JP4831765B2 - Method for separating iodine ions - Google Patents

Method for separating iodine ions Download PDF

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JP4831765B2
JP4831765B2 JP2007115620A JP2007115620A JP4831765B2 JP 4831765 B2 JP4831765 B2 JP 4831765B2 JP 2007115620 A JP2007115620 A JP 2007115620A JP 2007115620 A JP2007115620 A JP 2007115620A JP 4831765 B2 JP4831765 B2 JP 4831765B2
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奈緒 島
實 高川
正典 藤島
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株式会社 東邦アーステック
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Description

本発明は、複置換電気透析法による水溶液中のヨウ素イオンの分離方法に関する。   The present invention relates to a method for separating iodine ions in an aqueous solution by a double displacement electrodialysis method.

ヨウ素イオンを含むヨウ化水素酸は、化学原料あるいは医薬品の製造原料として重要な物質である。   Hydroiodic acid containing iodine ions is an important substance as a chemical raw material or a pharmaceutical production raw material.

従来、ヨウ化水素酸の製造方法としては、ヨウ素と水との懸濁液に次亜リン酸などの還元剤を添加し、反応後に反応液からヨウ化水素酸を蒸留にて留出させる方法が知られている（例えば、特許文献１参照。）。   Conventionally, as a method for producing hydroiodic acid, a reducing agent such as hypophosphorous acid is added to a suspension of iodine and water, and hydroiodic acid is distilled from the reaction solution by distillation after the reaction. Is known (for example, see Patent Document 1).

また、原料ヨウ素の製造方法としては、ヨウ素イオンを溶解する水溶液へ塩素などの酸化剤を導入し、ヨウ素イオンを遊離のヨウ素とした後、空気で追い出して亜硫酸水素ナトリウムなどの還元性溶液に吸収させて濃縮した後（ブローイングアウト法）、再度、塩素などの酸化剤を導入して、ヨウ素イオンを遊離のヨウ素として分離した後に精製している。   In addition, as a raw material iodine production method, an oxidant such as chlorine is introduced into an aqueous solution that dissolves iodine ions to convert the iodine ions into free iodine, which is then expelled with air and absorbed into a reducing solution such as sodium bisulfite. And then concentrating (blowing out method), an oxidant such as chlorine is introduced again to separate iodine ions as free iodine, and then purified.

すなわち、これら従来の方法では、ヨウ素イオンを溶解する水溶液へ酸化剤を導入して一旦遊離ヨウ素とした後に、還元および濃縮してから、再度酸化させて遊離ヨウ素として単離および精製した後、再度還元して、ヨウ化水素酸とする方法である。   That is, in these conventional methods, an oxidizing agent is introduced into an aqueous solution in which iodine ions are dissolved to form free iodine, then reduced and concentrated, then oxidized again, isolated and purified as free iodine, and then again. This is a method of reducing to hydroiodic acid.

また、このヨウ化水素酸の製造方法としては、ヨウ化水素と他の無機酸およびこれらの塩のいずれかとを含む原液から、電気透析法にてヨウ化水素酸を選択的に分離する方法が知られている（例えば、特許文献２参照。）。   In addition, as a method for producing this hydroiodic acid, there is a method of selectively separating hydroiodic acid by electrodialysis from a stock solution containing hydrogen iodide and other inorganic acids and salts thereof. It is known (for example, refer to Patent Document 2).

そして、この特許文献２では、２つの試料室に交互に仕切られて構成された２室１組の電気透析槽を用いる方法と、３つの試料室で構成された３室１組の電気透析槽を用いる方法と、４つの試料室で構成された４室１組の電気透析槽を用いる方法との三通りの方法があり、容易にヨウ化水素酸を選択的に分離できる。これら三通りの方法のうちでヨウ化水素酸の分離率および選択率が良い方法は、４室１組の電気透析槽を用いた複置換電気透析法による反応である。
特開平８−５９２０５号公報 特開２００５−５８８９６号公報 And in this patent document 2, the method of using the electrodialysis tank of 1 set of 2 chambers divided and comprised by two sample chambers, and the electrodialysis tank of 3 chambers comprised of 3 sample chambers There are three methods, a method using 4 and a method using a set of four chambers consisting of four sample chambers, and hydroiodic acid can be easily selectively separated. Of these three methods, the method with good separation rate and selectivity of hydroiodic acid is a reaction by a double displacement electrodialysis method using a set of four chambers of an electrodialysis tank.
JP-A-8-59205 JP 2005-58896 A

しかしながら、上記特許文献２に記載の方法で電気透析法を用いてヨウ化水素酸を選択的に分離したところ、ヨウ素イオンの移動速度、すなわちイオン交換膜の透過速度が小さく、十分な移動速度を得るためには大きな電力が必要であり、ヨウ素イオンの移動速度を大きくしつつ消費電力量を小さくすることは容易でないという問題を有している。   However, when hydroiodic acid was selectively separated using the electrodialysis method according to the method described in Patent Document 2, iodine ion migration rate, that is, the permeation rate of the ion exchange membrane was small, and sufficient migration rate was obtained. In order to obtain it, large electric power is required, and there is a problem that it is not easy to reduce the power consumption while increasing the moving speed of iodine ions.

本発明は、このような点に鑑みなされたもので、ヨウ素イオンの移動速度を大きくしつつ消費電力量を小さくできるヨウ素イオンの分離方法を提供することを目的とする。   This invention is made | formed in view of such a point, and it aims at providing the isolation | separation method of the iodine ion which can make a power consumption small while enlarging the moving speed of an iodine ion.

請求項１記載のヨウ素イオンの分離方法は、ヨウ素イオンを含む水溶液である原液から複置換電気透析法にてヨウ素イオンを分離するヨウ素イオンの分離方法であって、ヨウ素イオンの対アニオンとしての塩素イオンを含む水溶液である酸液を用い、一対の正極側の電極室と負極側の電極室との間を正極側から前記電極室に供給される極液を仕切る陽イオン交換膜につづいて、第１の陰イオン交換膜と第１の陽イオン交換膜と第２の陰イオン交換膜と第２の陽イオン交換膜とが交互に繰り返し設けられ、これら第１の陰イオン交換膜、第１の陽イオン交換膜、第２の陰イオン交換膜および第２の陽イオン交換膜にて４つの試料室に交互に仕切った電気透析槽の前記第１の陰イオン交換膜と前記第１の陽イオン交換膜との間および前記第２の陰イオン交換膜と前記第２の陽イオン交換膜との間のいずれか一方に前記原液を供給し、他方に前記酸液を供給し、前記原液に接する陰イオン交換膜として一価陰イオン選択透過膜を用い、前記原液中のヨウ素イオンと前記酸液中の水素イオンとから複置換電気透析法によってヨウ化水素酸を生成するものである。 The method for separating iodine ions according to claim 1 is a method for separating iodine ions by separating iodine ions from a stock solution, which is an aqueous solution containing iodine ions, by double displacement electrodialysis , wherein chlorine as a counter anion of iodine ions is used. Using an acid solution that is an aqueous solution containing ions , followed by a cation exchange membrane that partitions the polar solution supplied from the positive electrode side to the electrode chamber between a pair of positive electrode chambers and a negative electrode chamber, The first anion exchange membrane, the first cation exchange membrane, the second anion exchange membrane, and the second cation exchange membrane are alternately and repeatedly provided. The first anion exchange membrane and the first cation exchange membrane of an electrodialysis tank partitioned alternately into four sample chambers by a cation exchange membrane, a second anion exchange membrane and a second cation exchange membrane Between the ion exchange membrane and the second shade Supplying the stock solution to one of between the ON exchange membrane second cation-exchange membrane, and supplying the acid solution in the other, a monovalent anion permselective as an anion-exchange membrane in contact with the stock solution Using a membrane, hydroiodic acid is generated from iodine ions in the stock solution and hydrogen ions in the acid solution by a double displacement electrodialysis method .

請求項２記載のヨウ素イオンの分離方法は、請求項１記載のヨウ素イオンの分離方法において、酸液に接する陰イオン交換膜として一価陰イオン選択透過膜を用いるものである。The method for separating iodine ions according to claim 2 is the method for separating iodine ions according to claim 1, wherein a monovalent anion selective permeable membrane is used as the anion exchange membrane in contact with the acid solution.

