JPH0694362B2 - How to recover iodine - Google Patents
How to recover iodineInfo
- Publication number
- JPH0694362B2 JPH0694362B2 JP61235395A JP23539586A JPH0694362B2 JP H0694362 B2 JPH0694362 B2 JP H0694362B2 JP 61235395 A JP61235395 A JP 61235395A JP 23539586 A JP23539586 A JP 23539586A JP H0694362 B2 JPH0694362 B2 JP H0694362B2
- Authority
- JP
- Japan
- Prior art keywords
- iodine
- ion exchanger
- resin
- solution containing
- group
- 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
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- Treatment Of Liquids With Adsorbents In General (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明はイオン交換体を用いた新規な沃素の回収方法に
関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a novel method for recovering iodine using an ion exchanger.
沃素は医農薬、飼料添加剤および衛生用品等の原料とし
て有用な物質である。Iodine is a substance useful as a raw material for medical and agricultural chemicals, feed additives, hygiene products and the like.
〈従来の技術〉 沃素の回収は、30〜200ppmの沃素を含有する油田かん水
および天然ガスかん水などから活性炭法、およびイオン
交換樹脂法等によって行われていることが知られてい
る。このうちで製造工程の簡便さや、収率が良いことな
どからイオン交換樹脂法〔改訂 製造工程図全集Ｉ、51
4（1977）：化学工業社、および特開昭51-148693号公
報）が近年注目を集めている。<Prior Art> It is known that iodine is recovered from an oil field brackish water and natural gas brackish water containing 30 to 200 ppm of iodine by an activated carbon method, an ion exchange resin method or the like. Among them, the ion-exchange resin method [revised manufacturing process diagram complete I, 51
4 (1977): Chemical Industry Co., Ltd. and Japanese Patent Laid-Open No. 51-148693) have been attracting attention in recent years.
〈発明が解決しようとする問題点〉 イオン交換樹脂法による沃素の回収には、強塩基性イオ
ン交換樹脂が用いられているが、溶離が困難であるた
め、溶離剤として濃厚な酸を用い、前処理として亜硫酸
を通液後、加温下で溶離を行っている。<Problems to be Solved by the Invention> A strongly basic ion exchange resin is used for the recovery of iodine by the ion exchange resin method, but since elution is difficult, a concentrated acid is used as an eluent. As a pretreatment, after passing through sulfurous acid, elution is performed under heating.
したがって樹脂の官能基である四級アンモニウム塩の劣
化がおこりやすく、長時間の使用によって交換容量の低
下や樹脂の破壊がおこり、樹脂の補充、交換の頻度が高
くなるという問題や、高濃度の溶離剤を用いていること
で、沃素濃度が100ppm以下の溶液からは経済的に沃素を
回収するのは難しいという欠点を有している。Therefore, deterioration of the quaternary ammonium salt, which is a functional group of the resin, easily occurs, the exchange capacity is reduced and the resin is destroyed by long-term use, and the frequency of replenishment and replacement of the resin increases, The use of an eluent has a drawback that it is difficult to economically recover iodine from a solution having an iodine concentration of 100 ppm or less.
かかる事情に鑑み、本発明者らは上記のような不都合を
克服した沃素の回収方法を開発すべく検討を行った結
果、特定官能基を有するイオン交換体と沃素を含有する
溶液を接触せしめた後、加温した水と接触させることに
より沃素を効率よく回収できることを見出し、本発明を
完成するに至った。In view of such circumstances, the present inventors have conducted studies to develop a method for recovering iodine that overcomes the above-mentioned inconveniences, and as a result, brought an ion exchanger having a specific functional group into contact with a solution containing iodine. After that, they found that iodine can be efficiently recovered by contacting it with heated water, and completed the present invention.
〈問題点を解決するための手段〉 すなわち本発明は、沃素を含有する溶液から沃素を回収
するにあたり、分子中に一級もしくは二級のアミノ基を
有するイオン交換体と沃素を含有する溶液とを接触させ
て沃素を吸着させた後、該イオン交換体を加温した水と
接触させることにより沃素を脱着させることを特徴とす
る沃素の回収方法を提供するにある。<Means for Solving Problems> That is, in the present invention, in recovering iodine from a solution containing iodine, an ion exchanger having a primary or secondary amino group in the molecule and a solution containing iodine are prepared. Another object of the present invention is to provide a method for recovering iodine, which comprises desorbing iodine by bringing the ion exchanger into contact with heated water after adsorbing iodine.
