gene Proteins 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000003608 radiolysis reaction Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000012607 strong cation exchange resin Substances 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)
Abstract
Description
【発明の詳細な説明】
〈発明の対象〉
本発明は、重水減速沸騰軽水冷却型原子炉においてイオ
ン交換樹脂を用いた重水浄化塔に係わシ、特に重水浄化
塔の処理能力を向上させる〈従来技術〉
現在、動力用原子炉の一つに新型転換炉である重水減速
沸騰軽水冷却型原子炉が発電に供されている。原子炉に
は核分裂反応を制御する減速材と、核分裂反応によって
発生した熱を取り出す媒体である冷却材が使用されてい
る。[Detailed Description of the Invention] <Object of the Invention> The present invention relates to a heavy water purification tower using an ion exchange resin in a heavy water-moderated boiling light water-cooled nuclear reactor, and particularly to improving the processing capacity of the heavy water purification tower. Prior Art Currently, a heavy water-moderated boiling light water-cooled nuclear reactor, which is a new converter reactor, is used as one of the power reactors for power generation. Nuclear reactors use a moderator that controls the nuclear fission reaction and a coolant that is a medium that extracts the heat generated by the nuclear fission reaction.
この重水減速沸騰軽水冷却型原子炉の減速材は、重水系
およびヘリウム系から構成されている。本発明の対象で
ある重水には、反応度補償のためにホウ酸が注入されて
おり、この重水は性陽イオン交換樹脂と弱塩基性陰イオ
ン交換樹脂とから成る混床式脱塩塔が使用されている。The moderator of this heavy water-moderated boiling light water-cooled nuclear reactor is composed of heavy water and helium. Boric acid is injected into the heavy water that is the object of the present invention to compensate for reactivity, and this heavy water is processed through a mixed bed demineralization tower consisting of a strong cation exchange resin and a weakly basic anion exchange resin. It is used.
弱塩基性陰イオン交換樹脂が用いられているのは、弱酸
であるホウ酸をほとんど吸着せずに不純物のみを吸着す
るため、重水中のホウ酸濃度を変化させず原子炉の反応
度に影響を及ぼさない理由による。また冷却材は軽水が
使用され、発生した蒸気はタービンに導かれ循環再使用
さが著しく、重水系構造材の健全性を保つために必要な
電導度とするためには、比較的頻繁に重水浄化塔樹脂の
樹脂交換を行う必要のあることが判った。重水浄化塔樹
脂の樹脂交換を行うには、樹脂に含まれる軽水が重水中
に侵入し重水濃度を低下させるだめ、予めこの軽水を重
水に置換する重水化操作が必要であるが、浄化塔ｌ塔分
の樹脂′交換に約３ｍ３ の重水を要し、又この重水が
極めて高価であるためできるだけ樹脂交換頻度を下げる
必要があった。Weakly basic anion exchange resin is used because it adsorbs only impurities without adsorbing much of boric acid, which is a weak acid, so it does not affect the reactivity of the reactor without changing the boric acid concentration in heavy water. For reasons that do not affect In addition, light water is used as a coolant, and the generated steam is led to a turbine and is reused in a significant amount of circulation.In order to maintain the electrical conductivity required to maintain the integrity of heavy water-based structural materials, heavy water is used relatively frequently. It was found that it was necessary to replace the resin in the purification tower. In order to replace the resin in the heavy water purification tower, the light water contained in the resin will enter the heavy water and reduce the concentration of heavy water, so it is necessary to replace this light water with heavy water in advance. Approximately 3 m3 of heavy water was required to replace the resin in the column, and since this heavy water was extremely expensive, it was necessary to reduce the frequency of resin replacement as much as possible.
一方、重水電導度上昇の原因は、重水が放射線分解反応
で生成する過酸化重水素が重水を浄化する時重水浄化塔
に流入してイオン交換樹脂を酸化分解し、その結果イオ
ン交換容量が低下するとともにこの分解生成物がさらに
炉心部で放射線分解され炭酸及び硝酸イオンなどの陰イ
オンを生成し水質劣化させている。On the other hand, the reason for the increase in heavy water conductivity is that when heavy water is purified by radiolysis reaction, deuterium peroxide flows into the heavy water purification tower and oxidizes and decomposes the ion exchange resin, resulting in a decrease in ion exchange capacity. At the same time, these decomposition products are further subjected to radiolysis in the reactor core, producing anions such as carbonate and nitrate ions, deteriorating water quality.
従来の設計では、陽イオン性不純物と陰イオン不純物の
浄化塔への負荷は同程度と見積もり、イオン交換容量比
を等しくするため、重水浄化塔の強酸性陽イオン交換樹
脂と弱塩基性陰イオン交換樹脂の樹脂量混合比を／：／
としていたが、このように陰イオンが選択的に生成した
場合には著しく陰イオン交換樹脂容量が不足していた。In conventional designs, the load on the purification tower of cationic impurities and anionic impurities is estimated to be the same, and in order to equalize the ion exchange capacity ratio, the heavy water purification tower's strongly acidic cation exchange resin and weakly basic anion are used. The resin amount mixing ratio of the replacement resin is /:/
However, when anions were selectively generated in this way, the capacity of the anion exchange resin was significantly insufficient.
