JP5130454B2 - Iodine adsorption and recovery method - Google Patents
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Description
本発明はヨウ素の吸着および回収方法に関する。さらに詳しくは、不溶性のシクロデキストリン（以下、ＣＤとする）またはその誘導体を有効成分とするヨウ素吸着剤を用いるヨウ素の吸着および回収方法に関する。 The present invention relates to a method for adsorption and recovery of iodine. More specifically, the present invention relates to an iodine adsorption and recovery method using an iodine adsorbent containing insoluble cyclodextrin (hereinafter referred to as CD) or a derivative thereof as an active ingredient.
ヨウ素はうがい薬やレントゲン造影剤等の医薬分野、写真フィルムの感光剤、工業用触媒、タイヤやエアバック等の化学繊維耐熱安定剤の化学分野の他に、除草剤、殺菌・防カビ剤、飼料添加物等の幅広い分野で利用されている。最近では、液晶の偏光フィルムや半導体エッチング剤等のＩＴ分野においても利用され、太陽電池としての次世代クリーンエネルギー分野への応用も期待される貴重な地下資源である。 In addition to chemical fields such as pharmaceuticals such as gargles and X-ray contrast agents, photographic film photosensitizers, industrial catalysts, and heat resistant stabilizers for chemical fibers such as tires and airbags, weeds, fungicides and fungicides, It is used in a wide range of fields such as feed additives. Recently, it is a valuable underground resource that is also used in IT fields such as liquid crystal polarizing films and semiconductor etching agents, and is expected to be applied to the next-generation clean energy field as a solar cell.
このように、様々な分野において有用なヨウ素は、カン水（ヨウ素含有量５０−１１０ＰＰｍ）として、地下５００〜１５００メートルの沖積層砂岩中に埋蔵されているヨウ素マイナスイオンを得ることで製造されている。特に千葉県には全世界の約７０％が埋蔵されているといわれており、現在この千葉県を中心に年間９，０００トンのヨウ素が製造されている。 Thus, iodine useful in various fields is produced by obtaining iodine negative ions buried in alluvial sandstone 500 to 1500 meters underground as can water (iodine content 50-110 PPm). Yes. In particular, it is said that approximately 70% of the world is buried in Chiba Prefecture, and 9,000 tons of iodine are produced annually mainly in Chiba Prefecture.
カン水等からヨウ素を得る方法としては、ヨウ素化合物を化学反応等でヨウ素分子にした後空気で追い出すブローイングアウト法、ヨウ素を活性炭で吸着・回収する活性炭吸着法、ヨウ素を銅または銀と反応させてヨウ化銅またはヨウ化銀の沈殿として回収する銅法・銀法およびイオン交換樹脂で吸着・回収するイオン交換樹脂吸着法等が知られている。
また、鉄を担持したチタン酸アルカリに接触させることで、ヨウ素を回収する方法（例えば、特許文献１参照）や、イオン交換樹脂吸着法をベースとした、油田カン水からヨウ素を得る方法も開発されている（例えば、特許文献２参照）。
Methods for obtaining iodine from canned water include the blow-out method in which iodine compounds are converted into iodine molecules by chemical reaction and then expelled with air, activated carbon adsorption method in which iodine is adsorbed and recovered with activated carbon, and iodine is reacted with copper or silver. There are known a copper method and a silver method for collecting copper iodide or silver iodide as a precipitate, and an ion exchange resin adsorption method for adsorbing and recovering with an ion exchange resin.
Also developed are methods for recovering iodine by bringing it into contact with iron-supported alkali titanate (see, for example, Patent Document 1) and methods for obtaining iodine from oil field canned water based on the ion exchange resin adsorption method. (For example, refer to Patent Document 2).