請求項３記載のヨウ素イオンの分離方法は、ヨウ素イオンを含む水溶液である原液から複置換電気透析法にてヨウ素イオンを分離するヨウ素イオンの分離方法であって、ヨウ素イオンの対アニオンとしての硫酸イオンを含む水溶液である酸液を用い、一対の正極側の電極室と負極側の電極室との間を正極側から前記電極室に供給される極液を仕切る陽イオン交換膜につづいて、第１の陰イオン交換膜と第１の陽イオン交換膜と第２の陰イオン交換膜と第２の陽イオン交換膜とが交互に繰り返し設けられ、これら第１の陰イオン交換膜、第１の陽イオン交換膜、第２の陰イオン交換膜および第２の陽イオン交換膜にて４つの試料室に交互に仕切った電気透析槽の前記第１の陰イオン交換膜と前記第１の陽イオン交換膜との間および前記第２の陰イオン交換膜と前記第２の陽イオン交換膜との間のいずれか一方に前記原液を供給し、他方に前記酸液を供給し、前記原液に接する陰イオン交換膜として一価陰イオン選択透過膜を用い、前記酸液に接する陰イオン交換膜として任意の陰イオンを透過させる陰イオン選択透過膜を用い、前記原液中のヨウ素イオンと前記酸液中の水素イオンとから複置換電気透析法によってヨウ化水素酸を生成するものである。 The method for separating iodine ions according to claim 3 is a method for separating iodine ions by separating iodine ions from a stock solution that is an aqueous solution containing iodine ions by double displacement electrodialysis , wherein sulfuric acid is used as a counter anion of iodine ions. Using an acid solution that is an aqueous solution containing ions , followed by a cation exchange membrane that partitions the polar solution supplied from the positive electrode side to the electrode chamber between a pair of positive electrode chambers and a negative electrode chamber, The first anion exchange membrane, the first cation exchange membrane, the second anion exchange membrane, and the second cation exchange membrane are alternately and repeatedly provided. The first anion exchange membrane and the first cation exchange membrane of an electrodialysis tank partitioned alternately into four sample chambers by a cation exchange membrane, a second anion exchange membrane and a second cation exchange membrane Between the ion exchange membrane and the second shade Supplying the stock solution to one of between the ON exchange membrane second cation-exchange membrane, and supplying the acid solution in the other, a monovalent anion permselective as an anion-exchange membrane in contact with the stock solution A double displacement electrodialysis method using an anion selective permeation membrane that allows permeation of any anion as an anion exchange membrane in contact with the acid solution using a membrane, and iodine ions in the stock solution and hydrogen ions in the acid solution To produce hydroiodic acid .

請求項４記載のヨウ素イオンの分離方法は、請求項１ないし３のいずれかに記載のヨウ素イオンの分離方法において、原液として、ブローイングアウト法にて得られたヨウ素吸収液を用いるものである。 The method of separation according to claim 4, wherein the iodide ion is a method for separating iodine ions according to any one of claims 1 to 3, as a stock solution, Ru der those using iodine absorption liquid obtained by blowing out method .

本発明によれば、ヨウ素イオンを含む水溶液からヨウ素イオンを分離する際のヨウ素イオンの移動速度を大きくしつつ消費電力量を小さくできるから、このヨウ素イオンを効率良く分離できる。   According to the present invention, since the power consumption can be reduced while increasing the moving speed of iodine ions when separating iodine ions from an aqueous solution containing iodine ions, the iodine ions can be efficiently separated.

以下、本発明のヨウ素イオンの分離方法を用いた電気透析槽の一実施の形態の構成を図１を参照して説明する。   Hereinafter, the configuration of an embodiment of an electrodialysis tank using the iodine ion separation method of the present invention will be described with reference to FIG.

図１において、１は電気透析装置としての電気透析槽であり、この電気透析槽１は、４つの試料室に交互に仕切られて構成された４室１組の複置換電気透析法を用いたものである。具体的に、この電気透析槽１の両側には、一対の電極1a,1bが配設されている。そして、これら一対の電極1a,1bの一方、すなわち電極1aが正極としての陽極とされる。ここで、この陽極の電極1aとしては、白金(Ｐｔ)や、チタン(Ｔｉ)／白金、カーボン(Ｃ)、ニッケル(Ｎｉ)、ルテニウム(Ｒｕ)／チタン、イリジウム(Ｉｒ)／チタンなどが用いられる。   In FIG. 1, 1 is an electrodialysis tank as an electrodialysis apparatus, and this electrodialysis tank 1 uses a set of four-chamber multi-displacement electrodialysis methods that are configured by being alternately partitioned into four sample chambers. Is. Specifically, a pair of electrodes 1a and 1b are disposed on both sides of the electrodialysis tank 1. One of the pair of electrodes 1a and 1b, that is, the electrode 1a is used as an anode as a positive electrode. Here, platinum (Pt), titanium (Ti) / platinum, carbon (C), nickel (Ni), ruthenium (Ru) / titanium, iridium (Ir) / titanium, etc. are used as the electrode 1a of the anode. It is done.

また、これら一対の電極1a,1bの他方、すなわち電極1bが負極として陰極とされる。ここで、この陰極の電極1bとしては、鉄(Ｆｅ)や、ニッケル、白金、チタン／白金、カーボン、ステンレス鋼としてのクロム(Ｃｒ)鋼などが用いられる。そして、これら電極1a,1bは、細長矩形平板状であるノベ板状やメッシュ状、格子状などに形成されている。   The other of the pair of electrodes 1a and 1b, that is, the electrode 1b is used as a negative electrode as a cathode. Here, as the cathode electrode 1b, iron (Fe), nickel, platinum, titanium / platinum, carbon, chromium (Cr) steel as stainless steel, or the like is used. The electrodes 1a and 1b are formed in a long rectangular flat plate shape such as a groove plate shape, a mesh shape, or a lattice shape.

さらに、電気透析槽１は、図示しない切欠部を有する枠体としての室枠２を備えており、この室枠２の長手方向に沿った両端部の内側に一対の電極1a,1bが取り付けられている。そして、この室枠２内には、この室枠２の電極1aが配設された側である正極側から、正極側の電極室11aに供給される極液Ｐを仕切る陽イオン交換膜Ｋにつづいて、第１の陰イオン交換膜Ａ１、第１の陽イオン交換膜Ｋ１、第２の陰イオン交換膜Ａ２および第２の陽イオン交換膜Ｋ２が室枠２の幅方向に沿って所定の間隔、例えば等間隔に離間された状態で交互に繰り返し配列されている。 The electrodialysis tank 1 further includes a chamber frame 2 as a frame body having a notch (not shown), and a pair of electrodes 1a and 1b are attached to the inside of both end portions along the longitudinal direction of the chamber frame 2. ing. In the chamber frame 2, a cation exchange membrane K that partitions the polar liquid P supplied to the electrode chamber 11a on the positive electrode side from the positive electrode side where the electrode 1a of the chamber frame 2 is disposed. Subsequently, the first anion exchange membrane A 1 , the first cation exchange membrane K 1 , the second anion exchange membrane A 2 and the second cation exchange membrane K 2 are arranged in the width direction of the chamber frame 2. Are arranged alternately and repeatedly at predetermined intervals, for example, at regular intervals.

また、これら陽イオン交換膜Ｋ、第１の陰イオン交換膜Ａ１、第１の陽イオン交換膜Ｋ１、第２の陰イオン交換膜Ａ２および第２の陽イオン交換膜Ｋ２のそれぞれは、これら各陽イオン交換膜Ｋ、第１の陰イオン交換膜Ａ１、第１の陽イオン交換膜Ｋ１、第２の陰イオン交換膜Ａ２および第２の陽イオン交換膜Ｋ２に張力を持たせるために、室枠２の幅方向である長手方向および上下方向のそれぞれに沿って引っ張られて緊張された状態で、これら陽イオン交換膜Ｋ、第１の陰イオン交換膜Ａ１、第１の陽イオン交換膜Ｋ１、第２の陰イオン交換膜Ａ２および第２の陽イオン交換膜Ｋ２のそれぞれの両端が室枠２の両側面に締め付け固定されている。 Each of the cation exchange membrane K, the first anion exchange membrane A 1 , the first cation exchange membrane K 1 , the second anion exchange membrane A 2 and the second cation exchange membrane K 2 The cation exchange membrane K, the first anion exchange membrane A 1 , the first cation exchange membrane K 1 , the second anion exchange membrane A 2 and the second cation exchange membrane K 2 In order to give tension, the cation exchange membrane K and the first anion exchange membrane A 1 are pulled and tensioned along the longitudinal direction and the vertical direction that are the width direction of the chamber frame 2. Both ends of the first cation exchange membrane K 1 , the second anion exchange membrane A 2, and the second cation exchange membrane K 2 are fastened and fixed to both side surfaces of the chamber frame 2.

さらに、これら第１の陰イオン交換膜Ａ１、第１の陽イオン交換膜Ｋ１、第２の陰イオン交換膜Ａ２および第２の陽イオン交換膜Ｋ２にて仕切られた室枠２それぞれの内面には、この室枠２の内部に連通した図示しない液供給口および液排出口のそれぞれが設けられている。また、室枠２内には、この室枠２内の厚みを均一にする配流作用を有する図示しないスペーサが設けられている。 Further, the chamber frame 2 partitioned by the first anion exchange membrane A 1 , the first cation exchange membrane K 1 , the second anion exchange membrane A 2 and the second cation exchange membrane K 2 . Each inner surface is provided with a liquid supply port and a liquid discharge port (not shown) communicating with the inside of the chamber frame 2. In the chamber frame 2, a spacer (not shown) having a flow distribution function for making the thickness in the chamber frame 2 uniform is provided.

