KR102221524B1 - Treating method and treating device for polarizer manufacturing waste liquid - Google Patents

Treating method and treating device for polarizer manufacturing waste liquid Download PDF

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KR102221524B1
KR102221524B1 KR1020190041668A KR20190041668A KR102221524B1 KR 102221524 B1 KR102221524 B1 KR 102221524B1 KR 1020190041668 A KR1020190041668 A KR 1020190041668A KR 20190041668 A KR20190041668 A KR 20190041668A KR 102221524 B1 KR102221524 B1 KR 102221524B1
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potassium iodide
polarizing plate
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사토루 히라노
요시히로 후지와라
마스오 유아사
히데키 하마무라
나오키 가와카미
요시아키 기타니
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가부시키가이샤 사사꾸라
닛토덴코 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
    • B01D35/02—Filters adapted for location in special places, e.g. pipe-lines, pumps, stop-cocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D36/00—Filter circuits or combinations of filters with other separating devices
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/12—Iodides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32

Abstract

(과제) 본 발명은, 편광판 제조폐액으로부터 고품질의 요오드화칼륨 용액을 효율적으로 회수할 수 있는 편광판 제조폐액의 처리장치를 제공한다.
(해결 수단) 편광판 제조폐액으로부터 요오드화칼륨을 회수하는 편광판 제조폐액의 처리장치(1)로서, 편광판 제조폐액을 농축한 후에 정석을 함으로써 생성된 석출물을 고액분리하여 붕소 및 폴리비닐알코올을 포함하는 불순물이 저감된 요오드화칼륨 용액을 생성하는 제1처리장치(10)와, 얻어진 요오드화칼륨 용액에 잔존하는 폴리비닐알코올을 폴리비닐알코올 흡착체에 흡착시키는 제1불순물 흡착장치(30)와, 제1불순물 흡착장치(30)를 거친 요오드화칼륨 용액에 잔존하는 붕소를 붕소선택 흡착수지에 흡착시키는 제2불순물 흡착장치(40)를 구비한다.(Problem) The present invention provides a polarizing plate manufacturing waste solution capable of efficiently recovering a high-quality potassium iodide solution from the polarizing plate manufacturing waste solution.
(Solving means) As a polarizing plate manufacturing waste liquid treatment apparatus 1 that recovers potassium iodide from the polarizing plate manufacturing waste liquid, the precipitates generated by crystallizing after concentrating the polarizing plate manufacturing waste liquid are solid-liquid separating impurities including boron and polyvinyl alcohol A first treatment device 10 for generating this reduced potassium iodide solution, a first impurity adsorption device 30 for adsorbing polyvinyl alcohol remaining in the obtained potassium iodide solution on the polyvinyl alcohol adsorbent, and a first impurity A second impurity adsorption device 40 for adsorbing boron remaining in the potassium iodide solution passed through the adsorption device 30 to the boron-selective adsorption resin is provided.

Figure R1020190041668
Figure R1020190041668

Description

편광판 제조폐액의 처리방법 및 처리장치{TREATING METHOD AND TREATING DEVICE FOR POLARIZER MANUFACTURING WASTE LIQUID}Polarizing plate manufacturing waste liquid treatment method and treatment device {TREATING METHOD AND TREATING DEVICE FOR POLARIZER MANUFACTURING WASTE LIQUID}

본 발명은, 편광판 제조폐액(偏光板 製造廢液)의 처리방법(處理方法) 및 처리장치(處理裝置)에 관한 것으로서, 더 상세하게는, 편광판의 제조공정(製造工程)에서 발생하는 폐액으로부터 요오드화칼륨(KI)을 회수하는 편광판 제조폐액의 처리방법 및 처리장치에 관한 것이다.The present invention relates to a treatment method and a treatment device for a polarizing plate manufacturing waste liquid, and more particularly, from a waste liquid generated in the manufacturing process of a polarizing plate. The present invention relates to a method and apparatus for treating a polarizing plate manufacturing waste solution for recovering potassium iodide (KI).

액정 디스플레이(液晶 display) 등에 사용되는 편광판의 제조공정에서 발생하는 폐액에는, 요오드나 붕소, 칼륨 등의 무기물성분(無機物成分)이나, 폴리비닐알코올(PVA) 등의 유기물성분(有機物成分)이 포함되어 있고, 이러한 폐액의 처리방법이 종래부터 검토되고 있다.The waste liquid generated in the manufacturing process of polarizing plates used in liquid crystal displays, etc., contains inorganic substances such as iodine, boron, and potassium, and organic substances such as polyvinyl alcohol (PVA). And such waste liquid treatment methods have been studied in the past.