このうち、ブローイングアウト法およびイオン交換樹脂吸着法が主に利用されているが、ブローイングアウト法はヨウ素の採取率が８０〜９０％であり、ヨウ素採取後のカン水中に、アンモニア、臭素等の溶解物と共にヨウ素が低濃度ながら残存してしまうという問題があった。また、イオン交換樹脂吸着法では、樹脂自体の吸着効率が低いために十分にヨウ素が採取できないという問題や、樹脂からヨウ素イオンを脱離する際に大量のアルカリを必要とするため、樹脂の劣化が起こるという問題があった。さらに、これらの従来知られている方法は、いずれも複雑な工程が必要となるという問題があった。従って、簡便な工程からなり、カン水から１００％近くヨウ素を吸着でき、さらに吸着したヨウ素を回収して工業的に利用できる、ヨウ素の吸着および回収方法の提供が望まれていた。 Among these, the blowing out method and the ion exchange resin adsorption method are mainly used, but the blowing out method has an iodine collection rate of 80 to 90%. There existed a problem that iodine remained with a melt | dissolution with low concentration. In addition, the ion exchange resin adsorption method has a problem that iodine cannot be collected sufficiently because the adsorption efficiency of the resin itself is low, and a large amount of alkali is required when desorbing iodine ions from the resin. There was a problem that happened. Furthermore, all of these conventionally known methods have a problem that a complicated process is required. Therefore, it has been desired to provide an iodine adsorption and recovery method that consists of simple steps, can adsorb nearly 100% of iodine from can water, and can recover the adsorbed iodine for industrial use.
ヨウ素はＣＤ、特にαＣＤに包接されることで、水溶液中に安定に保持できることが知られている（例えば、特許文献３参照）。そして、ＣＤに包接したヨウ素は、安定した状態でヨウ素を利用できるとして、抗菌消臭スプレー等に利用されている。
本発明者らは、このようなヨウ素およびＣＤの関係に着眼して、カン水等に含まれるヨウ素をＣＤで包接することにより、ヨウ素を吸着させ、さらに回収ができるか否かを検討している。カン水等からのヨウ素の吸着および回収において、ＣＤを用いることを検討したのは、本発明が初めてのことである。
The present inventors focused on such a relationship between iodine and CD, and examined whether iodine can be adsorbed and further collected by inclusion of iodine contained in canned water or the like with CD. Yes. The present invention is the first to consider the use of CD in the adsorption and recovery of iodine from canned water or the like.
本発明はヨウ素の吸着および回収方法を提供することを課題とする。さらに詳しくは、不溶性のＣＤまたはその誘導体を有効成分とするヨウ素吸着剤を用いるヨウ素の吸着および回収方法の提供を課題とする。 An object of the present invention is to provide a method for adsorption and recovery of iodine. More specifically, an object of the present invention is to provide an iodine adsorption and recovery method using an iodine adsorbent containing insoluble CD or a derivative thereof as an active ingredient.
本発明者らは前記課題を解決するために鋭意研究を行った結果、不溶性のＣＤまたはその誘導体を有効成分とするヨウ素吸着剤を用いることで、カン水等に含まれるヨウ素を１００％近く吸着できること見出し、本発明を完成するに至った。本発明で見出されたヨウ素の吸着方法では、ヨウ素を含む溶液と、ヨウ素吸着剤を混合することで、溶液に含まれるヨウ素をヨウ素吸着剤に吸着することができる。このようにしてヨウ素吸着剤に吸着したヨウ素は、加圧加熱や、水蒸気蒸留等によって、容易にＣＤから脱離することができるため、従来の回収方法に比べて工程が簡便である。また、カン水等より吸着したヨウ素を回収して、工業的に利用できる。
さらに、本発明のヨウ素の回収方法では、吸着したヨウ素の回収にあたり、ＮａＯＨ、ＮａＨＳＯ3、ＳＯ2水溶液等の薬剤を必要としないため、有効成分であるＣＤやその誘導体が劣化しにくく、ヨウ素の吸着および回収に繰り返し用いることができる。また、使用後のヨウ素吸着剤を廃棄する場合でも、不溶性のＣＤやその誘導体は毒性がないので埋設のみで処理できるという利点がある。
As a result of intensive studies to solve the above problems, the present inventors have adsorbed nearly 100% of iodine contained in canned water by using an iodine adsorbent containing insoluble CD or a derivative thereof as an active ingredient. We found out what we can do and came to complete the present invention. In the iodine adsorption method found in the present invention, iodine contained in the solution can be adsorbed to the iodine adsorbent by mixing the iodine-containing solution with the iodine adsorbent. Since iodine adsorbed on the iodine adsorbent in this way can be easily desorbed from CD by pressure heating, steam distillation or the like, the process is simpler than the conventional recovery method. Further, iodine adsorbed from canned water or the like can be recovered and used industrially.
Furthermore, since the iodine recovery method of the present invention does not require chemicals such as NaOH, NaHSO 3 , SO 2 aqueous solution, etc. in recovering the adsorbed iodine, the active ingredient CD and its derivatives are unlikely to deteriorate, It can be used repeatedly for adsorption and recovery. Even when the iodine adsorbent after use is discarded, there is an advantage that insoluble CD and its derivatives are not toxic and can be treated only by embedding.