この結果、電気透析槽１内における電極1a,1b間は、第１の陰イオン交換膜Ａ１、第１の陽イオン交換膜Ｋ１、第２の陰イオン交換膜Ａ２および第２の陽イオン交換膜Ｋ２によって交互に仕切られている。 As a result, between the electrodes 1a and 1b in the electrodialysis tank 1, the first anion exchange membrane A 1 , the first cation exchange membrane K 1 , the second anion exchange membrane A 2 and the second cation exchange membrane A 1 are separated. It is partitioned alternately by an ion-exchange membrane K 2.

ここで、第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２としては、例えば一般的な強塩基性スチレン−ジビニルベンゼン系均一陰イオン交換膜などが使用される。具体的に、これら第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２としては、例えばセレミオンＡＭＶ膜(旭硝子株式会社製)、ネオセプタＡＭ−２膜(株式会社トクヤマ製)、アシプレックスＡ１０１膜(旭化成株式会社製)などが用いられる。 Here, as the first anion-exchange membrane A 1 and the second anion-exchange membrane A 2, for example, general strongly basic styrene - divinylbenzene based homogeneous anion exchange membrane is used. Specifically, as these first anion exchange membrane A 1 and second anion exchange membrane A 2 , for example, Selemion AMV membrane (Asahi Glass Co., Ltd.), Neocepta AM-2 membrane (Tokuyama Corp.), Aciplex A101 membrane (Asahi Kasei Co., Ltd.) or the like is used.

さらに、これら第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２として一価陰イオンの選択透過性を高めた膜である一価陰イオン選択透過膜を用いることにより、ヨウ素イオン(Ｉ−)の選択透過性がより高くなるので、より効果的である。そして、この一価陰イオン選択透過膜としては、例えばセレミオンＡＳＶ膜(旭硝子株式会社製)、ネオセプタＡＣＳ膜(株式会社トクヤマ製)、アシプレックスＡ１９２膜(旭化成株式会社製)などが用いられる。 Furthermore, by using monovalent anion selective permeable membranes, which are membranes with enhanced selective permeability of monovalent anions, as the first anion exchange membrane A 1 and the second anion exchange membrane A 2 , iodine can be obtained. Since the selective permeability of the ions (I − ) becomes higher, it is more effective. As the monovalent anion selective permeable membrane, for example, Selemion ASV membrane (manufactured by Asahi Glass Co., Ltd.), Neoceptor ACS membrane (manufactured by Tokuyama Co., Ltd.), Aciplex A192 membrane (manufactured by Asahi Kasei Co., Ltd.) and the like are used.

ここで、第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２としては、一価の陰イオン以外の任意の陰イオンを透過させる選択性を有しない一般の陰イオン選択透過膜と、一価の陰イオンを選択的に透過させる一価陰イオン選択透過膜とがある。そして、ヨウ素イオンが一価であるため、このヨウ素イオンを透過させる効率を考慮すると、一価陰イオン選択透過膜が好ましい。また、このヨウ素イオンの対アニオンとして二価の硫酸イオン(ＳＯ４ ２−)を用いるときは、一般の陰イオン選択透過膜を用いることが好ましく、このヨウ素イオンの対アニオンとして一価の塩素イオン(Ｃｌ−)を用いるときは一価陰イオン選択透過膜を用いることが好ましい。 Here, as the first anion exchange membrane A 1 and the second anion exchange membrane A 2 , a general anion selective permeation that does not have a selectivity for transmitting any anion other than a monovalent anion. There are a membrane and a monovalent anion selective permeable membrane that selectively transmits monovalent anions. And since iodine ion is monovalent, when the efficiency which permeate | transmits this iodine ion is considered, a monovalent | monohydric anion selective permeation membrane is preferable. When divalent sulfate ion (SO 4 2− ) is used as the counter anion of iodine ion, it is preferable to use a general anion selective permeable membrane, and monovalent chloride ion as the counter anion of iodine ion When using (Cl − ), it is preferable to use a monovalent anion selective permeable membrane.

また、陽イオン交換膜Ｋ、第１の陽イオン交換膜Ｋ１および第２の陽イオン交換膜Ｋ２としては、例えば強酸性スチレン−ジビニルベンゼン系均一陽イオン交換膜などが使用される。具体的に、これら陽イオン交換膜Ｋ、第１の陽イオン交換膜Ｋ１および第２の陽イオン交換膜Ｋ２としては、例えばセレミオンＣＭＶ膜(旭硝子株式会社製)、ネオセプタＣＭ−１膜(株式会社トクヤマ製)、アシプレックスＫ１０１膜(旭化成株式会社製)などが用いられる。 Further, the cation exchange membrane K, as the first cation exchange membrane K 1 and the second cation exchange membrane K 2, for example, strongly acidic styrene - divinylbenzene based homogeneous cation exchange membrane is used. Specifically, these cation exchange membranes K, as the first cation exchange membrane K 1 and the second cation exchange membrane K 2, for example, Selemion CMV membrane (manufactured by Asahi Glass Co., Ltd.), NEOSEPTA CM-1 membranes ( Tokuyama Corporation), Aciplex K101 membrane (Asahi Kasei Corporation), etc. are used.

一方、電気透析槽１の内部に電極1a,1bが収容されており、陰極側が陽イオン交換膜Ｋにて仕切られた電気透析槽１の室枠２内が極液室としての電極室11aとなる。また、陽極側が第２の陽イオン交換膜Ｋ２にて仕切られた電気透析槽１の室枠２内が極液室としての電極室11bとなる。 Meanwhile, inside electrodes 1a of the electrodialysis cell 1, 1b are accommodated, the electrode chambers 11a of the shade electrode side in compartment frame 2 of the electrodialysis cell 1 is partitioned by a cation exchange membrane K as the electrode liquid chamber It becomes. Further, positive electrode side second cation exchange membrane K 2 at partitioned electrodialysis cell 1 chamber frame within 2 is an electrode chamber 11b as electrode liquid chamber.

さらに、この電気透析槽１の陰極側の電極室11bに隣接して原液室としての試料室である第１の溶液室12が設けられている。この第１の溶液室12は、陰極側が第２の陽イオン交換膜Ｋ２にて仕切られ、陽極側が第２の陰イオン交換膜Ａ２にて仕切られている。この第１の溶液室12には、ヨウ化水素酸(ＨＩ)と他の無機塩およびこれらの塩のいずれかとを含む水溶液である原液Ｄが供給される。また、この第１の溶液室12の長手方向に沿った室枠２の両側面に位置する液供給口および液排出口は、原液Ｄの入口および出口となる原液入口および原液出口とされている。そして、この原液入口から原液Ｄが供給されるとともに、原液出口から原液Ｄが導出される。 Further, a first solution chamber 12 which is a sample chamber as a stock solution chamber is provided adjacent to the electrode chamber 11b on the cathode side of the electrodialysis tank 1. The first solution chamber 12, the cathode side is partitioned by the second cation exchange membrane K 2, the anode side is partitioned by the second anion-exchange membrane A 2. The first solution chamber 12 is supplied with a stock solution D which is an aqueous solution containing hydroiodic acid (HI), another inorganic salt, and any of these salts. Further, the liquid supply port and the liquid discharge port located on both side surfaces of the chamber frame 2 along the longitudinal direction of the first solution chamber 12 are a stock solution inlet and a stock solution outlet that serve as an inlet and an outlet for the stock solution D, respectively. . The stock solution D is supplied from the stock solution inlet, and the stock solution D is led out from the stock solution outlet.

ここで、この原液Ｄは、ヨウ素イオンを含む水溶液であって、この原液Ｄ中のヨウ化水素酸濃度は、希薄であると電流値が低くなり製造効率が低下することから、通常は０．１質量％以上３０質量％以下程度の範囲に調整されている。また、この原液Ｄ中に含まれるヨウ化水素酸以外の無機酸あるいはこれらの塩としては、一般的に、塩化水素酸(ＨＣｌ)や、臭化水素酸(ＨＢｒ)、硫酸(Ｈ２ＳＯ４)、リン酸(Ｈ３ＰＯ４)、硫酸水素ナトリウム(ＮａＨＳＯ４)、リン酸水素二ナトリウム(Ｎａ２ＨＰＯ４)、ヨウ化ナトリウム(ＮａＩ)などであり、これら無機酸あるいはこれらの塩の濃度は、０．０１質量％以上１０質量％以下の範囲である。 Here, the stock solution D is an aqueous solution containing iodine ions. When the concentration of hydroiodic acid in the stock solution D is dilute, the current value decreases and the production efficiency decreases. It is adjusted to a range of about 1% by mass or more and 30% by mass or less. Further, inorganic acids other than hydroiodic acid or salts thereof contained in the stock solution D are generally hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid (H 2 SO 4). ), Phosphoric acid (H 3 PO 4 ), sodium hydrogen sulfate (NaHSO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ), sodium iodide (NaI), etc., and the concentration of these inorganic acids or salts thereof Is the range of 0.01 mass% or more and 10 mass% or less.

