200911691 九、發明說明 【發明所屬之技術領域】 本發明係關於自於偏光薄膜製造時所產生的之廢液回 收碘的自製造偏光薄膜之廢液中回收碘之方法；尤其是關 於碘回收後可回收硼之自製造偏光薄膜之廢液中回收碘之 方法。 【先前技術】 於液晶顯示器等所使用的偏光薄膜之製造步驟中會產 生含有碘離子、硼酸、鉀離子及水溶性有機物等之廢液。 此等偏光薄膜製造廢液，通常藉由凝集法及過濾法等，將 其中所含有的特定成分處理成廢水排放基準所規定之値以 下後再作爲工業廢水排出，或藉由濃縮以減小容積後作爲 產業廢棄物處理。 然而，近年來廢水排放基準中之硼及化合物之基準値 趨於嚴苛至l〇mg/L，以以往之凝集法及過濾法要將廢水 中之硼濃度降到基準値以下有其困難。又，於產業廢棄物 方面，就處理費用及環保問題等考量，亦期望減少排放量 。因此，過去曾被提出之方法有：進行電透析將偏光薄膜 製造廢液中所含有的有機物成分和碘及硼等無機成分分離 ，使其後之濃縮處理容易化，藉此謀求廢棄物量之減少的 處理方法（參照專利文獻1 )。圖6爲專利文獻1中所記 載的偏光薄膜製造廢液之處理方法的示意圖。如圖6所示 般，於專利文獻1所記載的處理方法中，係將貯留於廢液 -4- 200911691 槽101之偏光薄膜製造廢液102用泵103送到脫鹽液槽 104中，自該槽再用泵1〇9送到電透析裝置105。與其同 時，用栗1 1 〇將貯留於濃縮液槽1 0 6的純水送到電透析裝 置1 0 5，開始進行電透析。然後，使於電透析裝置1 0 5分 離的含有有機物成分之脫鹽液1 0 7與含有無機成分之濃縮 液1 08分別送回到脫鹽液槽1 〇4及濃縮液槽〗〇6之後，再 度送到電透析裝置1 〇 5。藉由如上述般反復操作，以循環 處理方式進行電透析。 又，於專利文獻1中揭示出：使濃縮液1 0 8更進一步 藉由離子層析法或硼選擇性離子交換樹脂處理法將含碘液 與含硼液分離，以此等作爲偏光薄膜製造溶液可再利用。 然而，專利文獻1所記載之技術’畢竟是以減少容積化來 減少廢棄量爲目的者，係針對使偏光薄膜製造廢液容易進 行濃縮處理而以將有機物成分與無機成分分離爲目的之技 術。因此，其雖記載著藉由公知的方法可將分離後的無機 成分分離爲含碘液與含硼液之要旨’但有關其具體的步驟 及條件並無探討。通常’偏光薄膜製造廢液多爲由成分及 濃度不同的多種廢液混合而成，由於各成分之濃度並非恆 定，欲調整爲姚染色步驟及硼交聯步驟中所使用的碘及硼 濃度有其困難，再就偏光薄膜成品之品質維持之觀點考量 ’將此等直接作爲偏光板製造廢液再利用並非實務之作法 〇 再者，於自含有無機物成分的水溶液分離、回收硼之 情況，通常係使用硼選擇性離子交換樹脂’過去曾有可使 200911691 利用硼選擇性離子交換樹脂自廢水中吸附除去的硼以硼酸 之形態回收的硼選擇性離子交換樹脂之再生方法被提出（ 參照專利文獻2 )。又，藉由弱酸性陽離子交換樹脂將廢 水中的陽離子吸附除去，再藉由弱鹼性陰離子交換樹脂將 廢水中之硼以外的陰離子除去後，藉由調整爲OH型之強 鹼性陰離子交換樹脂或此陰離子交換樹脂與調整爲Η型之 強酸性陽離子交換樹脂混合者將廢水中之硼吸附除去的方 法亦曾被提出（參照專利文獻3及4 )。 另一方面’有關碘方面，過去以來曾開發出各種自廢 液中回收碘的方法（參照例如專利文獻5及6 )。例如， 於專利文獻5中曾揭示出使用離子交換樹脂自含有碘化氫 的水中冋收碘的方法。又，本發明者等於專利文獻6中曾 提出：使含有碘及/或無機碘化合物的廢液氧化或還原， 使所生成之游離碘分子在酸性條件下吸附到吸附有碘離子 之強鹼性陰離子交換樹脂中，將廢液中所含有之無機鹽 類及有機物分離後’使吸附於此強鹼性陰離子交換樹脂之 碘分子以碘化氫溶液的形態溶出，藉此自廢液中回收碘的 方法。 [專利文獻1 ]日本特開2 0 0 1 - 3 1 4 8 6 4號公報 [專利文獻2]日本特公平3_1〇378號公報 [專利文獻3]日本特許3727212號公報 [專利文獻4]日本特開2〇〇5_296953號公報 [專利文獻5]曰本特開平6-63547號公報 [專利文獻6]日本特開平6-157008號公報 200911691 【發明內容】 (發明所欲解決之問題） 如前述般’於以往的方法，基於濃度、品質維持及經 濟性等之理由’欲將偏光薄膜製造廢液直接作爲偏光薄膜 製造溶液再利用有其困難。因此，於欲再利用偏光薄膜製 造廢液之情況’以自其中將碘及硼等可再利用的成分個別 分離、回收’再精製而使用爲佳。然而，欲自偏光薄膜製 造廢液中分離、回收碘及硼，有下述之問題點存在。 亦即’如專利文獻1及2所記載般，欲自廢水等中將 硼分離、回收之情況，通常係使用硼選擇性螯合樹脂，由 於此硼選擇性螯合樹脂中也會吸附碘等之硼以外的成分， 故可吸附之硼量變少，又，處理液中若含有碘等之會使樹 脂劣化的成分，樹脂的壽命會變短，是問題所在。另一方 面，如專利文獻3及4中所記載之處理方法般，藉由事先 自偏光薄膜製造廢液中將有機物及碘等之會使樹脂劣化的 成分除去，可提高樹脂的壽命及硼之回收效率，但此方法 中之設備及步驟數多，是問題所在。又，專利文獻3及4 中所記載之處理方法爲對硼及碘等之除去對象成分的量少 之工業用廢水進行大量處理的方法，對硼及碘濃度高的偏 光薄膜製造廢液之處理既不適合且增加成本，而且必須頻 繁地更換樹脂而甚費事。200911691 IX. Description of the Invention [Technical Field] The present invention relates to a method for recovering iodine from a waste liquid for producing a polarizing film from the waste liquid produced by the production of a polarizing film; in particular, after iodine recovery A method for recovering iodine from a waste liquid for producing a polarizing film from which boron can be recovered. [Prior Art] A waste liquid containing iodide ions, boric acid, potassium ions, and water-soluble organic substances is produced in the production process of a polarizing film used in a liquid crystal display or the like. The polarizing film is used to produce a waste liquid, and the specific component contained therein is usually treated as a wastewater discharge standard by agglutination method or a filtration method, and then discharged as industrial wastewater, or concentrated to reduce the volume. After treatment as industrial waste. However, in recent years, the basis of boron and compounds in the wastewater discharge standard tends to be as severe as l〇mg/L, and it has been difficult to reduce the boron concentration in the wastewater below the reference enthalpy by the conventional agglutination method and filtration method. In addition, in terms of industrial waste, it is also expected to reduce emissions in terms of disposal costs and environmental issues. Therefore, a method which has been proposed in the past is to separate the organic component contained in the waste liquid for manufacturing a polarizing film and the inorganic component such as iodine and boron by electrodialysis, thereby facilitating the concentration treatment thereafter, thereby reducing the amount of waste. Processing method (refer to Patent Document 1). Fig. 6 is a schematic view showing a treatment method of a waste liquid for producing a polarizing film described in Patent Document 1. As shown in FIG. 6, in the processing method described in Patent Document 1, the polarizing film production waste liquid 102 stored in the waste liquid-4-200911691 tank 101 is sent to the desalination liquid tank 104 by the pump 103, from The tank is again sent to the electrodialysis unit 105 by the pump 1〇9. At the same time, the pure water stored in the concentrate tank 1 0 6 was sent to the electrodialysis unit 105 using the pump 1 1 ,, and electrodialysis was started. Then, the desalting liquid 107 containing the organic component separated from the electrodialysis apparatus 105 and the concentrated liquid 108 containing the inorganic component are returned to the desalting solution tank 1 and the concentrate tank 〇6, respectively, and then again Send to the electrodialysis unit 1 〇5. Electrodialysis was carried out in a cycled manner by repeating the operation as described above. Further, Patent Document 1 discloses that the concentrated liquid 1 8 is further separated from the boron-containing liquid by ion chromatography or boron selective ion exchange resin treatment, and the like is used as a polarizing film. The solution can be reused. However, the technique described in the patent document 1 is a technique for reducing the amount of waste to reduce the amount of waste, and is a technique for separating the organic component and the inorganic component by making the waste film production waste liquid easy to be concentrated. Therefore, it is described that the separated inorganic component can be separated into an iodine-containing solution and a boron-containing solution by a known method, but the specific steps and conditions are not discussed. Usually, the waste liquid for polarizing film production is mostly composed of various waste liquids with different compositions and concentrations. Since the concentration of each component is not constant, the concentration of iodine and boron used in the step of Yao dyeing and boron crosslinking is adjusted. The difficulty of this, and the viewpoint of maintaining the quality of the finished product of the polarizing film, it is not a practical practice to reuse the waste liquid directly as a polarizing plate. Furthermore, in the case of separating and recovering boron from an aqueous solution containing an inorganic component, usually The use of a boron-selective ion exchange resin has been proposed in the past. A method for regenerating boron-selective ion exchange resins that can recover boron in the form of boric acid from boron adsorption-selective ion exchange resin in the past is proposed (refer to the patent literature). 