すなわち、本発明は次の（１）〜（８）のヨウ素の回収方法、およびそれに用いるヨウ素吸着剤等に関する。
（１）不溶性のＣＤまたはその誘導体を有効成分として含むヨウ素吸着剤。
（２）ＣＤのポリマーである上記（１）に記載のヨウ素吸着剤。
（３）ＣＤがαＣＤである上記（１）または（２）に記載のヨウ素吸着剤。
（４）上記（１）〜（３）のいずれかに記載のヨウ素吸着剤を用いるヨウ素の吸着方法。
（５）次の工程（ａ）、（ｂ）からなる上記（４）に記載のヨウ素の吸着方法
（ａ）ヨウ素を含む溶液と、ヨウ素吸着剤を混合する
（ｂ）溶液に含まれるヨウ素をヨウ素吸着剤に吸着する。
（６）上記（１）〜（３）のいずれかに記載のヨウ素吸着剤を用いるヨウ素の回収方法。
（７）次の工程（ａ）〜（ｄ）からなる上記（６）に記載のヨウ素の回収方法
（ａ）ヨウ素を含む溶液と、ヨウ素吸着剤を混合する
（ｂ）溶液に含まれるヨウ素をヨウ素吸着剤に吸着する
（ｃ）ヨウ素吸着剤に吸着したヨウ素を脱離する
（ｄ）脱離したヨウ素を回収する。
（８）ヨウ素の脱離方法が、加圧加熱、有機酸あるいは無機酸添加または水蒸気蒸留のいずれかである上記（７）に記載の方法。
That is, the present invention relates to the following methods (1) to (8) for recovering iodine, iodine adsorbents used therefor, and the like.
(1) An iodine adsorbent containing insoluble CD or a derivative thereof as an active ingredient.
(2) The iodine adsorbent according to (1) above, which is a polymer of CD.
(3) The iodine adsorbent according to the above (1) or (2), wherein CD is αCD.
(4) An iodine adsorption method using the iodine adsorbent according to any one of (1) to (3) above.
(5) The iodine adsorption method according to the above (4) comprising the following steps (a) and (b): (a) a solution containing iodine and an iodine adsorbent are mixed; (b) iodine contained in the solution; Adsorbs on iodine adsorbent.
(6) A method for recovering iodine using the iodine adsorbent according to any one of (1) to (3) above.
(7) The iodine recovery method according to (6), comprising the following steps (a) to (d): (a) A solution containing iodine and an iodine adsorbent are mixed; (b) Iodine contained in the solution; Adsorb on iodine adsorbent (c) Desorb iodine adsorbed on iodine adsorbent (d) Collect desorbed iodine.
(8) The method according to the above (7), wherein the iodine desorption method is pressurization heating, addition of an organic acid or inorganic acid, or steam distillation.
本発明のヨウ素の吸着および回収方法によって、貴重な地下資源であるヨウ素を高効率に吸着し、回収できる。回収されたヨウ素は、工業製品等に再利用できる。 The iodine adsorption and recovery method of the present invention can adsorb and recover iodine, which is a valuable underground resource, with high efficiency. The recovered iodine can be reused for industrial products.
本発明の「ヨウ素吸着剤」とは、カン水等に含まれるヨウ素を吸着し、回収するための剤である。本発明の「ヨウ素吸着剤」はＣＤによってヨウ素を包接することにより、カン水等に含まれているヨウ素を吸着することから、ＣＤを有効成分とする剤であることが好ましい。本発明の「ヨウ素吸着剤」は、ＣＤ以外にヨウ素の吸着および回収において有効な成分や、剤を安定的に保持するための成分を含んでいても良いし、有効成分であるＣＤのみからなる剤であっても良い。 The “iodine adsorbent” of the present invention is an agent for adsorbing and recovering iodine contained in can water. The “iodine adsorbent” of the present invention is preferably an agent containing CD as an active ingredient because it adsorbs iodine contained in canned water or the like by inclusion of iodine by CD. The “iodine adsorbent” of the present invention may contain, in addition to CD, a component effective for adsorption and recovery of iodine, a component for stably holding the agent, or only CD which is an active component. It may be an agent.