また、第１の溶液室12の陽極側には、濃縮室としての試料室である第２の溶液室13が設けられている。この第２の溶液室13は、陰極側が第２の陰イオン交換膜Ａ２にて仕切られ、陽極側が第１の陽イオン交換膜Ｋ１にて仕切られている。そして、この第２の溶液室13は、ヨウ化水素酸の水溶液である濃縮液Ｃが供給される。この第２の溶液室13の長手方向に沿った室枠２の両側面に位置する液供給口および液排出口は、濃縮液Ｃの入口および出口となる濃縮液入口および濃縮液出口とされている。そして、この濃縮液入口から濃縮液Ｃが供給されるとともに、濃縮液出口から濃縮液Ｃが導出される。ここで、この濃縮液Ｃは、目的とされるものであり、この濃縮液Ｃ中のヨウ化水素酸の濃度は、通常は電気透析の開始時で０．１質量％以上５質量％以下程度に調整されている。 Further, on the anode side of the first solution chamber 12, a second solution chamber 13 which is a sample chamber as a concentration chamber is provided. The second solution chamber 13, the cathode side is partitioned by the second anion-exchange membrane A 2, the anode side is partitioned by the first cation exchange membrane K 1. The second solution chamber 13 is supplied with a concentrate C that is an aqueous solution of hydroiodic acid. The liquid supply port and the liquid discharge port located on both side surfaces of the chamber frame 2 along the longitudinal direction of the second solution chamber 13 are used as a concentrated liquid inlet and a concentrated liquid outlet serving as an inlet and an outlet for the concentrated liquid C, respectively. Yes. Then, the concentrate C is supplied from the concentrate inlet, and the concentrate C is led out from the concentrate outlet. Here, the concentrate C is intended, and the concentration of hydroiodic acid in the concentrate C is usually about 0.1% by mass to 5% by mass at the start of electrodialysis. Has been adjusted.

さらに、この第２の溶液室13の陽極側には、酸室としての試料室である第３の溶液室15が設けられている。この第３の溶液室15は、陰極側が第１の陽イオン交換膜Ｋ１にて仕切られ、陽極側が第１の陰イオン交換膜Ａ１にて仕切られている。そして、この第３の溶液室15には、塩酸または硫酸などの強酸の水溶液である酸液Ａが供給される。ここで、第３の溶液室15の長手方向に沿った室枠２の両側面に位置する液供給口および液排出口は、酸液Ａの入口および出口となる酸入口および酸出口とされている。そして、この酸入口から酸液Ａが供給されるとともに、酸出口から酸液Ａが導出される。この酸液Ａ中の酸の濃度は、希薄であると電流値が低くなり、ヨウ化水素酸の製造効率が低下することから、通常は１質量％以上２０質量％以下程度に調整されている。 Further, a third solution chamber 15 which is a sample chamber serving as an acid chamber is provided on the anode side of the second solution chamber 13. The third solution chamber 15, the cathode side is partitioned by the first cation exchange membrane K 1, the anode side is partitioned by a first anion exchange membrane A 1. The third solution chamber 15 is supplied with an acid solution A that is an aqueous solution of a strong acid such as hydrochloric acid or sulfuric acid. Here, the liquid supply port and the liquid discharge port located on both side surfaces of the chamber frame 2 along the longitudinal direction of the third solution chamber 15 are an acid inlet and an acid outlet that serve as an inlet and an outlet for the acid solution A, respectively. Yes. Then, the acid solution A is supplied from the acid inlet, and the acid solution A is led out from the acid outlet. The acid concentration in the acid solution A is usually adjusted to about 1% by mass or more and about 20% by mass or less because the current value becomes low and the production efficiency of hydroiodic acid is lowered when the acid solution A is dilute. .

また、この第３の溶液室15の陽極側には、濃縮室としての試料室である第４の溶液室16が設けられている。この第４の溶液室16は、陰極側が第１の陰イオン交換膜Ａ１にて仕切られ、極液Ｐを仕切る陽イオン交換膜Ｋにて陽極側が仕切られた塩室である。そして、この第４の溶液室16には、第３の溶液室15に供給される酸に対応して副生される酸あるいは塩の水溶液である塩液Ｓが供給される。ここで、この第４の溶液室16の長手方向に沿った室枠２の両側面に位置する液供給口および液排出口は、塩液Ｓの入口および出口となる塩入口および塩出口とされている。そして、この塩入口から塩液Ｓが供給されるとともに、塩出口から塩液Ｓが導出される。この塩液Ｓ中の塩の濃度は、通常は電気透析の開始時で０．１質量％以上５質量％以下程度に調整されている。 Further, on the anode side of the third solution chamber 15, a fourth solution chamber 16 as a sample chamber as a concentration chamber is provided. The fourth solution chamber 16 is a salt chamber in which the cathode side is partitioned by the first anion exchange membrane A 1 and the anode side is partitioned by the cation exchange membrane K that partitions the polar liquid P. The fourth solution chamber 16 is supplied with a salt solution S, which is an acid or salt aqueous solution by-produced corresponding to the acid supplied to the third solution chamber 15. Here, the liquid supply port and the liquid discharge port located on both side surfaces of the chamber frame 2 along the longitudinal direction of the fourth solution chamber 16 are a salt inlet and a salt outlet that serve as an inlet and an outlet for the salt solution S, respectively. ing. Then, the salt solution S is supplied from the salt inlet, and the salt solution S is led out from the salt outlet. The concentration of the salt in the salt solution S is usually adjusted to about 0.1% by mass or more and 5% by mass or less at the start of electrodialysis.

さらに、各電極室11a,11bに供給する極液Ｐとしては、０．１質量％以上１０質量％以下程度の硫酸、リン酸あるいはこれらの塩、例えば硫酸水素ナトリウム(ＮａＨＳＯ４)などの水溶液が用いられる。これら電極室11a,11bの長手方向に沿った室枠２の両側面に位置する液供給口および液排出口は、極液Ｐの入口および出口となる極液入口および極液出口とされている。そして、この極液入口から極液Ｐが供給されるとともに、極液出口から極液Ｐが導出される。これら各電極室11a,11bの電極1a,1b間に供給される電気透析時の運転電流密度は、限界電流密度を予め測定した上で、限界電流密度以下と設定されている。また、電気透析槽１での電気透析時の原液Ｄ、濃縮液Ｃ、酸液Ａおよび塩液Ｓそれぞれの温度は、通滞５℃以上７０℃以下、好ましくは２０℃以上５０℃以下の範囲である。 Further, as the polar liquid P supplied to the electrode chambers 11a and 11b, an aqueous solution of sulfuric acid, phosphoric acid, or a salt thereof such as sodium hydrogen sulfate (NaHSO 4 ) of 0.1% by mass to 10% by mass is used. Used. The liquid supply port and the liquid discharge port located on both side surfaces of the chamber frame 2 along the longitudinal direction of the electrode chambers 11a and 11b are an polar liquid inlet and an polar liquid outlet that serve as an inlet and an outlet for the polar liquid P, respectively. . Then, the polar liquid P is supplied from the polar liquid inlet, and the polar liquid P is led out from the polar liquid outlet. The operating current density during electrodialysis supplied between the electrodes 1a and 1b of each of the electrode chambers 11a and 11b is set to be equal to or lower than the limit current density after the limit current density is measured in advance. The temperatures of the stock solution D, concentrated solution C, acid solution A, and salt solution S during electrodialysis in the electrodialysis tank 1 are within the range of 5 ° C. to 70 ° C., preferably 20 ° C. to 50 ° C. It is.

ここで、電気透析槽１の室枠２内の第１の陰イオン交換膜Ａ１、第１の陽イオン交換膜Ｋ１、第２の陰イオン交換膜Ａ２および第２の陽イオン交換膜Ｋ２の配列の繰り返し回数ｎは、目的に応じて選択でき、好ましくは５以上５００以下程度の繰り返し回数である。なお、電気透析槽１の電極室11a,11b、第１の溶液室12、第２の溶液室13、第３の溶液室15および第４の溶液室16への極液Ｐ、原液Ｄ、濃縮液Ｃ、酸液Ａおよび塩液Ｓそれぞれの各液の供給は連続的にする。 Here, the first anion exchange membrane A 1 , the first cation exchange membrane K 1 , the second anion exchange membrane A 2 and the second cation exchange membrane in the chamber frame 2 of the electrodialysis tank 1. number of repetitions n of the sequence of K 2 can be selected according to the purpose, preferably the number of repetitions of degree 5 to 500. The electrode chambers 11a and 11b, the first solution chamber 12, the second solution chamber 13, the third solution chamber 15 and the fourth solution chamber 16 of the electrodialysis tank 1 are concentrated in the polar solution P, the stock solution D, and concentrated. The liquid C, the acid liquid A, and the salt liquid S are supplied continuously.