本発明において使用されるイオン交換体は、分子中に一
級もしくは二級のアミノ基を有するイオン交換体であ
り、一般にはクロルメチル基、ニトリル基、塩素、臭素
等ハロゲン原子等を有したスチレン、エチレン、プロピ
レン、塩化ビニル、アクリロニトリル、α−クロルアク
リロニトリル、シアン化ビニリデン、メタアクリロニト
リル等の単量体を主成分とする重合体に、一級もしくは
二級のアミノ基を有し、窒素原子が１個以上ある原子団
を有するアミノ化合物、例えばアンモニア、モノメチル
アミン、モノエチルアミン、エチレンジアミン、トリメ
チレンジアミン、テトラメチレンジアミン、ペンタメチ
レンジアミン、ヘキサメチレンジアミン、オクタメチレ
ンジアミン、ヘキサメチレンテトラミン、ジエチレント
リアミン、トリエチレンテトラミン、テトラエチレンペ
ンタミン等のアミン類を反応させて得られるイオン交換
体またはこれらの硫酸、硝酸等の鉱酸塩等が挙げられ
る。The ion exchanger used in the present invention is an ion exchanger having a primary or secondary amino group in the molecule, and is generally chloromethyl group, nitrile group, styrene having a halogen atom such as chlorine or bromine, and ethylene. Polymers containing monomers such as propylene, vinyl chloride, acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and methacrylonitrile as a main component have a primary or secondary amino group and at least one nitrogen atom. Amino compounds having a certain atomic group, for example, ammonia, monomethylamine, monoethylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, hexamethylenetetramine, diethylenetriamine, triethyl Ntetoramin, tetraethylene pentamine, etc. amines and reacted with ion exchangers or their sulfate obtained include mineral acid salts such as nitric acid and the like.
なかでもポリアルキレンポリアミノ基を有するイオン交
換体が好ましく用いられる。Among them, an ion exchanger having a polyalkylene polyamino group is preferably used.
これらのイオン交換体に対する各ハロゲンイオンの選択
性の順序は、I-＞Br-＞Cl-＞F-であり、溶液中にCl-が
存在していてもI-が良く吸着される。Selectivity of order of each silver ions for these ion exchangers, I -> Br -> Cl -> F - a is, Cl in the solution - also be present I - is well adsorbed.
本発明に於ける沃素を含有する溶液としては、特に限定
されるものではないが、一般には弱塩基性または酸性の
沃素含有水溶液が適用される。The solution containing iodine in the present invention is not particularly limited, but a weakly basic or acidic aqueous solution containing iodine is generally applied.
かかる沃素を含有する溶液としては、天然ガスかん水、
油田かん水、プロセス廃水等沃素を含む水溶液が挙げら
れる。As the solution containing such iodine, natural gas brine,
Aqueous solutions containing iodine such as oilfield brackish water and process wastewater can be used.
本発明方法の実施に当り、上記イオン交換体と沃素を含
有する溶液との接触方法は特に制限されるものではな
く、例えば沃素を含有する溶液中へイオン交換体を浸漬
する方法、イオン交換体を充填した塔中へ沃素を含有す
る溶液を通す方法等が一般に採用されるが、処理操作が
容易なことからイオン交換体を充填した塔中へ沃素を含
有する溶液を通す方法が好ましく用いられる。In carrying out the method of the present invention, the method of contacting the above ion exchanger with a solution containing iodine is not particularly limited, and for example, a method of immersing the ion exchanger in a solution containing iodine, an ion exchanger A method of passing an iodine-containing solution into a column packed with is generally adopted, but a method of passing an iodine-containing solution into a column packed with an ion exchanger is preferably used because the treatment operation is easy. .
イオン交換体の使用量は特に制限されるものではなく、
処理対称とうる沃素をがんゆうする溶液中の沃素濃度、
用いるイオン交換体の種類等によっても変わるが、これ
は適宜予備実験を行うことにより設定することができ
る。The amount of ion exchanger used is not particularly limited,
Treatment symmetry and iodine concentration in the solution to treat iodine,
Although it varies depending on the type of ion exchanger used, this can be set by appropriately performing preliminary experiments.
イオン交換体と沃素を含有する溶液との接触は約０〜40
℃の温度で行われる。The contact between the ion exchanger and the solution containing iodine is about 0-40.
It is performed at a temperature of ° C.
０℃以下では凍結の恐れがあり、また40℃以上になると
吸着しにくくなり好ましくない。通常沃素の吸着は常温
で行われる。If the temperature is lower than 0 ° C, there is a risk of freezing, and if the temperature is higher than 40 ° C, adsorption becomes difficult, which is not preferable. Iodine is usually adsorbed at room temperature.