本発明の「ヨウ素吸着剤」に含まれるＣＤとしては、ヨウ素を吸着および回収できれば、αＣＤ、βＣＤ、γＣＤのいずれも用いることができ、これらの誘導体であってもよい。これらはヨウ素を回収する対象に応じて、用いるＣＤを選択することが好ましい。
ヨウ素を含む溶液を対象とする場合には、水に不溶なＣＤまたはその誘導体を用いることが重要である。例えば、エピクロロヒドリンや多価グリシジルエーテル等の架橋剤にて高分子化した、ＣＤポリマー（以下、ＣＤＰとする）、キトサン、ポリスチレン、ポリエチレン、ポロプロピレン、ポリエチレングリコール等の高分子やシリカゲル等の無機体にＣＤを化学修飾等により固定化したＣＤ修飾樹脂やＣＤモノマーのトリアセチル体等を用いることが適している。「ヨウ素吸着剤」に含まれるＣＤとしては、αＣＤを用いることが好ましく、特にαＣＤのポリマーであることが好ましい。ＣＤＰは繰り返し再利用できるため、経済的である。
As CD contained in the “iodine adsorbent” of the present invention, any of αCD, βCD, and γCD can be used as long as iodine can be adsorbed and recovered, and these derivatives may also be used. For these, it is preferable to select the CD to be used according to the target for recovering iodine.
When a solution containing iodine is targeted, it is important to use water-insoluble CD or a derivative thereof. For example, polymers such as CD polymers (hereinafter referred to as CDP), chitosan, polystyrene, polyethylene, polypropylene, polyethylene glycol, etc., which have been polymerized with a crosslinking agent such as epichlorohydrin or polyvalent glycidyl ether, silica gel, etc. It is suitable to use a CD-modified resin obtained by immobilizing CD on the inorganic material by chemical modification or the like, or a triacetyl form of CD monomer. As the CD contained in the “iodine adsorbent”, αCD is preferably used, and an αCD polymer is particularly preferable. CDP is economical because it can be reused repeatedly.
ＣＤＰは既知のいずれの方法でも調製できるが、例えば、水酸化ナトリウム水溶液にＣＤと非晶質ケイ酸を溶解させた溶液を入れ、６５℃で攪拌しながら、エピクロロヒドリンを滴下し加え、そのままの温度、攪拌条件下で８時間反応させ、析出物をろ過し、過洗浄を行った後、真空乾燥すること等で調製することができる（参考文献１、参照）。また、ＣＤと水酸化ナトリウムを水に溶解し、５０℃で攪拌しながら、エピクロロヒドリンを滴下し加え、そのままの温度、攪拌条件下で１時間反応させる。生成したゲルを粉砕後、水洗、アセトン洗浄で洗い、シリカゲルデシケータ中で一昼夜減圧乾燥すること等で調製することができる（参考文献２、参照）。
［参考文献１］ 特開２００６−１４３９５３号公報
［参考文献２］ 日本化学会誌，１９８７，（６），１０４０−１０４６
CDP can be prepared by any known method. For example, a solution prepared by dissolving CD and amorphous silicic acid in an aqueous sodium hydroxide solution is added, and epichlorohydrin is added dropwise while stirring at 65 ° C. The reaction can be carried out for 8 hours under the same temperature and stirring conditions, and the precipitate can be filtered, overwashed, and then vacuum dried (see Reference Document 1). Further, CD and sodium hydroxide are dissolved in water, epichlorohydrin is added dropwise with stirring at 50 ° C., and the mixture is allowed to react for 1 hour under the same temperature and stirring conditions. The produced gel can be prepared by pulverizing, washing with water, washing with acetone, and drying under reduced pressure in a silica gel desiccator for one day (refer to Reference 2).
[Reference Document 1] Japanese Patent Laid-Open No. 2006-143953 [Reference Document 2] Journal of Chemical Society of Japan, 1987, (6), 1040-1046
本発明の「ヨウ素吸着剤」は、ヨウ素を含んでいるものならいずれのものも対象とできる。例えば、カン水や、油田カン水等の溶液を対象とする以外に、ヨウ素を含む産業製品の廃品物等から副成物として得られるヨウ素を含む溶液等も対象とすることができ、再利用を目的としたヨウ素の吸着および回収を行うことができる。また、ヨウ素を含む固形物等も対象とすることができ、混練等によりヨウ素を吸着させて、ヨウ素を回収することもできる。 The “iodine adsorbent” of the present invention can be any one that contains iodine. For example, in addition to solutions such as canned water and oil field canned water, solutions containing iodine obtained as a by-product from industrial waste products containing iodine can also be used for reuse. Adsorption and recovery of iodine for the purpose can be performed. Moreover, the solid substance etc. which contain iodine can also be made into object, and iodine can also be adsorb | sucked by kneading | mixing etc. and iodine can also be collect | recovered.