また、これら極液Ｐ、原液Ｄ、濃縮液Ｃ、酸液Ａおよび塩液Ｓを供給させる図示しない外部タンクを設けて、これら極液Ｐ、原液Ｄ、濃縮液Ｃ、酸液Ａおよび塩液Ｓを電極室11a,11b、第１の溶液室12、第２の溶液室13、第３の溶液室15および第４の溶液室16と外部タンクとの間でそれぞれを循環させてもよい。さらに、原液Ｄは、ヨウ化水素酸と他の無機酸およびこれらの塩、すなわちヨウ化水素酸および他の無機酸それぞれの塩の少なくともいずれかとを含む水溶液であればよいが、例えばブローイングアウト法にて製造したヨウ素吸収液、あるいは有機ヨウ素化合物を酸で加水分解したヨウ化水素酸を含有した水溶液などが好ましい。   Further, an external tank (not shown) for supplying these polar solution P, undiluted solution D, concentrated solution C, acid solution A and salt solution S is provided, and these polar solution P, undiluted solution D, concentrated solution C, acid solution A and salt solution are provided. S may be circulated between the electrode chambers 11a and 11b, the first solution chamber 12, the second solution chamber 13, the third solution chamber 15, the fourth solution chamber 16, and the external tank. Furthermore, the stock solution D may be an aqueous solution containing hydroiodic acid and at least one of other inorganic acids and salts thereof, that is, hydroiodic acid and other inorganic acids, for example, a blowing-out method. Or an aqueous solution containing hydroiodic acid obtained by hydrolyzing an organic iodine compound with an acid.

次に、上記一実施の形態のヨウ素イオンの分離方法を説明する。   Next, the iodine ion separation method of the above-described embodiment will be described.

まず、分離工程として電気透析槽１の各電極室11a,11bに極液Ｐを供給するとともに、第１の溶液室12に原液Ｄを供給し、第２の溶液室13に濃縮液Ｃを供給する。また、第３の溶液室15に酸液Ａを供給し、第４の溶液室16に塩液Ｓを供給する。   First, as a separation step, the polar solution P is supplied to the electrode chambers 11 a and 11 b of the electrodialysis tank 1, the stock solution D is supplied to the first solution chamber 12, and the concentrated solution C is supplied to the second solution chamber 13. To do. Further, the acid solution A is supplied to the third solution chamber 15, and the salt solution S is supplied to the fourth solution chamber 16.

この状態で、各電極室11a,11bの電極1a,1b間に、予め測定した限界電流密度以下の電流を供給する。   In this state, a current equal to or lower than the limit current density measured in advance is supplied between the electrodes 1a and 1b of the electrode chambers 11a and 11b.

すると、図１に示すように、第１の溶液室12内の水素イオン(Ｈ＋)が第２の陽イオン交換膜Ｋ２を透過するとともに、この第１の溶液室12内のヨウ素イオン(Ｉ−)が第２の陰イオン交換膜Ａ２を透過する。 Then, as shown in FIG. 1, hydrogen ions (H + ) in the first solution chamber 12 permeate the second cation exchange membrane K 2 and iodine ions (in the first solution chamber 12 ( I − ) permeates the second anion exchange membrane A 2 .

このとき、このヨウ素イオン、硫酸イオン(ＳＯ４ ２−)、リン酸イオン(ＰＯ４ ３−)および塩素イオン(Ｃｌ−)などの陰イオンは、陽イオン交換膜Ｋ，第１の陽イオン交換膜Ｋ１および第２の陽イオン交換膜Ｋ２を透過できない。また、水素イオンは、第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２を透過できない。 At this time, the anions such as iodine ion, sulfate ion (SO 4 2− ), phosphate ion (PO 4 3− ), and chlorine ion (Cl − ) are converted into the cation exchange membrane K and the first cation exchange. It can not be transmitted through the film K 1 and the second cation exchange membrane K 2. The hydrogen ions can not pass through the first anion-exchange membrane A 1 and the second anion-exchange membrane A 2.

一方、第３の溶液室15内の水素イオンが第１の陽イオン交換膜Ｋ１を通過して陰極側の第２の溶液室13へ移動し、第３の溶液室15内のヨウ素イオンの対アニオンが第１の陰イオン交換膜Ａ１を透過する。 On the other hand, hydrogen ions in the third solution chamber 15 pass through the first cation exchange membrane K 1 and move to the second solution chamber 13 on the cathode side, and iodine ions in the third solution chamber 15 The counter anion permeates through the first anion exchange membrane A1.

上述したように、上記一実施の形態によれば、電気透析槽１を用いた複置換電気透析法により、第１の溶液室12内に供給した原液Ｄ中のヨウ素イオンと、第３の溶液室15内に供給した酸液Ａ中の水素イオンとから、ヨウ素イオンを含むヨウ化水素酸が生成され、第２の溶液室13内の濃縮液Ｃ中のヨウ化水素酸の濃度が上昇するとともに、第４の溶液室16内の塩液Ｓ中の酸あるいは塩の濃度が上昇する。   As described above, according to the embodiment, iodine ions in the stock solution D supplied into the first solution chamber 12 and the third solution by the double displacement electrodialysis method using the electrodialysis tank 1. Hydroiodic acid containing iodine ions is generated from the hydrogen ions in the acid solution A supplied into the chamber 15, and the concentration of hydroiodic acid in the concentrated solution C in the second solution chamber 13 increases. At the same time, the concentration of the acid or salt in the salt solution S in the fourth solution chamber 16 increases.

このため、原料系の第１の溶液室12内の原液Ｄ中のヨウ化水素酸の濃度および第３の溶液室15内の酸液Ａ中の酸の濃度が次第に低下するとともに、この濃度の低下に伴って電流値が低下する。   For this reason, the concentration of hydroiodic acid in the stock solution D in the first solution chamber 12 of the raw material system and the concentration of the acid in the acid solution A in the third solution chamber 15 are gradually reduced, and this concentration The current value decreases with the decrease.

そして、この電流値が低下した場合には、電気透析槽１による電気透析を一旦停止して、原料系の第１の溶液室12および第３の溶液室15内の原液Ｄおよび酸液Ａを処理液として適当量抜き出した後、これら第１の溶液室12および第３の溶液室15のそれぞれに原料液である原液Ｄおよび酸液Ａを補充する。   And when this electric current value falls, the electrodialysis by the electrodialysis tank 1 is once stopped, and the stock solution D and the acid solution A in the first solution chamber 12 and the third solution chamber 15 of the raw material system are removed. After an appropriate amount is extracted as the processing liquid, the first solution chamber 12 and the third solution chamber 15 are replenished with the raw solution D and the acid solution A, respectively.

さらに、生成系の第２の溶液室13および第４の溶液室16内の各濃縮液Ｃおよび塩液Ｓは、一部を次回の電気透析の原料として使用するために残し、残りを生成液として抜き出す。したがって、上記の分離工程を繰り返して、第２の溶液室13内のヨウ化水素酸の濃度が上昇した処理液、すなわち濃縮液Ｃを第２の溶液室13から抜き出すことによって、高濃度の目的とするヨウ化水素酸水溶液を得ることができる。   Further, a part of the concentrated solution C and the salt solution S in the second solution chamber 13 and the fourth solution chamber 16 of the production system are left to be used as raw materials for the next electrodialysis, and the remainder is produced. Extract as Therefore, by repeating the above separation step and extracting the treatment liquid having an increased concentration of hydroiodic acid in the second solution chamber 13, that is, the concentrated liquid C, from the second solution chamber 13, a high concentration object is obtained. An aqueous hydroiodic acid solution can be obtained.

このとき、この電気透析槽１の第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２としては、一般の陰イオン選択透過膜と一価陰イオン選択透過膜とがある。ここで、ヨウ素イオンが一価であることから、このヨウ素イオンを透過させる効率を考慮すると、一価陰イオン選択透過膜が好ましい。また、ヨウ素イオンの対アニオンとして二価の硫酸イオン(ＳＯ４ ２−)を用いるときは、対アニオンが通過する第１の陰イオン交換膜Ａ１として一般の陰イオン選択透過膜を用いることが好ましく、ヨウ素イオンの対アニオンとして一価の塩素イオン(Ｃｌ−)を用いるときは、第１の陰イオン交換膜Ａ１として一価陰イオン選択透過膜を用いることが好ましい。 At this time, as the first anion-exchange membrane A 1 and the second anion-exchange membrane A 2 of the electrodialysis cell 1, there is a general anionic permselective membranes and monovalent anion permselective membranes. Here, since iodine ions are monovalent, a monovalent anion selective permeable membrane is preferable in consideration of the efficiency of permeating the iodine ions. When divalent sulfate ion (SO 4 2− ) is used as a counter anion of iodine ion, a general anion selective permeable membrane may be used as the first anion exchange membrane A 1 through which the counter anion passes. Preferably, when a monovalent chlorine ion (Cl − ) is used as a counter anion for iodine ions, a monovalent anion selective permeable membrane is preferably used as the first anion exchange membrane A 1 .

そこで、これら第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２として一価陰イオン選択透過膜を用いつつ、第３の溶液室15に供給する酸液Ａとして塩酸の水溶液を用いることによって、ヨウ素の移動速度を大きくしつつ電力原単位をより小さくできる。同様に、第１の陰イオン交換膜Ａ１として一般の陰イオン選択透過膜を用いるとともに、第２の陰イオン交換膜Ａ２として一価陰イオン選択透過膜を用いつつ、第３の溶液室15に供給する酸液Ａとして硫酸の水溶液を用いることによって、ヨウ素の移動速度を大きくしつつ電力原単位をより小さくできる。 Therefore, these first as an anion-exchange membrane A 1 and the second anion-exchange membrane A 2 while using a monovalent anion permselective membrane, an aqueous solution of hydrochloric acid as a third solution chamber 15 to supply acid solution A By using this, the power consumption rate can be further reduced while increasing the moving speed of iodine. Similarly, with use of the common anion permselective membrane first as an anion-exchange membrane A 1, while using a monovalent anion permselective membrane as the second anion-exchange membrane A 2, the third solution chamber By using an aqueous solution of sulfuric acid as the acid solution A supplied to 15, the power consumption rate can be further reduced while increasing the moving speed of iodine.