また接触時間は特に制限されるものではなく、それぞれ
の条件に応じて適宜決定される。Further, the contact time is not particularly limited and is appropriately determined according to each condition.
前述の方法によって沃素を吸着捕集したイオン交換体は
加温した水と接触することによって沃素をイオン交換体
から脱着することができる。The ion exchanger that has adsorbed and collected iodine by the above-mentioned method can be desorbed from the ion exchanger by contacting with heated water.
イオン交換体と水との接触は約45〜100℃の温度で行わ
れる。45℃以下になると脱着しにくくなり、また100°
以上になると常圧下では沸騰するので好ましくない。The contact between the ion exchanger and water is carried out at a temperature of about 45-100 ° C. It becomes difficult to desorb at 45 ° C or lower, and 100 °
If the above is exceeded, it will boil under normal pressure, which is not preferable.
沃素を吸着したイオン交換体と加温した水との接触方法
は、加温が可能であれば特に制限されるものではないが
水中に沃素を吸着させたイオン交換体を含浸させる方
法、沃素を吸着させたイオン交換体を充填させたジャケ
ット付の塔中に水を加温して通液する方法等が一般に用
いられる。The method for contacting the ion exchanger adsorbing iodine with heated water is not particularly limited as long as heating is possible, but a method of impregnating the ion exchanger adsorbed iodine in water, iodine Generally used is a method in which water is heated and passed through a jacketed tower filled with the adsorbed ion exchanger.
また着脱の際の接触時間も特に制限されるものではな
い。Further, the contact time at the time of attachment / detachment is not particularly limited.
〈発明の効果〉 本発明の方法によれば、沃素を含有する溶液から沃素を
回収する際に、強塩基性イオン交換樹脂を用いた場合に
比べて、高濃度の溶離剤を使用することなく、単に加温
した水による脱着が可能であり、しかも樹脂の官能基の
劣化が抑えられ、その工業的価値は大きい。<Effects of the Invention> According to the method of the present invention, when iodine is recovered from a solution containing iodine, compared with the case of using a strongly basic ion exchange resin, a high concentration eluent is not used. However, it can be desorbed by simply heating the water, and the functional group of the resin can be prevented from deteriorating, and its industrial value is great.
〈実施例〉 以下に本発明を実施例によって説明するが、本発明はそ
の要旨を越えない限り、以下の実施例によって限定され
るものではない。<Examples> The present invention will be described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
実施例１ アクリロニトリル−ジビニルベンゼン共重合体を90重量
パーセント濃度のジエチレントリアミン水溶液と120〜1
40℃で４時間反応させて得たジエチレントリアミノ基を
有した樹脂（以下、本樹脂を吸着樹脂Ａと称する）50ml
を内径20mmφのジャケット付カラムに充填した。Example 1 Acrylonitrile-divinylbenzene copolymer was added to a diethylenetriamine aqueous solution having a concentration of 90% by weight and 120 to 1
50 ml of resin containing diethylenetriamino group obtained by reacting at 40 ° C for 4 hours (hereinafter, this resin is referred to as adsorption resin A)
Was packed in a column with a jacket having an inner diameter of 20 mmφ.
次に第１表に示す組成の地下かん水を常温下、樹脂層を
下向流で空間速度２Hr-1で10時間通液を行った後、70℃
に加温したイオン交換水300mlを３時間で通液し、樹脂
に吸着した沃素の脱着を行ったところ第２表に示すよう
な結果を得た。Next, after passing underground brackish water having the composition shown in Table 1 at room temperature for 10 hours at a space velocity of 2 Hr -1 in a downward flow through the resin layer, and then at 70 ° C.
When 300 ml of ion-exchanged water heated to the above was passed for 3 hours to desorb iodine adsorbed on the resin, the results shown in Table 2 were obtained.
実施例２〜４ 吸着樹脂B; クロルメチル化スチレン−ジビニルベンゼン共重合体に
ヘキサメチレンジアミンを５％水酸化ナトリウム水溶液
溶媒下、100〜105℃で４時間反応させて得たヘキサメチ
レンジアミノ基を有した樹脂。 Examples 2 to 4 Adsorption resin B: Hexamethylenediamino group obtained by reacting a chloromethylated styrene-divinylbenzene copolymer with hexamethylenediamine in a 5% sodium hydroxide aqueous solution solvent at 100 to 105 ° C. for 4 hours. Resin.
吸着樹脂C; 塩化ビニル重合体を80重量％エチレンジアミン水溶液と
120〜130℃で６時間反応させて得たエチレンジアミノ基
を有した樹脂。Adsorption resin C; vinyl chloride polymer and 80 wt% ethylenediamine aqueous solution
A resin having an ethylenediamino group obtained by reacting at 120 to 130 ° C. for 6 hours.