本発明の「ヨウ素の吸着方法」とは、カン水等のヨウ素を含む溶液と、本発明の「ヨウ素吸着剤」を混合することにより、「ヨウ素吸着剤」の有効成分であるＣＤにヨウ素を吸着させることをいう。この「ヨウ素の吸着方法」はカン水等からのヨウ素の採取等を目的として利用することができる。
また、本発明の「ヨウ素の回収方法」とは、上記の「ヨウ素の吸着方法」によってヨウ素を吸着したＣＤまたはその誘導体より、ヨウ素を回収することをいう。ＣＤまたはその誘導体に吸着したヨウ素を回収する方法としては、ヨウ素を吸着したＣＤまたはその誘導体、例えばＣＤＰ等をそのまま水の中に浸漬せしめ、加熱溶融することによって行うことができる。またはそのまま水蒸気蒸留することにより吸着したヨウ素を水蒸気と一緒に取り出すことができる。その他にも、ベンゼン、ピリジン、ヘキサン、シクロヘキサン、メタノール、エタノール等の炭化水素系溶媒、酢酸、フェノール、塩酸、硫酸等の有機および無機酸とそれらの塩を用いることにより、ヨウ素を回収することができる。
以下、本発明の詳細を実施例等で説明するが、本発明はこれらに限定されるものではない。
The “iodine adsorption method” of the present invention is a method of mixing iodine, which is an active ingredient of “iodine adsorbent”, by mixing a solution containing iodine such as can water and the “iodine adsorbent” of the present invention. It means adsorbing. This “iodine adsorption method” can be used for the purpose of collecting iodine from canned water or the like.
The “iodine recovery method” of the present invention means recovery of iodine from CD or a derivative thereof adsorbed with iodine by the above “iodine adsorption method”. As a method for recovering iodine adsorbed on CD or its derivative, CD or its derivative adsorbed on iodine, for example, CDP or the like can be immersed in water as it is and heated and melted. Alternatively, the adsorbed iodine can be taken out together with the water vapor by steam distillation as it is. In addition, iodine can be recovered by using hydrocarbon solvents such as benzene, pyridine, hexane, cyclohexane, methanol, ethanol, organic and inorganic acids such as acetic acid, phenol, hydrochloric acid, sulfuric acid and their salts. it can.
Hereinafter, the details of the present invention will be described with reference to examples and the like, but the present invention is not limited thereto.
１．ヨウ素吸着剤の調製
ヨウ素吸着剤に含む有効成分として、αＣＤＰ、βＣＤＰおよびγＣＤＰを次の方法によって作成した。また、αＣＤ＋βＣＤ複合Ｐ、βＣＤ＋γＣＤ複合ＰおよびγＣＤ＋αＣＤ複合Ｐを作成した。
ここで、αＣＤ＋βＣＤ複合Ｐとは、αＣＤとβＣＤを各質量混合したものを、エピクロロヒドリン等と反応させ、ポリマーとしたもののことをいう。βＣＤ＋γＣＤ複合ＰおよびγＣＤ＋αＣＤ複合Ｐも同様である。
１Ｌの丸形セパラブルフラスコと３ツ口セパラブルカバーを組み合わせた容器に、４０％（ｗ／ｖ）水酸化ナトリウム水溶液２００ｍＬに表１に示した質量のＣＤ（シクロケム製）と非晶質ケイ酸６０ｇを溶解させた溶液を入れ、６５℃で、フッ素樹脂製攪拌羽根（ラウンド型５０ｍｍ幅、４００ｒｐｍ）で攪拌しながら、エピクロロヒドリン４５．６ｇを滴下し加えた。そのままの温度、攪拌条件下で８時間反応させ、析出物をろ過し、さらに洗浄水が中性になるまでろ過洗浄を行った後、真空乾燥した。これらのＣＤＰをそのままヨウ素吸着剤とした。
1. Preparation of iodine adsorbent αCDP, βCDP and γCDP were prepared by the following method as active ingredients contained in the iodine adsorbent. In addition, αCD + βCD composite P, βCD + γCD composite P and γCD + αCD composite P were prepared.
Here, the αCD + βCD composite P refers to a polymer obtained by reacting a mass mixture of αCD and βCD with epichlorohydrin or the like. The same applies to βCD + γCD complex P and γCD + αCD complex P.