2 ). Further, the cations in the wastewater are adsorbed and removed by the weakly acidic cation exchange resin, and the anions other than boron in the wastewater are removed by the weakly basic anion exchange resin, and then the strong basic anion exchange resin is adjusted to the OH type. Further, a method of adsorbing and removing boron in waste water by mixing an anion exchange resin with a strong acid cation exchange resin adjusted to a ruthenium type has also been proposed (see Patent Documents 3 and 4). On the other hand, in the past, various methods for recovering iodine from waste liquid have been developed (see, for example, Patent Documents 5 and 6). For example, Patent Document 5 discloses a method of collecting iodine from water containing hydrogen iodide using an ion exchange resin. Further, the inventors of the present invention have found that the waste liquid containing iodine and/or inorganic iodine compound is oxidized or reduced, and the generated free iodine molecule is adsorbed under acidic conditions to a strong alkali adsorbed with iodide ions. In the anion exchange resin, after separating the inorganic salts and organic substances contained in the waste liquid, the iodine molecules adsorbed to the strongly basic anion exchange resin are eluted in the form of a hydrogen iodide solution, thereby recovering iodine from the waste liquid. Methods. [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei 6-63547 (Patent Document 6) JP-A-6-157008 (2009) In the conventional method, it is difficult to reuse the polarized film production waste liquid directly as a polarizing film production solution for reasons such as concentration, quality maintenance, and economy. Therefore, it is preferable to separate and recover the recyclable components such as iodine and boron from the case where the waste liquid is to be reused by the use of the polarizing film. However, in order to separate and recover iodine and boron from the waste liquid for manufacturing a polarizing film, the following problems exist. In other words, as described in Patent Documents 1 and 2, when boron is to be separated and recovered from waste water or the like, a boron selective chelating resin is usually used, and iodine or the like is also adsorbed in the boron selective chelating resin. In addition to the components other than boron, the amount of boron which can be adsorbed is reduced, and if the component which deteriorates the resin such as iodine is contained in the treatment liquid, the life of the resin is shortened, which is a problem. On the other hand, as in the processing methods described in Patent Documents 3 and 4, by removing the components which deteriorate the resin such as organic substances and iodine from the production liquid of the polarizing film in advance, the life of the resin and the boron can be improved. Recycling efficiency, but the number of equipment and steps in this method is the problem. In addition, the processing method described in the patent documents 3 and 4 is a method of performing a large amount of treatment on industrial waste water having a small amount of components to be removed such as boron and iodine, and treating waste liquid of a polarizing film having a high concentration of boron and iodine. It is neither suitable nor costly, and it is very troublesome to replace the resin frequently.
另一方面，於專利文獻5及6中所記載之以往的方法 ，皆須調整pH爲酸性側，以小於3爲佳，故須添加pH -7- 200911691 調整用之酸及用以氧化碘離子之氧化劑。因此，會力口 選擇性螯合樹脂之劣化，且碘吸附費時，無法將廢液 部的碘吸附於樹脂上，於處理後之廢液中殘留 0-1〜〇Jg/L。因此，欲自姚回收後的廢液中再回收硼 困難，是問題所在。 本發明乃鑑於上述問題點而提出者，目的在於提 偏光薄膜製造廢液中容易而有效率地回收碘及硼的自 薄膜製造廢液中回收碘之方法。 (用以解決課題之手段） 本申請案第1發明之自偏光薄膜製造廢液中回收 方法係自含有以全碘量計爲2〜35 g/L的碘、0.2〜8 g/L 及0.6〜11 g/L的鉀之偏光薄膜製造廢液回收碘之方法 特徵在於，包含有下述步驟：將該廢液調整爲pH小 之後，進行電透析，將該廢液中所含有之碘與鉀以碘 之形態分離的步驟；使該電透析後之廢液通過強鹼性 子交換樹脂，使殘留於該廢液中之碘吸附於該強鹼性 子交換樹脂的步驟；及自該碘化鉀及該強鹼性陰離子 樹脂回收碘的步驟。 本申請案第2發明之自製造偏光薄膜之廢液中回 之方法，係自含有以全碘量計爲2〜35g/L的碘、〇.2~ 的硼之製造偏光薄膜之廢液回收碘之方法；其特徵在 包含有下述步驟：將該廢液調整爲pH小於2之後， 廢液中所含有的碘吸附於吸附有碘離子之強鹼性陰離 速硼 中全 碘約 有其 供自 偏光 碘之 的硼 ;其 於7 化鉀 陰離 陰離 交換 收碘 8g/L 於， 使該 子交 -8- 200911691 換樹脂的步驟；使藉由該強鹼性陰離子交換樹脂進行吸附 處理後之廢液，更進一步通過其他強鹼性離子交換樹脂， 使殘留於該廢液中之碘吸附於該其他強鹼性離子交換樹脂 的步驟；及自該強驗性陰離子交換樹脂及該其他強驗性離 子交換樹脂回收碘的步驟。 本申請案第3發明之自製造偏光薄膜之廢液中回收碘 之方法，係自含有以全碘量計爲2〜35g/L的碘、0.2〜8g/L 的硼之製造偏光薄膜之廢液回收碘之方法；其特徵在於， 包含有將該廢液調整爲pH小於7之後，使其通過強鹼性 陰離子交換樹脂使該廢液中之碘吸附於該強鹼性陰離子交 換樹脂的步驟。 於則述本申請案第1 ~ 3發明之确回收方法中，亦可更 進一步包含有下述步驟：將碘分離後之廢液調整成pH爲 7以上後，使其通過硼選擇性螯合樹脂，使該廢液中的硼 吸附於該硼選擇性螯合樹脂的步驟；與自該硼選擇性螯合 樹脂回收硼的步驟。 (發明之效果） 依據本發明’由於係進行用電透析及陰離子交換樹脂 之吸附處理、用吸附有碘離子之強鹼性陰離子交換樹脂和 其他離子交換樹脂之2階段處理、或以強鹼性陰離子交換 樹脂單獨之吸附處理，故可自偏光薄膜製造廢液中容易且 有效率地回收碘。又，由於在碘分離後的廢液中不含碘， 故不會使硼選擇性螯合樹脂劣化，而可容易且有效率地回 -9- 200911691 收硼。 【實施方式】 以下，就本發明之實施形態之自製 中回收碘之方法參照附圖詳細地說明。 第1實施形態之碘回收方法作說明。本 理對象之偏光薄膜製造廢液爲PH3〜10 爲2〜35g/L的碘、0.2〜8g/L的硼及0.6 液’並有亦含有鋅1.5g/L以下及/或以 Total Organic Carbon))換算爲 lg/L 化合物的情況。又，此等偏光薄膜製造 還原電位（Oxidation Reduction Pol 100〜350mv 〇 圖1爲本實施形態之碘回收方法之 中橫坐標爲pH，縱坐標爲非解離硼酸（ 爲表示溶液之pH與硼之存在形態的關 1所示般，於本實施形態之碘回收方法 象之偏光薄膜製造廢液通入電透析裝置 使用之電透析裝置1爲例如’於陽極（ 間交替配置著陽離子交換膜4k與陰離二 此等陽離子交換膜4k與陰離子交換膜‘ (cell)。於對此電透析裝置1之陽極 加直流電流之狀態下’將廢液通入中央 液中的碘離子（I·)及鉀離子（K+)分 造偏光薄膜之廢液 首先，就本發明之 實施形態中作爲處 、含有以全碘量計 〜1 lg/L的鉀之水溶 TOC (全有機碳（ 以下之水溶性有機 廢液之ORP (氧化 ential ))爲例如 示意圖。又，圖2 :h3bo3 )之濃度， 係之曲線圖。如圖 中，首先將處理對 1。本實施形態中 + ) 2與陰極（·）3 ?交換膜4a，藉由 1 a構成複數的單元 2與陰極3之間施 之單元5a中，廢 別會往陽極側及陰 -10- 200911691 極側移動，在中央的單元5a之兩側的單兀5b、5c中生成 碘化鉀（ΚΙ)。然後，自電透析裝置1排出含有ΚΙ約 5 0〜1 5 0g/L的水溶液。 此處，如圖2所示般’於溶液之PH小於7之條件下 ，硼酸之大部分爲未解離而以硼酸分子的狀態存在。因此 ，於本實施形態之碘回收方法中’放入電透析裝置1之廢 液的p Η係設定爲小於7。藉此，可抑制硼酸之解離’故 即使進行電透析，硼酸亦不會移動’而以其原來的狀態排 出，可於廢液中之硼量未改變下使碘量減低至〇.5g/L以下 。另一方面’於廢液之P Η大於7之情況’由於硼酸會解 離致硼酸離子量變多，故於電透析時硼酸離子會混入碘濃 縮液中，致使自電透析裝置1排出之廢液中之硼量降低。 又，於廢液爲酸性之情況，會生成游離碘，使離子交換膜 劣化，導致電透析效率降低。因此，廢液之PH以調整爲 大於3爲佳。藉此，可抑制硕離子之因空氣氧化而導致游 離碘之生成。 然後，使自電透析裝置1排出之廢液通入強鹼性陰離 子交換樹脂6，藉由使碘吸附於此強鹼性陰離子交換樹脂 6，可減低廢液中的碘量至lmg/L以下。此時，廢液若爲 鹼性，硼酸會解離成爲硼酸離子而吸附於強鹼性陰離子交 換樹脂6。因此，於通入至強鹼性陰離子交換樹脂6時之 廢液的pH係與前述同樣地調整爲小於7，於廢液的pH偏 離此範圍之情況，可藉由公知的方法調整。又，廢液的 pH之較佳範圍爲大於3、小於7。 -11 - 200911691 然後，將通過強鹼性陰離子交換樹脂6之廢液，藉由 例如添加氫氧化鈉等公知的方法，將其pH調整爲大於7 後’使其通入到硼選擇性螯合樹脂7。藉此，可回收廢液 中之硼。此時，廢液的p Η若小於7，廢液中之硼酸離子 重會變少，致硼之回收效率降低。因此，通入到硼選擇性 螯合樹脂7之廢液的pH須調整爲大於7。 然後’藉由公知的方法，自電透析裝置1排出之KI 水溶液及自強鹼性陰離子交換樹脂6回收拂，自硼選擇性 螯合樹脂7回收硼。另一方面’對通過硼選擇性螯合樹脂 7之廢液，藉由凝集沉澱法等將Zn等之重金屬除去，並 藉由活性污泥法等將水溶性有機物除去，使此等之含有量 成爲廢水排放基準値以下。然後，調整pH成5.8〜8·6後 再放流。 如上述般’由於本實施形態之碘回收方法中，藉由電 透析及強鹼性陰離子交換樹脂將偏光薄膜製造廢液中之碘 分離’使廢液中之碘減低爲0.01g/L以下之後，藉由硼選 擇性螯合樹脂7將硼分離，並使各步驟中之廢液的pH最 適化’故可自偏光薄膜製造廢液以短時間有效地回收碘及 硼。