吸着樹脂D; シアン化ビニリデン−ジビニルベンゼン共重合体にヘキ
サメチレンテトラミンを水溶媒下、120〜150℃で２時間
反応させて得たヘキサメチレンテトラミノ基を有した樹
脂。Adsorption resin D: A resin having a hexamethylenetetramino group obtained by reacting vinylidene cyanide-divinylbenzene copolymer with hexamethylenetetramine in an aqueous solvent at 120 to 150 ° C for 2 hours.
以上のハロゲン吸着樹脂の各々5mlを実施例１と同様に
して沃素を含有する地下かん水を通液し、つづいて脱着
を行ったところ第２表に示すような結果が得られた。When 5 ml of each of the above halogen-adsorbing resins was passed through an underground brackish water containing iodine in the same manner as in Example 1 and then desorption was carried out, the results shown in Table 2 were obtained.
比較例１、２ 吸着樹脂Ａの代わりに、市販の四級アンモニウム塩基を
有するイオン交換樹脂であるデュライト Ａ−161（OH
タイプ）（ダイヤモンドシャムロック社製）及びピリジ
ン骨格構造を有する樹脂であるスミレート CR−２（住
友化学社製）を用いた以外は、実施例１と同様にして沃
素の吸着、脱着を行ったところ第３表に示すような結果
が得られた。 Comparative Examples 1 and 2 Instead of the adsorption resin A, a commercially available quaternary ammonium salt group was used.
Dulite, an ion exchange resin that has A-161 (OH
Type) (Diamond Shamrock) and Piriji
Which is a resin having a skeleton structure CR-2 (house
Iodine was prepared in the same manner as in Example 1 except that the
After adsorption and desorption of element, the results shown in Table 3
was gotten.
Claims (4)
するイオン交換体と沃素を含有する溶液とを接触させて
沃素を吸着させた後、該イオン交換体を加温した水と接
触させて沃素を脱着させることを特徴とする沃素の回収
方法。1. An ion exchanger having a primary or secondary amine group in the molecule is brought into contact with a solution containing iodine to adsorb iodine, and then the ion exchanger is brought into contact with warm water. A method for recovering iodine, which comprises desorbing iodine.
ミノ基である特許請求の範囲第１項記載の沃素の回収方
法。2. The method for recovering iodine according to claim 1, wherein the amino group in the molecule is a polyalkylene polyamino group.
触温度が０〜40℃である特許請求の範囲第１項記載の沃
素の回収方法。3. The method for recovering iodine according to claim 1, wherein the contact temperature between the ion exchanger and the solution containing iodine is 0 to 40 ° C.
45〜100℃である特許請求の範囲第１項記載の沃素の回
収方法。4. The contact temperature between the ion exchanger and heated water is
The method for recovering iodine according to claim 1, which has a temperature of 45 to 100 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61235395A JPH0694362B2 (en) | 1986-10-01 | 1986-10-01 | How to recover iodine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61235395A JPH0694362B2 (en) | 1986-10-01 | 1986-10-01 | How to recover iodine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6389403A JPS6389403A (en) | 1988-04-20 |
| JPH0694362B2 true JPH0694362B2 (en) | 1994-11-24 |
Family
ID=16985453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61235395A Expired - Lifetime JPH0694362B2 (en) | 1986-10-01 | 1986-10-01 | How to recover iodine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694362B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206346A (en) * | 1990-12-05 | 1993-04-27 | E. I. Du Pont De Nemours And Company | Method for iodination/purification |
| FR2700969B1 (en) * | 1993-02-03 | 1995-03-31 | Cogema | Process for separating the iodine present in a gas, usable in particular for trapping radioactive iodine from gaseous effluents from nuclear installations. |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51148693A (en) * | 1975-06-16 | 1976-12-21 | Sumitomo Chem Co Ltd | Method for collecting iodine |
| JPS5659603A (en) * | 1979-10-16 | 1981-05-23 | Toyo Soda Mfg Co Ltd | Bromine recovering method |
| JPS57129804A (en) * | 1981-02-03 | 1982-08-12 | Toyo Soda Mfg Co Ltd | Recovering method for bromine |
| JPS5941922A (en) * | 1982-09-01 | 1984-03-08 | Mitsubishi Electric Corp | Channel selecting device |
-
1986
- 1986-10-01 JP JP61235395A patent/JPH0694362B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6389403A (en) | 1988-04-20 |
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