In a container combining a 1 L round separable flask and a three-neck separable cover, 200 mL of a 40% (w / v) aqueous sodium hydroxide solution and the mass of CD (manufactured by Cyclochem) and amorphous silica are shown. A solution in which 60 g of acid was dissolved was added, and 45.6 g of epichlorohydrin was added dropwise at 65 ° C. while stirring with a fluororesin stirring blade (round type 50 mm width, 400 rpm). The reaction was allowed to proceed for 8 hours under the same temperature and stirring conditions, the precipitate was filtered, and further washed by filtration until the washing water became neutral, and then vacuum dried. These CDPs were directly used as iodine adsorbents.
２．擬似カン水の調製
次の１）〜３）の手法により擬似カン水を調製した。
１）ヨウ化ナトリウム（ＮａＩ＝１４９．８９）を２３６．３ｍｇ（ヨウ素（Ｉ2） １００ｍｇ含有）量り取り、１Ｌの水を加え、ヨウ素含有量＝約１００ｐｐｍ＝０．０１％の水溶液を調製した。
２）ヨウ素に対して有効塩素が１．１モル当量になるように、攪拌（スターラー）下で次亜塩素酸ナトリウム溶液（ＮａＣｌＯ＝７４．４４、有効塩素約５％）を１１４２．５μＬ加えた。
３）約１Ｍの塩酸を１０２５μＬ加え、ｐＨが中性付近（ｐＨ６．５−７．２）になるよう調整し、５分間攪拌させて、擬似カン水を得た。
2. Preparation of simulated Kang water Pseudo Kang water was prepared by the following methods 1) to 3).
1) 236.3 mg (containing 100 mg of iodine (I 2 )) of sodium iodide (NaI = 149.89) was weighed, 1 L of water was added, and an aqueous solution containing iodine content = about 100 ppm = 0.01% was prepared. .
2) 1142.5 μL of sodium hypochlorite solution (NaClO = 74.44, effective chlorine about 5%) was added under stirring (stirrer) so that the effective chlorine was 1.1 molar equivalents relative to iodine. .
3) 1025 μL of about 1 M hydrochloric acid was added to adjust the pH to be near neutral (pH 6.5 to 7.2), and the mixture was stirred for 5 minutes to obtain pseudo can water.
各ヨウ素吸着剤におけるヨウ素吸着率の測定
次の１）〜６）の手法により各ヨウ素吸着剤におけるヨウ素吸着率を測定した。
１）上記実施例１で調製した擬似カン水を１００ｇ×７個に分け、それぞれ測定用サンプルとした。
２）ブランク（０ｈ）用のサンプルから５０ｇ量り取り、０．０１ｍｏｌチオ硫酸ナトリウムで滴定した。このときのヨウ素濃度をＡとした。
３）他のビーカーのそれぞれに、αＣＤＰ、βＣＤＰ、γＣＤＰ、αＣＤ＋βＣＤ複合Ｐ、βＣＤ＋γＣＤ複合Ｐ、γＣＤ＋αＣＤ複合Ｐを１００ｍｇずつ入れて４ｈ攪拌した。
４）３）の試験液をろ紙を用いて自然ろ過した。
５）４）のろ液約５０ｇを量り取り、０．０１ｍｏｌチオ硫酸ナトリウムでヨウ素濃度滴定した。このときのヨウ素濃度をＢとした。
６）次の式１の計算式を用いて吸着率を算出した。
Measurement of iodine adsorption rate in each iodine adsorbent The iodine adsorption rate in each iodine adsorbent was measured by the following methods 1) to 6).
1) The pseudo can water prepared in Example 1 was divided into 100 g × 7 pieces, which were used as measurement samples.
2) 50 g was weighed from a sample for blank (0 h) and titrated with 0.01 mol sodium thiosulfate. The iodine concentration at this time was set to A.
3) 100 mg each of αCDP, βCDP, γCDP, αCD + βCD complex P, βCD + γCD complex P, and γCD + αCD complex P were added to each of the other beakers and stirred for 4 hours.
4) The test solution of 3) was naturally filtered using a filter paper.
5) About 50 g of the filtrate of 4) was weighed and titrated with 0.01 mol sodium thiosulfate. The iodine concentration at this time was set to B.
6) The adsorption rate was calculated using the following equation (1).