又’由於本實施形態之碘回收方法中，藉由電透析裝 置1使廢液中之碘量減低爲〇. 5 g/L，故其後使用之強鹸性 離子交換樹脂6之量（塡充量）可較以往者少。再者，於 本實施形態之碘回收方法中，藉由以電透析進行分離或吸 附於樹脂而自廢液中分離碘及硼，故不會混入其他成分而 可容易地再利用。 -12- 200911691 其次，就本發明之第2實施形態之碘回收方法作說曰月 。本實施形態中所處理之偏光薄膜製造廢液爲含有以全II 量計爲2~35g/L的碘、0.2〜8g/L的硼之水溶液，亦有亦含 有0.6~118/[的鉀、1.5§/1^的鋅及/或以丁〇(：(全有機碳） 換算爲1 g/L以下之水溶性有機化合物的情況。又，此偏 光薄膜製造廢液之pH爲例如3〜10，ORP (氧化還原電位 )爲例如100〜350mv。 圖3爲本實施形態之碘回收方法之示意圖。如圖3所 示般，於本實施形態之碘回收方法中，首先將偏光薄膜製 造廢液放入塡充有以碘離子飽和之強鹼性陰離子交換樹脂 12的槽11內’放入偏光薄膜製造廢液，將此等邊以攪拌 機1 5攪拌邊加入硫酸或鹽酸等酸調整PH成爲小於2。接 著，邊繼續攪拌下添加氯氣、次氯酸鈉（NaCIO )或過氧 化氫等之氧化劑，使廢液中之碘離子成爲碘分子（12 )， 再使此12以多碘分子（ΙΓ )之形態吸附於強鹼性陰 離子交換樹脂1 2。然後，將強鹼性陰離子交換樹脂1 2與 廢液分離。 然後，使自強鹼性陰離子交換樹脂1 2分離之廢液通 入未以碘離子飽和之通常的強鹼性離子交換樹脂1 3，使廢 液中所含有之未吸附的12、p Η調整用酸及來自氧化劑的 硫酸離子等陰離子吸附於此強鹼性離子交換樹脂1 3，而使 廢液中之全碘量成爲〇.〇1 g/L以下。 然後，將通過強鹼性離子交換樹脂1 3之廢液，藉由 例如添加氫氧化鈉等之公知的方法，調整其pH成爲大於 -13- 200911691 7之後，使其通過硼選擇性螯合樹脂丨4，將廢液中的硼吸 附。此時’將導入硼選擇性螯合樹脂1 4之廢液的ρ Η設定 爲大於7的理由係與前述第1實施形態者相同。 然後’將吸附於強鹼性陰離子交換樹脂1 2及強鹼性 離子交換樹脂13的碘（h、ΙΓ、ΐ5·)及吸附於硼選擇性 螯合樹脂1 4的硼回收再利用。具體而言，藉由使Na2 S 03 或N aH S 0 3等還原劑的水溶液通過強鹼性陰離子交換樹脂 1 2 ’將吸附於強鹼性陰離子交換樹脂〗2的碘以碘離子之 形態回收。又’藉由使N a Ο Η水溶液通過強鹼性離子交換 樹脂1 3 ’將吸附於強鹼性離子交換樹脂1 3的碘以碘離子 之形態回收。再藉由以Η 2 S Ο 4水溶液通過硼選擇性螯合樹 脂1 4，將吸附於硼選擇性螯合樹脂1 4之硼回收。另一方 面’對通過硼選擇性螯合樹脂1 4之廢液進行凝集沈澱法 及活性污泥法等處理’使Ζη等重金屬類及水溶性有機物 等之値成爲廢水排放基準値以下，再調整ρ Η爲既定範圍 內後，再放流。 如上述般，於本實施形態之碘回收方法中，由於係藉 由以碘離子飽和之強鹼性陰離子交換樹脂1 2將偏光薄膜 製造廢液中之碘離子以多碘分子之形態分離後，再以未以 碘離子飽和之通常的強鹼性離子交換樹脂1 3將廢液中之 未吸附的h分離，故較藉由以碘離子飽和之強鹼性陰離子 交換樹脂I 2只吸附碘離子的情況，可減低使用之離子交 換樹脂的量爲1 / 5〜1/ 3，並同時可提高碘之回收效率。又 ，本實施形態之碘回收方法中，由於係藉由使廢液通過強 -14- 200911691 鹼性陰離子交換樹脂1 2及強鹼性離子交換樹脂1 3，可將 廢液中之碘量減低至〇.〇1 g/L以下之後，藉由硼選擇性螯 合樹脂1 4分離硼，故可於不使硼選擇性螯合樹脂1 4劣化 之下，有效地回收硼。再者，於本實施形態之碘回收方法 中，由於係藉由吸附於樹脂而自廢液中分離碘及硼，故可 於不混入其他成分下容易地再利用回收物。 其次，就本發明之第3實施形態之碘回收方法作說明 。本實施形態中作爲處理對象之偏光薄膜製造廢液，係與 前述第2實施形態同樣地，爲含有含有以全碘量計爲 2〜35g/L的碘、0.2~8g/L的硼之水溶液，並亦有含有 0.6〜llg/L的鉀、鋅1.5g/L以下及/或以TOC換算爲lg/L 以下之水溶性有機化合物的情況。又，此等偏光薄膜製造 廢液之pH爲例如3〜10，ORP (氧化還原電位）爲例如 100〜350mv 〇 圖4爲表示本實施形態之碘回收方法的示意圖。如圖 4所示般，於本實施形態之碘回收方法中，首先，使藉由 公知的方法調整pH爲小於7之偏光薄膜製造廢液通入強 鹼性陰離子交換樹脂2 1，使碘離子吸附於此強鹼性陰離子 交換樹脂21。此時，由於廢液之PH係調整爲小於7，可 抑制廢液中之硼酸的解離，可防止強鹼性陰離子交換樹脂 21通過前後硼量之降低。 然後，對通過強鹼性陰離子交換樹脂2 1之廢液，藉 由例如添加氫氧化鈉等公知的方法將其p Η調整爲大於7 之後’再使其通入硼選擇性螯合樹脂22。藉此，可回收廢 -15- 200911691 液中之硼。此處，須將導入硼選擇性螯合樹脂22中之廢 液的ρ Η調整爲大於7之理由係與前述第1及第2實施形 態相同。 然後，將吸附於強鹼性陰離子交換樹脂2 1之碘、及 吸附於硼選擇性螯合樹脂22之硼分別回收再利用。另一 方面，對通過硼選擇性螯合樹脂22之廢液進行凝集沈澱 法及活性污泥法等處理，使Ζη等重金屬類及水溶性有機 物等之値成爲廢水排放基準値以下，再調整pH爲既定範 圍內後，再放流。 如上述般，本實施形態之碘回收方法中，由於係使偏 光薄膜製造廢液通入強鹼性陰離子交換樹脂2 1，只使其中 所含有碘離子吸附於樹脂，故可於短時間將廢液中之碘分 離。又’本實施形態中’由於係藉由吸附於樹脂而自廢液 中分離碘及硼，故可於回收之碘及硼中不混入其他成分下 容易地再利用。再者，於本實施形態之碘回收方法中，由 於不須以往須使用之pH調整用的酸及氧化劑等化學品類 ，故可省略來自此等化學品類之硫酸離子等之陰離子處理 〇 其次，就本發明之第4實施形態之碘回收方法作說明 。本實施形態之偏光薄膜製造廢液，與前述第2實施形態 同樣地’爲含有以全碘量計爲2〜35g/L的碘、0.2〜8g/L的 硼之水溶液，亦有亦含有0.6〜1 1 g/L的鉀、〗.5g/L的鋅及/ 或以TOC (全有機碳）換算爲1 g/L以下之水溶性有機化 合物的情況。又’此偏光薄膜製造廢液之ρ Η爲例如3〜；i 〇 -16- 200911691 ，ORP (氧化還原電位）爲例如1 〇〇〜350mv。 圖5爲本實施形態之碘回收方法之示意圖。如圖5所 示般，於本實施形態之碘回收方法中’首先’將偏光薄膜 製造廢液3 2放入槽3 1中，邊以攪拌機3 5攪拌下添加硫 酸或鹽酸，調整pH爲小於2。接著繼續進行攪拌，於偏 光薄膜製造廢液3 2中添加既定濃度的次亞氯酸鈉水溶液 。藉此，偏光薄膜製造廢液32中的碘會結晶化而析出， 沈降於槽3 1之底部。然後，用過濾機34將碘結晶33與 上部澄清液分離。然後，以水將碘結晶3 3洗淨，再使其 溶解於亞硫酸鈉等之還原劑水溶液後，以公知的方法精製 而再利用。另一方面，將上部澄清液及碘結晶3 3的洗淨 液通入強鹼性陰離子交換樹脂3 6，讓其吸附殘留的碘，使 廢液（上部澄清液及洗淨液）中之全挑量成爲〇 · 〇 1 g / L以 下。 然後，將通過強鹼性陰離子交換樹脂3 6之廢液（上 部澄清液及洗淨液），以例如添加氫氧化鈉等公知的方法 ’調整其pH爲大於7之後，通入硼選擇性螯合樹脂3 7。 藉此，可回收廢液中的硼。此處，須將導入硼選擇性螯合 樹脂3 7的廢液之p Η調整爲大於7的理由係與前述第1至 第3實施形態相同。 然後，將吸附於強鹼性陰離子交換樹脂3 6之碘、及 吸附於硼選擇性螯合樹脂3 7之硼分別回收再利用。另一 方面’對通過硼選擇性螯合樹脂37之廢液進行凝集沈薇 法及活丨生污泥法等處理’使Ζ η等重金屬類及水溶性有機 -17- 200911691 物等之値成爲廢水排放基準値以下，再調整pH爲既定範 圍內後，再放流。 如上述般，於本發明之碘回收方法中，由於係使偏光 薄膜製造廢液中的碘析出而回收，使其上部澄清液及洗淨 液通過強鹼性陰離子交換樹脂，使殘留於其中的碘吸附於 樹脂，故可大幅減低使用之強鹼性離子交換樹脂的量，並 同時可提高碘之回收效率。又，本實施形態之碘回收方法 中，由於係於廢液中之碘量減低爲0.0 1 g/L之後，再通入 硼選擇性螯合樹脂3 7，故可於不使硼選擇性螯合樹脂3 7 劣化之下，有效地回收硼。 (實施例1 ) 以下’就本發明之效果舉出實施例及比較例具體地作 說明。又’本發明之形態並非限定於此等。首先，就本發 明之實施例作說明。於本實施例中，首先，將全碘量爲 16g/L、硼量爲5.4g/L、鉀量爲4.9g/L之pH爲5.2的偏光 薄膜製造廢液5 L，用電透析裝置（阿斯托姆（股）製， 阿析萊扎S 3型），使用水1 L作爲透析液，於1 0 v定電壓 下進行透析1 .5小時。又，此電透析裝置之膜面積爲 0.05 5m2。陰離子交換膜使用 A-1 92、陽離子交換膜使用 K-501-SB。其結果’電透析後之廢液之碑量爲〇.4g/L，硼 量爲5_2g/L。又’自電透析裝置排出之κι水溶液之碘量 爲 74g/L、棚量爲 〇.7g/L。 然後’將強鹼性陰離子交換樹脂2 0 m 1塡充入塔柱內 -18- 200911691 徑20mm、長300mm之層析管中，以流速〇.15L /分鐘通入 電透析後之廢液。此時，作爲強鹼性陰離子交換樹脂（鍵 結於苯乙嫌-二乙稀基二苯共聚物之四級錢鹽）係使用三 菱化學公司製之岱亞宜翁NSA100。其結果，液體通入於 33分鐘完成’液體通入後之碑離子濃度爲（).〇〗g/L以下。 然後’以〇 _ 1莫耳/L之氫氧化鈉水溶液對通過強鹼性陰離 子交換樹脂後的廢液調整p Η成爲8之後，通入硼選擇性 蜜合樹脂。藉由上述之處理，碘回收率爲99.5%，硼回收 率爲9 9.8 %。 [實施例2] 其次，就本發明之實施例2作說明。於本實施例中， 首先，於燒杯中放入全碘量爲16 8/1^、硼量爲5.48/]^、？1^ 爲5.2之偏光薄膜製造廢液10L後，添加入以碘離子飽和 之強鹼性陰離子交換樹脂2 5 0 m 1。然後，邊以攪拌機攪拌 下添加入硫酸’調整P Η爲2。然後，以4小時的時間添 加入12質量％之次氯酸鈉水溶液3 3 0ml，使碘離子轉變爲 碘分子而吸附於離子交換樹脂。此時，作爲強鹼性陰離子 交換樹脂係使用三菱化學公司製之岱亞宜翁NSA100。其 結果，吸附完成後之廢液的碘量爲0.1 g/L、硼量爲5.4g/L 、碘吸附率爲99.4%。然後’將未以碘離子飽和之強鹼性 陰離子交換樹脂（三菱化學公司製之岱亞宜翁NSA100) 40ml塡充入塔柱內徑20mm、長300mm之層析管中，以 流速0· 1 5L/分鐘通入電透析後之廢液。其結果，液體通入 -19- 200911691 於70分鐘完成，液體通入後之碘離子濃度爲〇.〇lg/L以下 〇 然後，自吸附碘之樹脂出自廢液分離，移入2L燒杯 中，加入35質量％之NaHS03溶液200ml及水1600ml， 攪拌3小時。其結果’攪拌3小時後之溶液中的碘量爲 88g/L、硼量爲0.01g/L以下，脫附率爲99.6°/。。另一方面 ’以0 _ 1莫耳/ L之氫氧化鈉水溶液對通過強驗性陰離子交 換樹脂後的廢液調整p Η成爲8之後，通入硼選擇性螯合 樹脂。藉由上述之處理，碘回收率爲99.9%，硼回收率爲 9 9.8%。 [實施例3] 其次’就本發明之實施例3作說明。首先，將強鹼性 陰離子交換樹脂1L塡充入塔柱內徑50nlm、長7〇0mm之 層析管中’以全碘量爲16g/L、硼量爲5_4g/L、pH爲5.2 之偏光薄膜製造廢液，以流速〇 · 1 5 L /分鐘通入電透析後之 廢液。此時’作爲強鹼性陰離子交換樹脂係使用三菱化學 公司製之（5亞宜翁NSA1 00。其結果，液體開始通入之6〇 分鐘後於塔柱出口採取的液中之碘量爲〇 〇Ig/L以下，硼 量爲5.4g/L。又，液體開始通入之9〇分鐘後於塔柱出口 採取的液中之砩量爲16g/L以下，硼量爲5.4g/L。 然後，以I莫耳/L之NaCl溶液以流速lm"分鐘通入 吸附碘離子之離子交換樹脂後’使碘離子自樹脂脫附。其 結果，自通入液體開始之2 4小時後的碘離子脫附率爲 -20- 200911691 9 4 %。另一方面，以0 1莫耳/L之氫氧化鈉水溶液對以強 鹼性陰離子交換樹脂吸附處理後的廢液調整pH成爲8之 後，通入硼選擇性螯合樹脂。藉由上述之處理，碘回收率 爲9 9.9 %，硼回收率爲9 9.8 %。 (實施例4 ) 其次，就本發明之實施例4作說明。於本實施例中， 首先，於燒杯中放入全碘量爲16g/L、硼量爲5.4g/L、pH 爲5.2之偏光薄膜製造廢液1 0L後，邊以攪拌機攪拌下添 加入硫酸，調整p Η爲2。然後，添加入12質量％之次氯 酸鈉水溶液442ml，使廢液中的碘以碘結晶之形態析出。 然後，使碘結晶沈降，用過濾機將碘結晶與上部澄清液分 離。然後，將分離之碘結晶以2 L之自來水洗淨，並使該 洗淨液與上部澄清液以流速0.1 5L/分鐘通入於內徑2〇mm 、長300mm的層析管中塡充20ml的強鹼性陰離子交換樹 脂（三菱化學公司製之岱亞宜翁NS A 100)者。 此時，上部澄清液之全碘量爲〇.3g/L、硼量爲5.4g/L 、硫酸離子濃度爲7.8g/L、氯離子濃度爲3.0g/L、鈉濃度 爲1.9g/L。又，洗淨液之全碘量爲〇.3g/L、硼量爲 0.09g/L、硫酸離子濃度爲〇_lg/L、氯離子濃度爲〇.〇5g/L 、鈉濃度爲0.04 g/L。此上部澄清液的洗淨液之液體通入 於80分鐘完成，通入液體後之碘離子濃度爲〇.〇1 g/L以下 〇 然後，使分離之碘結晶溶解於3質量％之NaHS〇3溶 -21 - 200911691 液1 6 0 0 m 1中，以公知的方法精製，得到1 5 3 g的碘。又， 自廢液中分離吸附著碘之樹脂，移至200ml的燒杯中，加 入3 5質量％之NaHS03溶液3ml及水40m卜攪拌3小時 。其結果，攪拌3小時後的溶液中之碘量爲90g/L、硼量 爲0.0 1 g/L以下，脫附率爲99.0%。再以0. 1莫耳/L之氫 氧化鈉水溶液對以強鹼性陰離子交換樹脂吸附處理後的廢 液調整pH成爲8之後，使其通入硼選擇性螯合樹脂。藉 由上述之處理，碘回收率爲97.5%，硼回收率爲99.8%。 【圖式簡單說明】 圖1爲本發明之第1實施形態之碘回收方法之示意圖 〇 圖2爲以pH爲橫座標、以未解離硼酸（H3B〇3)的 濃度爲縱座標之溶液之PH與硼之存在形態的關係之曲線 圖。 圖3爲本發明之第2實施形態之碘回收方法之示意圖 〇 圖4爲本發明之第3實施形態之碘回收方法之示意圖 〇 圖5爲本發明之第4實施形態之碘回收方法之示意圖 〇 圖6爲專利文獻〗中所記載之偏光薄膜製造廢液的處 理方法之示意圖。 -22- 200911691 【主要元件符號說明】 1、105 :電透析裝置 2 :陽極 3 :陰極 4k :陽離子交換樹脂 4a :陰離子交換樹脂 5a、5b、5c:單元（cell) 6、 2 1、3 6 :強鹼性陰離子交換樹脂 7、 1 4、22、3 7 :硼選擇性離子交換樹脂 1 1、3 1 :槽 1 2 :強鹼性陰離子交換樹脂 1 3 :離子交換樹脂 1 5、3 5 :攪拌機 32、i 02 :偏光薄膜製造廢液 3 3 :碘結晶 3 4 :過濾機 1 01 :廢液槽 103、 109、 110：泵 104 :脫鹽液槽 1 〇 6 :濃縮液槽 1 〇 7 :脫鹽液 1 〇 8 :濃縮液 -23-On the other hand, in the conventional methods described in Patent Documents 5 and 6, it is necessary to adjust the pH to the acidic side, preferably less than 3, so it is necessary to add pH -7-200911691 to adjust the acid and to oxidize the iodide ion. Oxidizer. Therefore, it is possible to selectively chelate the resin to deteriorate, and iodine adsorption takes a long time to prevent the iodine in the waste liquid portion from being adsorbed on the resin, and 0-1 to 〇 Jg/L remains in the waste liquid after the treatment. Therefore, it is difficult to recover boron from the waste liquid recovered from Yao. The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for recovering iodine from a film production waste liquid in which a ionic liquid and a boron are easily and efficiently recovered in a waste film production waste liquid. (Means for Solving the Problem) The method for recovering the waste liquid for producing a self-polarizing film according to the first aspect of the present invention is to contain iodine, 0.2 to 8 g/L and 0.6 in terms of total iodine amount of 2 to 35 g/L. The method for recovering iodine from the waste liquid of ~11 g/L potassium polarizing film is characterized in that the method comprises the steps of: adjusting the waste liquid to a small pH, performing electrodialysis, and iodine contained in the waste liquid a step of separating potassium in the form of iodine; a step of passing the electrodialyzed waste liquid through a strong basic sub-exchange resin to adsorb iodine remaining in the waste liquid to the strong basic sub-exchange resin; and from the potassium iodide and the The step of recovering iodine from a strongly basic anion resin. The method for recovering the waste liquid from the production of the polarizing film according to the second invention of the present application is a waste liquid recovery from a polarizing film containing iodine or bismuth 2~35 of a total iodine amount of 2 to 35 g/L. The method of iodine; characterized by comprising the following steps: after adjusting the waste liquid to have a pH of less than 2, the iodine contained in the waste liquid is adsorbed to the strong alkaline alkaline irradiance boron adsorbed with iodide ions. Boron which is supplied from polarized iodine; it is exchanged for 8g/L of iodine in an anion exchange with potassium, and the step of replacing the resin with -8-200911691 is carried out by using the strongly basic anion exchange resin. a step of adsorbing the treated waste liquid, further passing another strong basic ion exchange resin to adsorb iodine remaining in the waste liquid to the other strong basic ion exchange resin; and from the strong anion exchange resin and The step of recovering iodine from the other strong ion exchange resins. The method for recovering iodine from the waste liquid for producing a polarizing film according to the third invention of the present application is a waste of a polarizing film produced by containing iodine having a total iodine amount of 2 to 35 g/L and boron of 0.2 to 8 g/L. A method for recovering iodine from a liquid; comprising the step of adjusting the effluent to a pH of less than 7, and passing the strong basic anion exchange resin to adsorb iodine in the waste liquid to the strongly basic anion exchange resin . In the method for recovering the first to third inventions of the present application, the method further comprises the steps of: adjusting the waste liquid after iodine separation to a pH of 7 or more, and selectively etching the boron through the boron. a resin, a step of adsorbing boron in the waste liquid to the boron selective chelating resin; and a step of recovering boron from the boron selective chelating resin. (Effects of the Invention) According to the present invention, 'the treatment by electrodialysis and anion exchange resin, the two-stage treatment with a strong basic anion exchange resin adsorbing iodide ions and other ion exchange resins, or the strong alkalinity The anion exchange resin is separately adsorbed, so that iodine can be easily and efficiently recovered from the waste film production waste liquid. Further, since the effluent in the iodine separation does not contain iodine, the boron selective chelating resin is not deteriorated, and boron can be easily and efficiently recovered. [Embodiment] Hereinafter, a method of recovering iodine in the self-made manner according to the embodiment of the present invention will be described in detail with reference to the drawings. The iodine recovery method of the first embodiment will be described. The polarizing film manufacturing waste liquid of the present invention is iodine having a pH of 3 to 10, a boring of 2 to 35 g/L, a boron of 0.2 to 8 g/L, and a liquid of 0.6%, and also containing less than 1.5 g/L of zinc and/or as Total Organic Carbon. )) The case of conversion to lg/L compound. Further, these polarizing films are used to produce a reduction potential (Oxidation Reduction Pol 100 to 350 mv.) In the iodine recovery method of the present embodiment, the abscissa is pH, and the ordinate is non-dissociated boric acid (indicating that the pH of the solution and the presence of boron are present). As shown in the first aspect of the present invention, the dialysis method of the iodine recovery method of the present embodiment is used to form a waste liquid into the electrodialysis apparatus. The electrodialysis apparatus 1 is, for example, 'at the anode (the cation exchange membrane 4k and the anion are alternately arranged). 