なお、第１の溶液室12に酸液Ａとして塩酸水溶液または硫酸水溶液を供給し、第３の溶液室15に原液Ｄを供給し、第２の溶液室13に塩液Ｓを供給し、第４の溶液室16に濃縮液Ｃを供給することにより、原液Ｄ中のヨウ素イオンを分離できる。ただし、電極室11a,11bに供給される極液Ｐは、塩酸水溶液または硫酸水溶液にする必要があり、腐食性の観点から、第１の溶液室12に原液Ｄを供給し、第３の溶液室15に酸液Ａを供給することが好ましい。   In addition, a hydrochloric acid aqueous solution or a sulfuric acid aqueous solution is supplied to the first solution chamber 12 as the acid solution A, the stock solution D is supplied to the third solution chamber 15, the salt solution S is supplied to the second solution chamber 13, By supplying the concentrated solution C to the solution chamber 16 of 4, the iodine ions in the stock solution D can be separated. However, the polar solution P supplied to the electrode chambers 11a and 11b needs to be an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution. From the viewpoint of corrosiveness, the stock solution D is supplied to the first solution chamber 12 and the third solution It is preferable to supply the acid solution A to the chamber 15.

さらに、この酸液Ａとして用いる酸としては、上記のように塩酸(ＨＣｌ)や硫酸(Ｈ２ＳＯ４)のいずれも使用できるが、塩酸の場合は陽極側で塩素イオン(Ｃｌ−)が酸化されて塩素(Ｃｌ２)となり、この塩素により陽イオン交換膜Ｋが酸化されて劣化するおそれがあるとともに、安価であるので、塩酸よりも硫酸が好ましい。 Further, as the acid used as the acid solution A, either hydrochloric acid (HCl) or sulfuric acid (H 2 SO 4 ) can be used as described above. In the case of hydrochloric acid, chlorine ions (Cl − ) are oxidized on the anode side. Then, it becomes chlorine (Cl 2 ), and the cation exchange membrane K may be oxidized and deteriorated by the chlorine, and since it is inexpensive, sulfuric acid is preferable to hydrochloric acid.

以下、本発明の比較例および実施例について説明する。   Hereinafter, comparative examples and examples of the present invention will be described.

（比較例１）
ブローイングアウト法により製造したヨウ素吸収液を原液Ｄとして、図１に示す旭化成株式会社製Ｇ４型の電気透析槽１(４室／１組、組込み数５組、有効膜面積０．０２ｍ２／枚)を用いて複置換電気透析をした。 (Comparative Example 1)
As an undiluted solution D, an iodine absorption solution produced by the blowing out method is used as a G4 type electrodialysis tank 1 (4 chambers / set, 5 sets, effective membrane area 0.02 m 2 / sheet) as shown in FIG. ) Was used for double displacement electrodialysis.

このとき、陽イオン交換膜Ｋ、第１の陽イオン交換膜Ｋ１および第２の陽イオン交換膜Ｋ２として、透過させる陽イオンについて選択性を有しない一般の陽イオン交換膜であるセレミオシＣＭＶ膜(旭硝子株式会社製)を用いた。 At this time, the cation exchange membrane K, first as a cation exchange membrane K 1 and the second cation exchange membrane K 2, a cation which transmits a cation exchange membrane of the general having no selectivity Seremioshi CMV A membrane (Asahi Glass Co., Ltd.) was used.

また、第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２として、一価の陰イオンを選択的に透過させる性質を有する一価陰イオン選択透過膜であるセレミオンＡＳＶ膜(旭硝子株式会社製)を用いた。 Further, as the first anion exchange membrane A 1 and the second anion exchange membrane A 2 , a selemion ASV membrane which is a monovalent anion selective permeable membrane having a property of selectively transmitting monovalent anions ( Asahi Glass Co., Ltd.) was used.

そして、ヨウ化水素が８．９質量％であり、硫酸水素ナトリウムが５．６質量％であり、塩化水素が０．３質量％である組成の原液Ｄ１４４０ｇを第１の溶液室12に循環供給し、１質量％のヨウ化水素酸水溶液である濃縮液Ｃ７１２ｇを第２の溶液室13に循環供給した。同時に、３．３質量％の硫酸水溶液である酸液Ａ１６２１ｇを第３の溶液室15に循環供給し、１．７質量％の硫酸水素ナトリウム水溶液である塩液Ｓ１０００ｇを第４の溶液室16に循環供給した。また、各電極室11a,11bに５質量％の硫酸水素ナトリウム水溶液である極液Ｐ１０００ｇを循環供給した。   Then, 1440 g of a stock solution having a composition of 8.9% by mass of hydrogen iodide, 5.6% by mass of sodium hydrogen sulfate, and 0.3% by mass of hydrogen chloride is circulated and supplied to the first solution chamber 12. Then, 712 g of concentrated liquid C, which is a 1 mass% hydroiodic acid aqueous solution, was circulated and supplied to the second solution chamber 13. At the same time, 1621 g of acid solution A, which is a 3.3% by mass sulfuric acid aqueous solution, is circulated and supplied to the third solution chamber 15, and 1000 g of salt solution S, which is a 1.7% by mass sodium hydrogen sulfate aqueous solution, is supplied to the fourth solution chamber 16. Circulating supply. In addition, 1000 g of polar liquid P, which is a 5% by mass aqueous sodium hydrogen sulfate solution, was circulated and supplied to each electrode chamber 11a, 11b.

この状態で、８．５Ｖ定電圧で４時間電気透析処理した後、各室の液組成をイオンクロマトグラフィにて分析した。この結果、第１の溶液室12内の原液Ｄのイオン濃度は、ヨウ素イオン濃度が０．７質量％で、硫酸イオン濃度が４．０質量％で、塩素イオン濃度が０．２質量％であった。   In this state, after electrodialysis for 4 hours at a constant voltage of 8.5 V, the liquid composition in each chamber was analyzed by ion chromatography. As a result, the ion concentration of the stock solution D in the first solution chamber 12 is an iodine ion concentration of 0.7 mass%, a sulfate ion concentration of 4.0 mass%, and a chlorine ion concentration of 0.2 mass%. there were.

また、第２の溶液室13内の濃縮液Ｃのイオン濃度は、ヨウ素イオン濃度が１２．６質量％で、硫酸イオン濃度が０．４質量％で、塩素イオン濃度が０．１質量％であった。さらに、第３の溶液室15内の酸液Ａのイオン濃度は、硫酸イオン濃度が０．１質量％であった。また、第４の溶液室16内の塩液Ｓのイオン濃度は、硫酸イオン濃度が５．１質量％であった。 The ion concentration of the concentrate C in the second solution chamber 13 is 12.6 mass% iodine ion concentration, 0.4 mass% sulfate ion concentration, and 0.1 mass% chlorine ion concentration. there were. Further, the ion concentration in the third acid solution A solution chamber 15, sulfate ion concentration was 0.1 mass%. Further, the ion concentration of the salt solution S in the fourth solution chamber 16 was 5.1% by mass as the sulfate ion concentration.

（実施例１）
比較例１と同一の電気透析槽１、陽イオン交換膜Ｋ、第１の陽イオン交換膜Ｋ１、第２の陽イオン交換膜Ｋ２、第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２を用いて複置換電気透析をした。 Example 1
Same electrodialysis tank 1, cation exchange membrane K, first cation exchange membrane K 1 , second cation exchange membrane K 2 , first anion exchange membrane A 1 and second and a multi-substituted electrodialysis using an anion-exchange membrane a 2.

そして、ヨウ化水素が８．９質量％であり、硫酸水素ナトリウムが５．６質量％であり、塩化水素が０．３質量％である組成の原液Ｄ１４４０ｇを第１の溶液室12に循環供給し、１質量％のヨウ化水素酸水溶液である濃縮液Ｃ７１２ｇを第２の溶液室13に循環供給した。同時に、２．５質量％の塩酸水溶液である酸液Ａ１６３７ｇを第３の溶液室15に循環供給し、１．７質量％の塩化ナトリウム水溶液である塩液Ｓ１０００ｇを第４の溶液室16に循環供給した。また、各電極室11a,11bに５質量％の硫酸水素ナトリウム水溶液である極液Ｐ１０００ｇを循環供給した。   Then, 1440 g of a stock solution having a composition of 8.9% by mass of hydrogen iodide, 5.6% by mass of sodium hydrogen sulfate, and 0.3% by mass of hydrogen chloride is circulated and supplied to the first solution chamber 12. Then, 712 g of concentrated liquid C, which is a 1 mass% hydroiodic acid aqueous solution, was circulated and supplied to the second solution chamber 13. At the same time, 1637 g of acid solution A, which is a 2.5% by mass hydrochloric acid aqueous solution, is circulated and supplied to the third solution chamber 15, and 1000 g of salt solution S, which is a 1.7% by mass sodium chloride aqueous solution, is circulated to the fourth solution chamber 16. Supplied. In addition, 1000 g of polar liquid P, which is a 5% by mass aqueous sodium hydrogen sulfate solution, was circulated and supplied to each electrode chamber 11a, 11b.