［式１］ 吸着率＝（Ａ−Ｂ）／Ａ×１００
[Formula 1] Adsorption rate = (A−B) / A × 100
結果
表２に示すように、いずれのＣＤＰでもヨウ素が吸着されることが確認できた。このうち、特にαＣＤＰを用いた場合に吸着率が高かった。
Results As shown in Table 2, it was confirmed that iodine was adsorbed by any CDP. Of these, the adsorption rate was particularly high when αCDP was used.
吸着時間によるヨウ素吸着率の測定
次の１）〜６）の手法により各ヨウ素吸着剤におけるヨウ素吸着率を測定した。
１）上記実施例１で調製した擬似カン水を１２０ｇ入れ、これをブランク溶液とした。
２）チオ硫酸ナトリウム（０．０１ｍｏｌ）を用いてブランク溶液のヨウ素濃度を滴定した。このときのヨウ素濃度をＡとした。
３）予めαＣＤＰ１２０ｍｇを入れたビーカーを上記１）とは別に６個用意し、上記実施例１で調製した擬似カン水を１２０ｇ入れ、それぞれ測定用サンプルとした。
４）３）の測定用サンプルは、それぞれの吸着時間攪拌後、ろ過してαＣＤＰを取り除いた。
５）ろ液を量り取り、チオ硫酸ナトリウム（０．０１ｍｏｌ）でヨウ素濃度を滴定した。このときのヨウ素濃度をＢとした。
６）上記実施例２で示した式１の計算式を用いて吸着率を算出した。
Measurement of iodine adsorption rate by adsorption time The iodine adsorption rate in each iodine adsorbent was measured by the following methods 1) to 6).
1) 120 g of pseudocan water prepared in the above Example 1 was added to make a blank solution.
2) The iodine concentration of the blank solution was titrated with sodium thiosulfate (0.01 mol). The iodine concentration at this time was set to A.
3) Six beakers containing αCDP 120 mg in advance were prepared separately from the above 1), and 120 g of pseudo canned water prepared in Example 1 was added, and each was used as a measurement sample.
4) The measurement sample of 3) was filtered after stirring for each adsorption time to remove αCDP.
5) The filtrate was weighed and the iodine concentration was titrated with sodium thiosulfate (0.01 mol). The iodine concentration at this time was set to B.
6) The adsorption rate was calculated using the formula of Formula 1 shown in Example 2 above.
結果
表３に示すように、０．２５ｈで６０％以上の吸着が見られた。２時間経過後には９０％をこし、２４時間で９５％以上の吸着率が示された。これによりαＣＤＰは高いヨウ素吸着能を有することが示された。
Results As shown in Table 3, 60% or more of adsorption was observed at 0.25 h. After 2 hours, 90% was rubbed, and an adsorption rate of 95% or more was shown in 24 hours. This showed that αCDP has a high iodine adsorption capacity.
加圧加熱によるヨウ素の回収
ヨウ素を１０％吸着（包接）したαＣＤＰ１ｋｇを水１０リッターの入った２０リッター耐熱耐圧ガラス容器に入れ、このものを加圧密閉下、加熱により１２０℃−１３０℃２時間加熱後、（ヨウ素を分離したαＣＤＰはガラス容器の中で、ヨウ素と２層をなし、αＣＤＰはヨウ素の上に浮いた状態になる）下部ノズルより、αＣＤＰから分離し容器底に溶融したヨウ素を１１５−１２０℃に加熱保温したノズルより取り出し、琺瑯容器に受ける。このものを十分冷却後、固形ヨウ素として取り出した。純度９９．９％の固形ヨウ素が９８ｇ得られた。ヨウ素の回収率は９８％であった。
Recovery of iodine by pressure heating 1 kg of αCDP adsorbed (inclusion) with 10% iodine is put into a 20 liter heat-resistant pressure-resistant glass container containing 10 liters of water, and this is heated at 120 ° C. to 130 ° C. under heating under pressure. After heating for a while (the αCDP from which iodine has been separated forms two layers with iodine in the glass container, and the αCDP floats on the iodine) From the lower nozzle, the iodine that has been separated from the αCDP and melted at the bottom of the container Is taken out from a nozzle heated and kept at 115-120 ° C. and received in a container. This was sufficiently cooled and then taken out as solid iodine. 98 g of solid iodine having a purity of 99.9% was obtained. The iodine recovery rate was 98%.