2. The cation exchange membrane 4k and the anion exchange membrane '(cell). In the state of applying a direct current to the anode of the electrodialysis device 1, the waste liquid is passed into the iodide ion (I·) and the potassium ion in the central liquid. (K+) Separation of waste liquid of polarizing film First, in the embodiment of the present invention, water-soluble TOC (all organic carbon (hereinafter referred to as water-soluble organic waste liquid) containing potassium in a total iodine amount of ~1 lg/L The ORP (oxidation) is, for example, a schematic diagram. Further, the concentration of the graph of h2bo3) is shown in Fig. 2. In the figure, the pair is treated first. In this embodiment, +) 2 and cathode (·) 3 ? Exchange membrane 4a, by In the unit 5a between the unit 2 and the cathode 3, which constitutes a plurality of elements, the waste moves to the anode side and the cathode-10-200911691 pole side, and is generated in the single sides 5b, 5c on both sides of the central unit 5a. Potassium iodide (ΚΙ). Then, an aqueous solution containing about 50 to 150 g/L is discharged from the electrodialysis apparatus 1. Here, as shown in Fig. 2, the pH of the solution is less than 7, and the boric acid is large. In the iodine recovery method of the present embodiment, the p enthalpy of the waste liquid placed in the electrodialysis apparatus 1 is set to be less than 7. Therefore, the dissociation of boric acid can be suppressed. Therefore, even if electrodialysis is performed, boric acid does not move and is discharged in its original state, so that the amount of boron in the waste liquid is not changed to reduce the amount of iodine to less than g5g/L. When the liquid P Η is greater than 7 'Because boric acid dissociates and the amount of boric acid ions increases, boric acid ions are mixed into the iodine concentrate during electrodialysis, causing the amount of boron in the waste liquid discharged from the electrodialysis device 1 to decrease. In the case where the waste liquid is acidic, free iodine is generated to make the ions The membrane change is deteriorated, resulting in a decrease in the electrodialysis efficiency. Therefore, it is preferable that the pH of the waste liquid is adjusted to be greater than 3. Thereby, generation of free iodine due to air oxidation of the super-organic ions can be suppressed. The discharged waste liquid is passed into the strongly basic anion exchange resin 6, and by adsorbing iodine to the strongly basic anion exchange resin 6, the amount of iodine in the waste liquid can be reduced to less than 1 mg/L. Basically, boric acid is dissociated into boric acid ions and adsorbed to the strongly basic anion exchange resin 6. Therefore, the pH of the waste liquid when it is introduced into the strongly basic anion exchange resin 6 is adjusted to be less than 7, in the same manner as described above. The case where the pH of the waste liquid deviates from this range can be adjusted by a known method. Further, the pH of the waste liquid is preferably in the range of more than 3 and less than 7. -11 - 200911691 Then, the waste liquid of the strongly basic anion exchange resin 6 is adjusted to a value greater than 7 by a known method such as adding sodium hydroxide, and then it is selectively chelated to boron. Resin 7. Thereby, boron in the waste liquid can be recovered. At this time, if the p Η of the waste liquid is less than 7, the amount of boric acid ions in the waste liquid becomes less, and the recovery efficiency of boron is lowered. Therefore, the pH of the waste liquid which is introduced into the boron selective chelating resin 7 must be adjusted to be greater than 7. Then, by means of a known method, KI aqueous solution discharged from the electrodialysis apparatus 1 and ruthenium from the strong basic anion exchange resin 6 are recovered, and boron is recovered from the boron selective chelating resin 7. On the other hand, the heavy metal such as Zn is removed by a coagulation sedimentation method or the like, and the water-soluble organic substance is removed by an activated sludge method or the like to remove the content of the waste liquid. Became the standard for wastewater discharge below 値. Then, the pH was adjusted to 5.8 to 8·6 and then discharged. As described above, in the iodine recovery method of the present embodiment, the iodine in the waste film production waste liquid is separated by electrodialysis and a strong basic anion exchange resin, and the iodine in the waste liquid is reduced to 0.01 g/L or less. By separating the boron by the boron selective chelating resin 7 and optimizing the pH of the waste liquid in each step, it is possible to efficiently recover iodine and boron from the polarizing film manufacturing waste liquid in a short time. Further, in the iodine recovery method of the present embodiment, the amount of iodine in the waste liquid is reduced to 〇5 g/L by the electrodialysis apparatus 1, so that the amount of the strong ion exchange resin 6 used thereafter is Charges can be less than in the past. Further, in the iodine recovery method of the present embodiment, iodine and boron are separated from the waste liquid by separation or adsorption to the resin by electrodialysis, so that it can be easily reused without mixing other components. -12- 200911691 Next, the iodine recovery method according to the second embodiment of the present invention is described as a month. The waste liquid for producing a polarizing film to be treated in the present embodiment is an aqueous solution containing 2 to 35 g/L of iodine and 0.2 to 8 g/L of boron in terms of total II, and also contains 0.6 to 118/[potassium, 1.5 § / 1 ^ zinc and / or butyl hydrazine (: (all organic carbon) conversion of 1 g / L or less of water-soluble organic compounds. Moreover, the pH of the polarizing film manufacturing waste liquid is, for example, 3 to 10 The ORP (redox potential) is, for example, 100 to 350 mv. Fig. 3 is a schematic view showing the iodine recovery method of the present embodiment. As shown in Fig. 3, in the iodine recovery method of the present embodiment, the polarizing film is first used to manufacture a waste liquid. Put into a tank 11 filled with a strong alkaline anion exchange resin 12 saturated with iodide ions to put a polarizing film to produce a waste liquid, and add the acid such as sulfuric acid or hydrochloric acid to the mixture while stirring with the mixer 15 to adjust the pH to be smaller than 2. Next, an oxidizing agent such as chlorine gas, sodium hypochlorite (NaCIO) or hydrogen peroxide is added while stirring, so that the iodide ion in the waste liquid becomes an iodine molecule (12), and the 12 is in the form of a polyiodide molecule (ΙΓ). Adsorption to strongly basic anion exchange resin 1 2. Then, will be strongly alkaline The exchange resin 1 2 is separated from the waste liquid. Then, the waste liquid separated from the strong basic anion exchange resin 12 is passed through a usual strong basic ion exchange resin 13 which is not saturated with iodide ions, so that it is contained in the waste liquid. An anion such as an unadsorbed 12, p Η adjusting acid and a sulfate ion derived from an oxidizing agent is adsorbed to the strongly basic ion exchange resin 13 to make the total iodine amount in the waste liquid 〇.