この状態で、８．５Ｖ定電圧で１．４２時間電気透析処理した後、各室の液組成をイオンクロマトグラフィにて分析した。この結果、第１の溶液室12内の原液Ｄのイオン濃度は、ヨウ素イオン濃度が０．６質量％で、硫酸イオン濃度が４．０質量％で、塩素イオン濃度が０．２質量％であった。   In this state, after electrodialysis for 1.42 hours at a constant voltage of 8.5 V, the liquid composition in each chamber was analyzed by ion chromatography. As a result, the ion concentration of the stock solution D in the first solution chamber 12 is an iodine ion concentration of 0.6% by mass, a sulfate ion concentration of 4.0% by mass, and a chlorine ion concentration of 0.2% by mass. there were.

また、第２の溶液室13内の濃縮液Ｃのイオン濃度は、ヨウ素イオン濃度が１２．４質量％で、硫酸イオン濃度が０．２質量％で、塩素イオン濃度が０．１質量％であった。さらに、第３の溶液室15内の酸液Ａのイオン濃度は、塩素イオン濃度が０．１質量％であった。また、第４の溶液室16内の塩液Ｓのイオン濃度は、塩素イオン濃度が４．５質量％であった。   The ion concentration of the concentrate C in the second solution chamber 13 is 12.4 mass% iodine ion concentration, 0.2 mass% sulfate ion concentration, and 0.1 mass% chlorine ion concentration. there were. Further, the ion concentration of the acid solution A in the third solution chamber 15 was 0.1% by mass as the chlorine ion concentration. The ion concentration of the salt solution S in the fourth solution chamber 16 was 4.5% by mass as the chlorine ion concentration.

（実施例２）
比較例１と同一の電気透析槽１を用い、第１の陽イオン交換膜Ｋ１および第２の陽イオン交換膜Ｋ２として、セレミオンＣＭＶ膜(旭硝子株式会社製)を用いた。また、第１の陰イオン交換膜Ａ１として、透過させる陰イオンについて選択性を有しない一般の陰イオン選択透過膜であるセレミオンＡＭＶ膜(旭硝子株式会社製)を用い、第２の陰イオン交換膜Ａ２として、セレミオンＡＳＶ膜(旭硝子株式会社製)を用いて複置換電気透析をした。 (Example 2)
Using Comparative Example 1 the same electrodialysis cell 1 and, as the first cation exchange membrane K 1 and the second cation exchange membrane K 2, was used Selemion CMV membrane (manufactured by Asahi Glass Co., Ltd.). Further, as the first anion exchange membrane A 1 , a selemion AMV membrane (manufactured by Asahi Glass Co., Ltd.), which is a general anion selective permeation membrane having no selectivity for the permeated anion, is used, and the second anion exchange membrane is used. as film a 2, and the double substitution electrodialysis using Selemion ASV membranes (Asahi Glass Co., Ltd.).

そして、ヨウ化水素が８．９質量％であり、硫酸水素ナトリウムが５．６質量％であり、塩化水素が０．３質量％である組成の原液Ｄ１４４０ｇを第１の溶液室12に循環供給し、１質量％のヨウ化水素酸水溶液である濃縮液Ｃ７１２ｇを第２の溶液室13に循環供給した。同時に、３．３質量％の硫酸水溶液である酸液Ａ１６３３ｇを第３の溶液室15に循環供給し、１．７質量％の硫酸水素ナトリウム水溶液である塩液Ｓ１０００ｇを第４の溶液室16に循環供給した。また、各電極室11a,11bに５質量％の硫酸水素ナトリウム水溶液である極液Ｐ１０００ｇを循環供給した。   Then, 1440 g of a stock solution having a composition of 8.9% by mass of hydrogen iodide, 5.6% by mass of sodium hydrogen sulfate, and 0.3% by mass of hydrogen chloride is circulated and supplied to the first solution chamber 12. Then, 712 g of concentrated liquid C, which is a 1 mass% hydroiodic acid aqueous solution, was circulated and supplied to the second solution chamber 13. At the same time, 1633 g of an acid solution A which is a 3.3% by mass sulfuric acid aqueous solution is circulated and supplied to the third solution chamber 15, and 1000 g of a salt solution S which is a 1.7% by mass sodium hydrogen sulfate aqueous solution is supplied to the fourth solution chamber 16. Circulating supply. In addition, 1000 g of polar liquid P, which is a 5% by mass aqueous sodium hydrogen sulfate solution, was circulated and supplied to each electrode chamber 11a, 11b.

この状態で、８．５Ｖ定電圧で２．０８時間電気透析処理した後、各室の液組成をイオンクロマトグラフィにて分析した。この結果、第１の溶液室12内の原液Ｄのイオン濃度は、ヨウ素イオン濃度が０．８質量％で、硫酸イオン濃度が４．２質量％で、塩素イオン濃度が０．２質量％であった。   In this state, after electrodialysis for 2.08 hours at a constant voltage of 8.5 V, the liquid composition in each chamber was analyzed by ion chromatography. As a result, the ion concentration of the stock solution D in the first solution chamber 12 is an iodine ion concentration of 0.8 mass%, a sulfate ion concentration of 4.2 mass%, and a chlorine ion concentration of 0.2 mass%. there were.

また、第２の溶液室13内の濃縮液Ｃのイオン濃度は、ヨウ素イオン濃度が１２．４質量％で、硫酸イオン濃度が０．３質量％で、塩素イオン濃度が０．１質量％であった。さらに、第３の溶液室15内の酸液Ａのイオン濃度は、硫酸イオン濃度が０．１質量％であった。また、第４の溶液室16内の塩液Ｓのイオン濃度は、硫酸イオン濃度が５．０質量％であった。   The ion concentration of the concentrate C in the second solution chamber 13 is 12.4 mass% iodine ion concentration, 0.3 mass% sulfate ion concentration, and 0.1 mass% chlorine ion concentration. there were. Further, the ion concentration of the acid solution A in the third solution chamber 15 was 0.1% by mass as the sulfate ion concentration. Moreover, the ion concentration of the salt solution S in the fourth solution chamber 16 was 5.0 mass% in sulfate ion concentration.

ここで、実施例１および実施例２の結果から、第１の溶液室12内のヨウ素イオンが第２の陰イオン交換膜Ａ２を透過するときの移動速度を表１に示す。この結果、これら実施例１および実施例２では、同一電圧においては比較例１に比ベヨウ素イオン移動速度が著しく大きくなっている。 Here, based on the results of Examples 1 and 2, Table 1 shows the moving speed when iodine ions in the first solution chamber 12 pass through the second anion exchange membrane A2. As a result, in Example 1 and Example 2, the rate of movement of iodine ions is significantly higher than that of Comparative Example 1 at the same voltage.

Figure 0004831765
Figure 0004831765

（実施例３）
比較例１と同一の電気透析槽１、第１の陽イオン交換膜Ｋ１、第２の陽イオン交換膜Ｋ２、第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２を用いて複置換電気透析をした。 (Example 3)
The same electrodialysis tank 1, the first cation exchange membrane K 1 , the second cation exchange membrane K 2 , the first anion exchange membrane A 1 and the second anion exchange membrane A 2 as in Comparative Example 1. Was used for double displacement electrodialysis.

そして、運転電圧を６Ｖ定電圧とし、各室の仕込み溶液の供給を実施例１と同じ条件にした。４時間電気透析処理した後、各室の液組成をイオンクロマトグラフィにて分析した結果、原液Ｄのイオン濃度は、ヨウ素イオン濃度が０．８質量％で、硫酸イオン濃度が４．０質量％で、塩素イオン濃度が０．２質量％であった。また、濃縮液Ｃのイオン濃度は、ヨウ素イオン濃度が１２．４質量％で、硫酸イオン濃度が０．３質量％で、塩素イオン濃度が０．１質量％であった。さらに、酸液Ａのイオン濃度は、塩素イオン濃度が０．１質量％で、塩液Ｓの塩素イオン濃度が４．５質量％であった。   The operating voltage was set to a constant voltage of 6 V, and the supply of the charged solution in each chamber was performed under the same conditions as in Example 1. After electrodialysis for 4 hours, the liquid composition in each chamber was analyzed by ion chromatography. As a result, the ion concentration of the stock solution D was 0.8% by mass for iodine ions and 4.0% by mass for sulfate ions. The chlorine ion concentration was 0.2% by mass. Concentration C had an ion concentration of 12.4% by mass for iodine ion, 0.3% by mass for sulfate ion, and 0.1% by mass for chloride ion. Furthermore, the ion concentration of the acid solution A was 0.1% by mass for the chlorine ion concentration and 4.5% by mass for the chloride ion concentration of the salt solution S.