このだめ、陰イオン性不純物が十分に除去されず、重水
の電導度を上昇させる結果となそこで本発明者等は重水
浄化塔の処理能力を向上させることを目的として鋭意検
討した結果、従来装荷されていた強酸性陽イオン交換樹
脂と弱塩基性陰イオン交換樹脂の樹脂量比を変更するこ
とによって重水浄化塔の処理能力を向上させることがで
きる事を見出し本発明に到達した。As a result, anionic impurities are not removed sufficiently, resulting in an increase in the conductivity of heavy water.The inventors of the present invention conducted extensive studies with the aim of improving the processing capacity of heavy water purification towers, and found that conventional loading The inventors have discovered that the processing capacity of a heavy water purification tower can be improved by changing the ratio of the amounts of strongly acidic cation exchange resins and weakly basic anion exchange resins, and have arrived at the present invention.
〈発明の構成〉
本発明は、従来装荷されていた強酸性陽イオン交換樹脂
と弱塩基性陰イオン交換樹脂の樹脂量混合比／：／を変
更し樹脂量混合比ｌ：ｌからｌ：ｊの範囲に、望ましく
ｌｌ−１：／ニー２からｌ：３にすることによって重水
浄化塔の処理能力を向上させるものである。<Structure of the Invention> The present invention changes the resin amount mixing ratio /:/ of the strongly acidic cation exchange resin and the weakly basic anion exchange resin that was conventionally loaded, and changes the resin amount mixing ratio from l:l to l:j. The processing capacity of the heavy water purification tower is improved by adjusting the ratio to be within the range of 1:/k, preferably from 1:2 to 1:3.
以下に、本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
重水中の不純物には、陽イオンであるリチウムが、陰イ
オンでは炭酸および硝酸のほか少量の塩素・亜硝酸・硫
酸が含まれている。また、重水の放射線分解により生成
する過酸化重水素が含まれる。Impurities in heavy water include lithium, which is a cation, and carbonic acid and nitric acid, as well as small amounts of chlorine, nitrite, and sulfuric acid, as anions. It also includes deuterium peroxide, which is produced by radiolysis of heavy water.
この様な不純物の陽イオンは強酸性陽イオン交換樹脂に
陰イオンは弱塩基性陰イオン交換樹脂に吸着される。こ
れら不純物を含む重水を重水浄化塔に通水すると、通水
初期はイオン状の不純物が全て除去されるが、通水を続
けるに従ってイオン交換樹脂の吸着能力が飽和され重水
炭酸ついで硝酸の陰イオンが最初に漏出し、陽イオンで
あるリチウムが漏出してくるのは、かなり時間を経た後
であることが判明した。この事は弱塩基性陰イオン交換
樹脂の吸着能力が先に飽和されていることを示している
。一方、強酸性陽イオン交換樹脂および弱塩基性陰イオ
ン交換樹脂の単位樹脂容積当たりのイオン交換容量は一
定である。これらのことから重水浄化塔は弱塩基性陰イ
オン交換樹脂のイオン交換容量が不足していて、強酸性
陽イオン交換樹脂が余剰であることが判明した。このだ
め、重水浄化塔に従来用いられ、できだ樹脂量混合比／
：／を改善し、強酸性陽イオン交換樹脂量を減少させ、
弱塩基性陰イオン交換樹脂量を増加させることによって
重水浄化塔の処理能力が向上出来ると以下の条件で、通
水実験を行った。Cations of such impurities are adsorbed on a strongly acidic cation exchange resin, and anions are adsorbed on a weakly basic anion exchange resin. When heavy water containing these impurities is passed through a heavy water purification tower, all ionic impurities are removed at the beginning of the water flow, but as the water continues to flow, the adsorption capacity of the ion exchange resin becomes saturated and the anions of heavy water carbonate and nitric acid are removed. It was found that lithium, a positive ion, leaked out first, and lithium, a cation, leaked out only after a considerable time had passed. This indicates that the adsorption capacity of the weakly basic anion exchange resin is saturated first. On the other hand, the ion exchange capacity per unit resin volume of the strongly acidic cation exchange resin and the weakly basic anion exchange resin is constant. These results revealed that the heavy water purification tower lacked the ion exchange capacity of the weakly basic anion exchange resin and had a surplus of the strongly acidic cation exchange resin. This tank is conventionally used in heavy water purification towers, resulting in resin amount mixing ratio /
:/Improve the amount of strongly acidic cation exchange resin,
A water flow experiment was conducted under the following conditions, assuming that the processing capacity of the heavy water purification tower could be improved by increasing the amount of weakly basic anion exchange resin.