〇1 g/L or less. The waste liquid of the strongly basic ion exchange resin 13 is passed through a boron-selective chelating resin after the pH is adjusted to be greater than -13-200911691 by a known method such as adding sodium hydroxide or the like. 4. The boron in the waste liquid is adsorbed. At this time, the reason why the ρ Η of the waste liquid into which the boron selective chelating resin 14 is introduced is set to be larger than 7 is the same as that of the first embodiment. The iodine (h, ΙΓ, ΐ5·) of the strongly basic anion exchange resin 1 2 and the strongly basic ion exchange resin 13 and the boron adsorbed to the boron selective chelating resin 14 are recovered and reused. Specifically, An aqueous solution of a reducing agent such as Na2 S 03 or N aH S 0 3 is passed through The anion exchange resin 1 2 'the iodine adsorbed on the strongly basic anion exchange resin 〖2 is recovered in the form of iodide ions. Further, by adsorbing the aqueous solution of Na a Ο 通过 through the strong basic ion exchange resin 1 3 ' The iodine of the strongly basic ion exchange resin 13 is recovered in the form of iodide ions, and the boron adsorbed to the boron selective chelating resin 14 is further passed through the boron selective chelating resin 14 by using an aqueous solution of Η 2 S Ο 4 . On the other hand, 'the agglomeration method of the boron-selective chelating resin 14 is subjected to agglomeration precipitation method and activated sludge method, etc.', so that heavy metals such as Ζη and water-soluble organic substances become the wastewater discharge standard ,, After adjusting ρ Η to within the established range, release the flow again. As described above, in the iodine recovery method of the present embodiment, the iodide ions in the waste liquid of the polarizing film production are separated into the form of polyiodide molecules by the strong basic anion exchange resin 1 saturated with iodide ions. Further, the unadsorbed h in the waste liquid is separated by a usual strong basic ion exchange resin 13 which is not saturated with iodide ions, so that only the iodide ion is adsorbed by the strong basic anion exchange resin I 2 saturated with iodide ions. In the case, the amount of the ion exchange resin to be used can be reduced by 1 / 5 to 1 / 3, and at the same time, the recovery efficiency of iodine can be improved. Further, in the iodine recovery method of the present embodiment, the amount of iodine in the waste liquid can be reduced by passing the waste liquid through the strong-14-200911691 basic anion exchange resin 1 2 and the strong basic ion exchange resin 13 After 〇1 g/L or less, boron is separated by the boron selective chelating resin 14, so that boron can be efficiently recovered without deteriorating the boron selective chelating resin 14. Further, in the iodine recovery method of the present embodiment, since iodine and boron are separated from the waste liquid by adsorption to the resin, the recovered product can be easily reused without mixing other components. Next, an iodine recovery method according to a third embodiment of the present invention will be described. In the same manner as in the second embodiment, the waste liquid containing the iodine in an amount of 2 to 35 g/L and the boron in an amount of 0.2 to 8 g/L of the total amount of iodine is used in the same manner as in the second embodiment. Further, there are cases where a water-soluble organic compound containing 0.6 to llg/L of potassium, zinc of 1.5 g/L or less, and/or TOC of lg/L or less is also contained. Further, the pH of the waste liquid for producing a polarizing film is, for example, 3 to 10, and the ORP (oxidation reduction potential) is, for example, 100 to 350 mv. Fig. 4 is a schematic view showing the iodine recovery method of the present embodiment. As shown in Fig. 4, in the iodine recovery method of the present embodiment, first, a waste liquid for producing a polarizing film having a pH of less than 7 by a known method is introduced into the strongly basic anion exchange resin 2 1, and an iodide ion is used. The strongly basic anion exchange resin 21 is adsorbed to this. At this time, since the pH of the waste liquid is adjusted to be less than 7, the dissociation of boric acid in the waste liquid can be suppressed, and the decrease in the amount of boron before and after the passage of the strongly basic anion exchange resin 21 can be prevented. Then, the waste liquid which has passed through the strongly basic anion exchange resin 21 is adjusted to have a p Η of more than 7 by a known method such as addition of sodium hydroxide, and then the boron selective chelating resin 22 is introduced. In this way, boron in the liquid can be recovered from waste -15- 200911691. Here, the reason why the ρ Η of the waste liquid introduced into the boron selective chelating resin 22 is adjusted to be larger than 7 is the same as in the first and second embodiments described above. Then, iodine adsorbed to the strongly basic anion exchange resin 21 and boron adsorbed to the boron selective chelating resin 22 are separately recovered and reused. On the other hand, the waste liquid which has passed through the boron selective chelating resin 22 is subjected to a treatment such as a coagulation sedimentation method or an activated sludge method, and the like, such as heavy metals such as Ζη and water-soluble organic substances, are used as the wastewater discharge standard 値, and then the pH is adjusted. After being within the established range, release it again. As described above, in the iodine recovery method of the present embodiment, since the waste liquid for manufacturing a polarizing film is introduced into the strongly basic anion exchange resin 21, only the iodide ions contained therein are adsorbed to the resin, so that the waste can be scrapped in a short time. The iodine in the liquid is separated. Further, in the present embodiment, since iodine and boron are separated from the waste liquid by adsorption to the resin, it is possible to easily reuse the recovered iodine and boron without mixing other components. Further, in the iodine recovery method of the present embodiment, since an acid such as an acid or an oxidizing agent for pH adjustment which is conventionally used is not required, an anion treatment such as a sulfate ion from such a chemical can be omitted, and The iodine recovery method according to the fourth embodiment of the present invention will be described. In the same manner as in the second embodiment, the waste liquid for producing