（実施例４）
比較例１と同一の電気透析槽１を用い、第１の陽イオン交換膜Ｋ１、第２の陽イオン交換膜Ｋ２、第１の陰イオン交換膜Ａ１および第２の陰イオン交換膜Ａ２については実施例２と同一のものを用いて複置換電気透析をした。 Example 4
Using the same electrodialysis tank 1 as in Comparative Example 1, the first cation exchange membrane K 1 , the second cation exchange membrane K 2 , the first anion exchange membrane A 1 and the second anion exchange membrane for a 2 was a multi-substituted electrodialysis using the same as in example 2.

そして、運転電圧を６Ｖ定電圧とし、各室の仕込み溶液の供給を実施例２と同じ条件にした。４時間電気透析処理した後、各室の液組成をイオンクロマトグラフィにて分析した結果、原液Ｄのイオン濃度は、ヨウ素イオン濃度が０．７質量％で、硫酸イオン濃度が４．１質量％で、塩素イオン濃度が０．２質量％であった。また、濃縮液Ｃのイオン濃度は、ヨウ素イオン濃度が１２．５質量％で、硫酸イオン濃度が０．３質量％で、塩素イオン濃度が０．１質量％であった。さらに、酸液Ａのイオン濃度は、硫酸イオン濃度が０．１質量％であり、塩液Ｓのイオン濃度は、硫酸イオン濃度が５．０質量％であった。   And the operating voltage was set to 6V constant voltage, and supply of the charging solution of each chamber was made into the same conditions as Example 2. After electrodialysis for 4 hours, the liquid composition in each chamber was analyzed by ion chromatography. As a result, the ion concentration of the stock solution D was 0.7% by mass for iodine ions and 4.1% by mass for sulfate ions. The chlorine ion concentration was 0.2% by mass. Concentration C had an ion concentration of 12.5% by mass for iodine ion, 0.3% by mass for sulfate ion, and 0.1% by mass for chloride ion. Further, the ion concentration of the acid solution A was 0.1% by mass, and the ion concentration of the salt solution S was 5.0% by mass.

ここで、実施例３および実施例４の結果から、電気透析処理中の消費電力量の比較を表２に示す。この結果、これら実施例３および実施例４のヨウ素イオンの移動速度はほぼ同じであったが、比較例１に比べ約３０％程度低い消費電力量となっている。   Here, based on the results of Example 3 and Example 4, a comparison of power consumption during electrodialysis is shown in Table 2. As a result, the movement speeds of iodine ions in Examples 3 and 4 were almost the same, but the power consumption was about 30% lower than that in Comparative Example 1.

Figure 0004831765
Figure 0004831765

本発明の一実施の形態のヨウ素イオンの分離方法を用いた電気透析槽を示す説明図である。It is explanatory drawing which shows the electrodialysis tank using the separation method of the iodine ion of one embodiment of this invention.

１ 電気透析槽
11a,11b 電極室
Ａ１ 陰イオン交換膜としての第１の陰イオン交換膜
Ａ２ 陰イオン交換膜としての第２の陰イオン交換膜
Ｋ 陽イオン交換膜
Ｋ１ 陽イオン交換膜としての第１の陽イオン交換膜
Ｋ２ 陽イオン交換膜としての第２の陽イオン交換膜
Ｄ 原液
Ａ 酸液 1 Electrodialysis tank
11a, 11b Electrode chamber A First anion exchange membrane as an anion exchange membrane A Second anion exchange membrane as an anion exchange membrane K First anion exchange membrane as a K1 cation exchange membrane Second cation exchange membrane as a K2 cation exchange membrane
D stock solution
A acid solution

Claims (4)

ヨウ素イオンを含む水溶液である原液から複置換電気透析法にてヨウ素イオンを分離するヨウ素イオンの分離方法であって、
ヨウ素イオンの対アニオンとしての塩素イオンを含む水溶液である酸液を用い、
一対の正極側の電極室と負極側の電極室との間を正極側から前記電極室に供給される極液を仕切る陽イオン交換膜につづいて、第１の陰イオン交換膜と第１の陽イオン交換膜と第２の陰イオン交換膜と第２の陽イオン交換膜とが交互に繰り返し設けられ、これら第１の陰イオン交換膜、第１の陽イオン交換膜、第２の陰イオン交換膜および第２の陽イオン交換膜にて４つの試料室に交互に仕切った電気透析槽の前記第１の陰イオン交換膜と前記第１の陽イオン交換膜との間および前記第２の陰イオン交換膜と前記第２の陽イオン交換膜との間のいずれか一方に前記原液を供給し、他方に前記酸液を供給し、
前記原液に接する陰イオン交換膜として一価陰イオン選択透過膜を用い、
前記原液中のヨウ素イオンと前記酸液中の水素イオンとから複置換電気透析法によってヨウ化水素酸を生成する
ことを特徴としたヨウ素イオンの分離方法。 A method for separating iodine ions by separating iodine ions from a stock solution that is an aqueous solution containing iodine ions by double displacement electrodialysis,
Using an acid solution is an aqueous solution containing chlorine ions as counter anions of iodine ions,
The first anion exchange membrane and the first anion exchange membrane are separated from the pair of the positive electrode chamber and the negative electrode chamber by the cation exchange membrane that partitions the polar liquid supplied to the electrode chamber from the positive electrode side. A cation exchange membrane, a second anion exchange membrane, and a second cation exchange membrane are alternately and repeatedly provided. The first anion exchange membrane, the first cation exchange membrane, and the second anion. Between the first anion exchange membrane and the first cation exchange membrane of the electrodialysis tank partitioned alternately into four sample chambers by an exchange membrane and a second cation exchange membrane, and the second cation exchange membrane Supplying the stock solution to one of the anion exchange membrane and the second cation exchange membrane, and supplying the acid solution to the other,
Using a monovalent anion selective permeable membrane as an anion exchange membrane in contact with the stock solution ,
A method for separating iodine ions, comprising producing hydroiodic acid from iodine ions in the stock solution and hydrogen ions in the acid solution by a double displacement electrodialysis method. 酸液に接する陰イオン交換膜として一価陰イオン選択透過膜を用いるA monovalent anion selective permeation membrane is used as the anion exchange membrane in contact with the acid solution.
ことを特徴とした請求項１記載のヨウ素イオンの分離方法。The method for separating iodine ions according to claim 1. ヨウ素イオンを含む水溶液である原液から複置換電気透析法にてヨウ素イオンを分離するヨウ素イオンの分離方法であって、
ヨウ素イオンの対アニオンとしての硫酸イオンを含む水溶液である酸液を用い、
一対の正極側の電極室と負極側の電極室との間を正極側から前記電極室に供給される極液を仕切る陽イオン交換膜につづいて、第１の陰イオン交換膜と第１の陽イオン交換膜と第２の陰イオン交換膜と第２の陽イオン交換膜とが交互に繰り返し設けられ、これら第１の陰イオン交換膜、第１の陽イオン交換膜、第２の陰イオン交換膜および第２の陽イオン交換膜にて４つの試料室に交互に仕切った電気透析槽の前記第１の陰イオン交換膜と前記第１の陽イオン交換膜との間および前記第２の陰イオン交換膜と前記第２の陽イオン交換膜との間のいずれか一方に前記原液を供給し、他方に前記酸液を供給し、
前記原液に接する陰イオン交換膜として一価陰イオン選択透過膜を用い、
前記酸液に接する陰イオン交換膜として任意の陰イオンを透過させる陰イオン選択透過膜を用い、
前記原液中のヨウ素イオンと前記酸液中の水素イオンとから複置換電気透析法によってヨウ化水素酸を生成する
ことを特徴としたヨウ素イオンの分離方法。 A method for separating iodine ions by separating iodine ions from a stock solution that is an aqueous solution containing iodine ions by double displacement electrodialysis,
Using an acid solution is an aqueous solution containing sulfuric acid ions as counter anions of iodine ions,
The first anion exchange membrane and the first anion exchange membrane are separated from the pair of the positive electrode chamber and the negative electrode chamber by the cation exchange membrane that partitions the polar liquid supplied to the electrode chamber from the positive electrode side. A cation exchange membrane, a second anion exchange membrane, and a second cation exchange membrane are alternately and repeatedly provided. The first anion exchange membrane, the first cation exchange membrane, and the second anion. Between the first anion exchange membrane and the first cation exchange membrane of the electrodialysis tank partitioned alternately into four sample chambers by an exchange membrane and a second cation exchange membrane, and the second cation exchange membrane Supplying the stock solution to one of the anion exchange membrane and the second cation exchange membrane, and supplying the acid solution to the other,
Using a monovalent anion selective permeable membrane as an anion exchange membrane in contact with the stock solution ,
Using an anion selective permeable membrane that allows arbitrary anions to permeate as an anion exchange membrane in contact with the acid solution ,
A method for separating iodine ions, comprising producing hydroiodic acid from iodine ions in the stock solution and hydrogen ions in the acid solution by a double displacement electrodialysis method. 原液として、ブローイングアウト法にて得られたヨウ素吸収液を用いる
ことを特徴とした請求項１ないし３のいずれか記載のヨウ素イオンの分離方法。 The iodine ion separation method according to any one of claims 1 to 3, wherein an iodine absorption solution obtained by a blowing-out method is used as a stock solution .
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