０ 使用樹脂
強酸性陽イオン交換樹脂
ダイヤイオン ５ＫＮ−７
（三菱化成工業■製）
弱塩基性陰イオン交換樹脂
ダイヤイオン ＷＡ−２１
（三菱化成工業■製）
○液組成
ホウ酸 ３．ｊ ｐｐｍ ａｓ Ｂ過酸化
水素 ７．０ ｐｐｍ ａｓ Ｈ，０２硝
酸 タタ’ ｐｌ）ｂ ａｓ Ｎ
ｏ。0 Resin used Strongly acidic cation exchange resin Diamond 5KN-7 (manufactured by Mitsubishi Chemical Industries ■) Weakly basic anion exchange resin Diamond WA-21 (manufactured by Mitsubishi Chemical Industries ■) ○Liquid composition Boric acid 3. j ppm as B hydrogen peroxide 7.0 ppm as H,02 nitrate
acid tata' pl)b as N
o.
炭 酸 ／！ｒ００ ｐｐｂ
ａｓ ＣＯ３０通水流量 ２ｏ ＢＶ／
ｈＯカラム３０消φ×／ｊ００ＨＨ
（ジャケット付）
Ｏ樹脂量および混合比
樹 脂 量 混合比
実施例−／ ３３３ｑｌ ｔｔ７Ｈ１／ ：
２実施例−２２ｓｏ７ ｑｓｏ７ ｔ； ３
実施例−３／１７Ｈ１１３３ａｌ ／：ｊ比較例
実施例のイオン交換樹脂量をＷＡ−２／はｊ ００ｉｌ
、 ＳＫ Ｎ −／はｊ ００７１１１として、そのほ
かは同一条件で通水実験を行った。Carbonic acid /! r00 ppb
as CO30 water flow rate 2o BV/
hO column 30mm φ×/j00HH (with jacket) O resin amount and mixing ratio Resin amount Mixing ratio example -/ 333ql tt7H1/:
2 Example-22so7 qso7t; 3
Example-3/17H1133al /:j Comparative Example The amount of ion exchange resin in Example WA-2/ is j 00il
, SK N −/ was set to j 007111, and a water flow experiment was conducted under the same conditions except for the following.
〈発明の効果〉
重水型導度の寄与が大きい硝酸イオンを代表とし、原液
中の硝酸イオンが７０係漏出した時点の樹脂のイオン吸
着量を求め、比較例を基準とした実施例−／および実施
例−２、実施例−３の吸着量の比を第１図に示した。<Effects of the Invention> Using nitrate ions, which have a large contribution from heavy water type conductivity, as a representative example, the amount of ion adsorption of the resin at the time when 70% of nitrate ions in the stock solution leaked out was determined, and an example based on a comparative example was carried out. The adsorption amount ratio of Example-2 and Example-3 is shown in FIG.
これらの結果から、強酸性陽イオン交換樹脂と弱塩基性
陰イオン交換樹脂の樹脂量混合比／：／を超えｌ：夕の
範囲までいづれの比もそのイオン吸着量は、従来の混合
比の値を上回った。From these results, it can be seen that for any resin mixing ratio of strongly acidic cation-exchange resin and weakly basic anion-exchange resin, the ion adsorption amount exceeds the range of /:/ to the range of 1:2. exceeded the value.
特に混合比が／：３の場合が最大値を示し従来第１図は
、吸着量の比を樹脂量混合比に対してプロットした図で
ある。Particularly, when the mixing ratio is /:3, the maximum value is obtained. Conventionally, FIG. 1 is a graph in which the adsorption amount ratio is plotted against the resin amount mixing ratio.
Claims (2)
樹脂とから成る重水浄化用混床式脱塩塔において、強酸
性陽イオン交換樹脂と弱塩基性陰イオン交換樹脂の樹脂
量混合比１：１から１：５の範囲を特徴とする重水の浄
化方法(1) In a mixed-bed demineralization tower for heavy water purification consisting of a strongly acidic cation exchange resin and a weakly basic anion exchange resin, the resin amount mixing ratio of the strongly acidic cation exchange resin and the weakly basic anion exchange resin Heavy water purification method characterized by a ratio of 1:1 to 1:5
オン交換樹脂に吸着される成分が、リチウムおよび炭酸
、硝酸の各イオンであるところの特許請求の範囲第１項
記載の方法(2) The method according to claim 1, wherein the components adsorbed on the strongly acidic cation exchange resin and the weakly basic anion exchange resin are lithium, carbonic acid, and nitric acid ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62326243A JPH01167202A (en) | 1987-12-23 | 1987-12-23 | Purification of heavy water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62326243A JPH01167202A (en) | 1987-12-23 | 1987-12-23 | Purification of heavy water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01167202A true JPH01167202A (en) | 1989-06-30 |
| JPH0442323B2 JPH0442323B2 (en) | 1992-07-13 |
Family
ID=18185594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62326243A Granted JPH01167202A (en) | 1987-12-23 | 1987-12-23 | Purification of heavy water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01167202A (en) |
-
1987
- 1987-12-23 JP JP62326243A patent/JPH01167202A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0442323B2 (en) | 1992-07-13 |
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