a polarizing film of the present embodiment is an aqueous solution containing 2 to 35 g/L of iodine and 0.2 to 8 g/L of boron in terms of total iodine, and also contains 0.6. ～1 1 g/L of potassium, 〖.5g/L of zinc and/or a water-soluble organic compound of 1 g/L or less in terms of TOC (all organic carbon). Further, the ρ Η of the waste liquid for producing a polarizing film is, for example, 3 to; i 〇 -16 to 200911691, and the ORP (oxidation reduction potential) is, for example, 1 〇〇 to 350 mv. Fig. 5 is a schematic view showing the iodine recovery method of the embodiment. As shown in Fig. 5, in the iodine recovery method of the present embodiment, the polarizing film production waste liquid 3 2 is first placed in the tank 3 1 , and sulfuric acid or hydrochloric acid is added while stirring with a stirrer 35 to adjust the pH to be smaller than that. 2. Then, stirring was continued, and a predetermined concentration of sodium hypochlorite aqueous solution was added to the polarizing film production waste liquid 3 2 . As a result, iodine in the polarizing film production waste liquid 32 is crystallized and precipitated, and settles at the bottom of the tank 31. Then, the iodine crystal 33 is separated from the upper clear liquid by a filter 34. Then, the iodine crystals 3 3 are washed with water, dissolved in a reducing agent aqueous solution such as sodium sulfite, and then purified by a known method and reused. On the other hand, the supernatant liquid of the upper clarified liquid and the iodine crystal 3 is introduced into the strongly basic anion exchange resin 3, and the residual iodine is adsorbed to make the waste liquid (the upper clarified liquid and the washing liquid) The amount is 〇· 〇 1 g / L or less. Then, the waste liquid (the upper clear liquid and the washing liquid) of the strongly basic anion exchange resin 3 is adjusted to have a pH of more than 7 by a known method such as adding sodium hydroxide, and then boron selective chelation is introduced. Resin 3 7 . Thereby, boron in the waste liquid can be recovered. Here, the reason why the p Η of the waste liquid introduced into the boron selective chelating resin 3 7 is adjusted to be larger than 7 is the same as that of the first to third embodiments. Then, the iodine adsorbed to the strongly basic anion exchange resin 36 and the boron adsorbed to the boron selective chelating resin 37 are separately recovered and reused. On the other hand, 'the agglomeration of the waste liquid by the boron selective chelating resin 37 is agglomerated and the live sludge method, etc.', and the heavy metals such as ηη and the water-soluble organic -17-200911691 are discharged into the wastewater. Below the standard 値, adjust the pH to within the specified range, and then release the flow. As described above, in the iodine recovery method of the present invention, iodine in the waste liquid for manufacturing a polarizing film is precipitated and recovered, and the upper clear liquid and the cleaning liquid are passed through a strong basic anion exchange resin to remain therein. The adsorption of iodine on the resin greatly reduces the amount of strong alkaline ion exchange resin used, and at the same time increases the recovery efficiency of iodine. Further, in the iodine recovery method of the present embodiment, since the amount of iodine in the waste liquid is reduced to 0.01 g/L, and then the boron selective chelating resin 3 is introduced, the boron can be selectively chelated. Under the deterioration of the resin 3 7 , boron is efficiently recovered. (Example 1) Hereinafter, examples and comparative examples will be specifically described on the effects of the present invention. Further, the form of the present invention is not limited thereto. First, an embodiment of the present invention will be described. In the present embodiment, first, a waste liquid of 5 L having a total iodine amount of 16 g/L, a boron amount of 5.4 g/L, a potassium amount of 4.9 g/L and a pH of 5.2 was used, and an electrodialysis apparatus was used. Astor (share) system, Adelaide S 3 type), using 1 L of water as dialysate, and dialysis for 1.5 hours at a constant voltage of 10 v. Further, the membrane area of this electrodialysis apparatus was 0.05 5 m 2 . The anion exchange membrane used A-1 92 and the cation exchange membrane used K-501-SB. As a result, the amount of waste liquid after electrodialysis was 〇.4 g/L, and the amount of boron was 5_2 g/L. Further, the iodine amount of the κι aqueous solution discharged from the electrodialysis apparatus was 74 g/L, and the amount of shed was 〇7 g/L. Then, the strong alkaline anion exchange resin 20 m 1 塡 was charged into the column -18-200911691 20 mm long and 300 mm long, and the waste liquid after electrodialysis was passed at a flow rate of 1515 L / min. In this case, as a strongly basic anion exchange resin (a quaternary salt of a styrene-diethyldiphenyl copolymer), a scorpion NSA 100 manufactured by Mitsubishi Chemical Corporation was used. As a result, the liquid was passed through for 33 minutes to complete the liquid crystal concentration after the liquid introduction was (). 〇 g/L or less. Then, the pulverization of the waste liquid after passing through the strong alkaline anion exchange resin was adjusted to 8 by a NaOH solution of 〇 1 mol/L of sodium hydroxide, and then boron-selective honey-supplement resin was introduced. By the above treatment, the iodine recovery rate was 99.5%, and the boron recovery rate was 99.8%. [Embodiment 2] Next, a second embodiment of the present invention will be described. In the present embodiment, first, the total amount of iodine in the beaker is 16 8/1^, and the amount of boron is 5.48/]^. 1^ After 10 L of a waste liquid was produced as a polarizing film of 5.2, a strong basic anion exchange resin saturated with iodide ions was added to 250 m 1 . Then, the sulfuric acid was added while stirring with a stirrer to adjust P Η to 2. Then, 1300 ml of a 12% by mass aqueous sodium hypochlorite solution was added over 4 hours to convert iodide ions into iodine molecules and adsorbed to the ion exchange resin. In this case, as a strong basic anion exchange resin, Nylon NSA100 manufactured by Mitsubishi Chemical Corporation was used. As a result, the amount of iodine in the waste liquid after the completion of the adsorption was 0.1 g/L, the amount of boron was 5.4 g/L, and the iodine adsorption rate was 99.4%. Then, 40 ml of a strong alkaline anion exchange resin (manufactured by Mitsubishi Chemical Corporation, Namigen NSA100) not saturated with iodide ions was charged into a column with a column inner diameter of 20 mm and a length of 300 mm at a flow rate of 0·1. 