濃硫酸添加によるヨウ素の回収
ヨウ素を１０％吸着（包接）したαＣＤＰ１ｋｇを水７リッターの入った２０リッターガラス容器に入れる。上部を開放型とし、上部ノズルから濃硫酸１０リッターを加え（ギルビン法）、１２０℃ー１３０℃外部加熱（ヨウ素を分離したαＣＤＰはヨウ素と２層をなし、αＣＤＰと濃硫酸水溶液はヨウ素の上層にくる）により以下同様に１１５−１２０℃に加熱保温した下部ノズルよりヨウ素取り出し、溶融ヨウ素を琺瑯容器に受ける。このものを十分冷却後固形ヨウ素として取り出した。純度９９．８％の固形ヨウ素が９５ｇ得られた。ヨウ素の回収率は９５％であった。
Recovery of iodine by adding concentrated sulfuric acid 1 kg of αCDP adsorbed (inclusion) with 10% iodine is placed in a 20-liter glass container containing 7 liters of water. The upper part is an open type, 10 liters of concentrated sulfuric acid is added from the upper nozzle (Gilbin method), and external heating is performed at 120 ° C to 130 ° C (αCDP from which iodine is separated has two layers with iodine. In the same manner, the iodine is taken out from the lower nozzle heated and kept at 115 to 120 ° C., and the molten iodine is received in the soot container. This was sufficiently cooled and then taken out as solid iodine. 95 g of solid iodine having a purity of 99.8% was obtained. The iodine recovery was 95%.
水蒸気蒸留によるヨウ素の回収
ヨウ素を１０％吸着（包接）したαＣＤＰ１ｋｇを水１０リッターの入った２０リッターガラス容器に入れ、ジャケット加熱により内温を７０−１００℃にまで上昇させながらヨウ素を水蒸気と一緒に蒸留し、このものを隣接する１０リッター入りガラス釜の水面下に差し込まれたガラス管を通して冷却しヨウ素を沈殿させる。
ヨウ素が流出しなくなった時点を終点とし、ろ過後、未乾燥ヨウ素を９５−１０５℃で５時間乾燥機にて乾燥後秤量したところ純度９９．９％の固形ヨウ素９５ｇが得られた。ヨウ素の回収率は９５％であった。
Recovery of iodine by steam distillation 1 kg of αCDP with 10% adsorption (inclusion) of iodine is placed in a 20 liter glass container containing 10 liters of water, and the jacket is heated to increase the internal temperature to 70-100 ° C., and the iodine is converted into steam. Distill together and cool it through a glass tube inserted under the water surface of an adjacent 10 liter glass kettle to precipitate iodine.
The time when iodine stopped flowing out was regarded as the end point, and after filtration, undried iodine was dried in a dryer at 95-105 ° C. for 5 hours and weighed to obtain 95 g of solid iodine having a purity of 99.9%. The iodine recovery was 95%.
本発明のヨウ素の回収方法によって、カン水からヨウ素を高効率に吸着させ、回収できる。不溶性のＣＤまたはその誘導体、ＣＤＰ等に吸着されたヨウ素は容易に回収でき、このヨウ素は工業製品等に利用可能である。 With the iodine recovery method of the present invention, iodine can be adsorbed from canned water with high efficiency and recovered. Iodine adsorbed on insoluble CD or its derivative, CDP or the like can be easily recovered, and this iodine can be used for industrial products and the like.
Claims (1)
（ａ）ヨウ素を含む溶液と、水酸化ナトリウム水溶液にαＣＤと非晶質ケイ酸を溶解させた溶液を入れ、これにエピクロロヒドリンを滴下して得られるαＣＤのポリマーを有効成分として含むヨウ素吸着剤を混合する
（ｂ）溶液に含まれるヨウ素をヨウ素吸着剤に吸着する
（ｃ）ヨウ素吸着剤に吸着したヨウ素を加圧加熱、無機酸添加または水蒸気蒸留のいずれかの脱離方法で脱離する
（ｄ）脱離したヨウ素を回収する。
Method for recovering iodine comprising the following steps (a) to (d) (a) A solution containing iodine and a solution in which αCD and amorphous silicic acid are dissolved in an aqueous sodium hydroxide solution are added, and epichlorohydride is added thereto. mixing the iodine adsorbent comprising a polymer of αCD obtained by dropwise addition of phosphorus as an active ingredient (b) iodine contained in the solution to adsorb iodine adsorbent (c) the iodine pressure heating adsorbed iodine adsorbent (D) Desorbed iodine is recovered by a desorption method of either inorganic acid addition or steam distillation.
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