5 L/min of waste liquid after electrodialysis. As a result, the liquid was introduced into the -19-200911691 at 70 minutes, and the iodide ion concentration after the liquid was introduced was 〇.〇lg/L or less. Then, the self-adsorbing iodine resin was separated from the waste liquid, transferred to a 2L beaker, and added. A 35 mass% NaHS03 solution (200 ml) and water 1600 ml were stirred for 3 hours. As a result, the amount of iodine in the solution after stirring for 3 hours was 88 g/L, the amount of boron was 0.01 g/L or less, and the desorption ratio was 99.6 °/. . On the other hand, after adjusting the p Η to 8 in the waste liquid after the resin was exchanged with the strong anion with a 0 _ 1 mol/L aqueous sodium hydroxide solution, a boron selective chelating resin was introduced. By the above treatment, the iodine recovery rate was 99.9%, and the boron recovery rate was 9 9.8%. [Embodiment 3] Next, Embodiment 3 of the present invention will be described. First, a strong alkaline anion exchange resin 1L was charged into a chromatographic tube with an inner diameter of 50 nm and a length of 7 mm. The polarized light was a total iodine amount of 16 g/L, a boron amount of 5 _4 g/L, and a pH of 5.2. The film was made into a waste liquid, and the waste liquid after electrodialysis was passed at a flow rate of 〇·15 L /min. At this time, 'as a strong basic anion exchange resin, it was made by Mitsubishi Chemical Co., Ltd. (5 y yung NSA 00. As a result, the amount of iodine in the liquid taken at the outlet of the column after 6 minutes from the start of the liquid is 〇 Below 〇Ig/L, the amount of boron is 5.4 g/L. Further, the amount of ruthenium in the liquid taken at the outlet of the column after 9 minutes of the start of the liquid is 16 g/L or less, and the amount of boron is 5.4 g/L. Then, the ion exchange resin adsorbing iodide ions is introduced into the NaCl solution of I mole/L at a flow rate of lm" minute to desorb the iodide ion from the resin. As a result, the iodine after 24 hours from the start of the liquid introduction The ion desorption rate was -20-200911691 9 4 %. On the other hand, the pH of the waste liquid adsorbed by the strong basic anion exchange resin was adjusted to 8 after using a 0 1 mol/L sodium hydroxide aqueous solution. The boron-selective chelating resin was subjected to the above treatment, and the iodine recovery rate was 99.9 %, and the boron recovery rate was 99.8%. (Example 4) Next, Example 4 of the present invention will be described. In the example, first, a polarizing film having a total iodine amount of 16 g/L, a boron amount of 5.4 g/L, and a pH of 5.2 was placed in a beaker. After 10 L of a waste liquid was added, sulfuric acid was added thereto with stirring with a stirrer to adjust p Η to 2. Then, 442 ml of a 12% by mass aqueous sodium hypochlorite solution was added to precipitate iodine in the waste liquid in the form of iodine crystals. The iodine crystals were sedimented, and the iodine crystals were separated from the upper clear liquid by a filter. Then, the separated iodine crystals were washed with 2 L of tap water, and the washing liquid and the upper clear liquid were passed at a flow rate of 0.1 5 L/min. A chromatographic tube having an inner diameter of 2 mm and a length of 300 mm is filled with 20 ml of a strong alkaline anion exchange resin (manufactured by Mitsubishi Chemical Corporation, NS A 100). At this time, the total iodine amount of the upper clear liquid is 〇3g/L, boron amount is 5.4g/L, sulfate ion concentration is 7.8g/L, chloride ion concentration is 3.0g/L, sodium concentration is 1.9g/L. Moreover, the total iodine amount of the cleaning solution is 〇3g/L, boron content is 0.09g/L, sulfate ion concentration is 〇_lg/L, chloride ion concentration is 〇.〇5g/L, sodium concentration is 0.04 g/L. Washing of the upper clarified liquid The liquid liquid is passed in for 80 minutes, and the iodide ion concentration after the liquid is introduced is 〇.〇1 g/L or less. Then, the separated iodine crystal is dissolved in 3 Amount % of NaHS〇3 dissolved-21 - 200911691 liquid 1 60 0 m 1 was purified by a known method to obtain 153 g of iodine. Further, the resin adsorbed with iodine was separated from the waste liquid and transferred to 200 ml. In a beaker, 3 ml of a 35 mass% NaHS03 solution and 40 m of water were added for 3 hours. As a result, the amount of iodine in the solution after stirring for 3 hours was 90 g/L, and the amount of boron was 0.01 g/L or less. The rate of attachment is 99.0%. Further, the pH of the waste liquid adsorbed by the strongly basic anion exchange resin was adjusted to pH 8 with 0.1 mol/L of the aqueous sodium hydroxide solution, and then the boron selective chelating resin was introduced. By the above treatment, the iodine recovery rate was 97.5%, and the boron recovery rate was 99.8%. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method for recovering iodine according to a first embodiment of the present invention. Fig. 2 is a diagram showing the pH of a solution having a concentration of undissociated boric acid (H3B〇3) as an ordinate with pH as an abscissa. A graph of the relationship with the form of boron. Fig. 3 is a schematic view showing a method for recovering iodine according to a second embodiment of the present invention. Fig. 4 is a view showing a method for recovering iodine according to a third embodiment of the present invention. Fig. 5 is a view showing a method for recovering iodine according to a fourth embodiment of the present invention. Fig. 6 is a schematic view showing a treatment method of a waste liquid for producing a polarizing film described in the patent document. -22- 200911691 [Description of main component symbols] 1. 105: Electrodialysis device 2: Anode 3: Cathode 4k: Cation exchange resin 4a: Anion exchange resin 5a, 5b, 5c: Cell 6, 2 1, 3 6 : strongly basic anion exchange resin 7, 14, 4, 22, 3 7 : boron-selective ion exchange resin 1 1 , 3 1 : tank 1 2 : strongly basic anion exchange resin 1 3 : ion exchange resin 1 5, 3 5 : Blender 32, i 02 : Polarizing film manufacturing waste liquid 3 3 : Iodine crystal 3 4 : Filter 1 01 : Waste liquid tank 103, 109, 110: Pump 104: Desalting liquid tank 1 〇 6 : Concentrated liquid tank 1 〇 7 : Desalting solution 1 〇8 : Concentrate -23-