예를 들면 특허문헌1에는, 편광판 제조폐액을 증발농축하여 붕산 및 폴리비닐알코올을 포함하는 석출물(析出物)을 생성하는 농축공정(濃縮工程)과, 증발농축 후의 편광판 제조폐액을 냉각정석하는 냉각정석공정(冷却晶析工程)과, 석출물을 고액분리한 여과액을 회수하는 고액분리공정(固液分離工程)을 구비하는 편광판 제조폐액의 처리방법이 개시되어 있다.For example, in Patent Document 1, a concentration step of evaporating and concentrating the polarizing plate manufacturing waste liquid to generate a precipitate containing boric acid and polyvinyl alcohol, and cooling and crystallization of the polarizing plate manufacturing waste liquid after evaporation and concentration. Disclosed is a method of treating a waste liquid for manufacturing a polarizing plate comprising a crystallization step and a solid-liquid separation step for recovering a filtrate obtained by solid-liquid separation of precipitates.

: 일본국 공개특허 특개2017-209607호 공보: Japanese Unexamined Patent Application Publication No. 2017-209607

상기의 편광판 제조폐액의 처리방법에 의하면, 편광판 제조폐액에 포함되는 붕소나 PVA 등의 불순물의 대부분을 제거할 수 있지만, 회수되는 요오드화칼륨 용액에는 불순물이 약간 잔류하고 있기 때문에, 요오드화칼륨 용액의 품질을 향상시키는 데에 있어서 더 개량의 여지가 있었다.According to the above-described method of treating the polarizing plate manufacturing waste solution, most of the impurities such as boron and PVA contained in the polarizing plate manufacturing waste solution can be removed, but since some impurities remain in the recovered potassium iodide solution, the quality of the potassium iodide solution There was room for further improvement in improving the

그래서 본 발명은, 편광판 제조폐액으로부터 고품질의 요오드화칼륨 용액을 효율적으로 회수할 수 있는 편광판 제조폐액의 처리방법 및 처리장치의 제공을 목적으로 한다.Accordingly, an object of the present invention is to provide a method and apparatus for treating a polarizing plate manufacturing waste solution capable of efficiently recovering a high-quality potassium iodide solution from a polarizing plate manufacturing waste solution.

본 발명의 상기 목적은, 편광판 제조폐액으로부터 요오드화칼륨을 회수하는 편광판 제조폐액의 처리방법으로서, 편광판 제조폐액을 농축한 후에 정석을 함으로써 생성된 석출물을 고액분리하여 붕소 및 폴리비닐알코올을 포함하는 불순물이 저감된 요오드화칼륨 용액을 생성하는 제1처리공정과, 얻어진 요오드화칼륨 용액에 잔존하는 폴리비닐알코올을 폴리비닐알코올 흡착체에 흡착시키는 제1불순물 흡착공정과, 상기 제1불순물 흡착공정을 거친 요오드화칼륨 용액에 잔존하는 붕소를 붕소선택 흡착수지에 흡착시키는 제2불순물 흡착공정을 구비하는 편광판 제조폐액의 처리방법에 의하여 달성된다.The above object of the present invention is a treatment method of a polarizing plate manufacturing waste solution for recovering potassium iodide from a polarizing plate manufacturing waste solution, and impurities including boron and polyvinyl alcohol by solid-liquid separating the precipitate produced by crystallizing after concentrating the polarizing plate manufacturing waste solution. A first treatment step of producing this reduced potassium iodide solution, a first impurity adsorption step of adsorbing polyvinyl alcohol remaining in the obtained potassium iodide solution to a polyvinyl alcohol adsorbent, and iodination through the first impurity adsorption step This is achieved by a method of treating a waste solution for manufacturing a polarizing plate including a second impurity adsorption step in which boron remaining in the potassium solution is adsorbed on a boron-selective adsorption resin.

이 편광판 제조폐액의 처리방법은, 상기 제1처리공정과 상기 제1불순물 흡착공정의 사이에, 상기 제1처리공정에서 얻어진 요오드화칼륨 용액의 상기 불순물을 더 저감하는 제2처리공정을 구비하는 것이 바람직하다.The polarizing plate manufacturing waste treatment method includes a second treatment step for further reducing the impurities in the potassium iodide solution obtained in the first treatment step between the first treatment step and the first impurity adsorption step. desirable.

상기 제2처리공정은, 상기 제1처리공정에서 얻어진 요오드화칼륨 용액을 더 농축하여 요오드화칼륨 결정을 석출시키는 공정과, 석출된 요오드화칼륨 결정을 고액분리하는 공정과, 고액분리된 요오드화칼륨 결정을 세정하여 불순물이 제거된 요오드화칼륨 결정을 회수하는 공정과, 회수한 요오드화칼륨 결정을 용매에 용해시켜서 요오드화칼륨 용액을 생성하는 공정을 구비할 수 있다. 이 경우에, 요오드화칼륨 결정의 용해에 의한 흡열반응에 의하여 용매에 대한 포화용해도가 저하되어 석출되는 불순물을 여과하는 공정을 더 구비하는 것이 바람직하다.The second treatment step includes a step of further concentrating the potassium iodide solution obtained in the first treatment step to precipitate potassium iodide crystals, a step of solid-liquid separation of the precipitated potassium iodide crystal, and a solid-liquid separation of potassium iodide crystals. Thus, a step of recovering the potassium iodide crystal from which impurities have been removed, and a step of dissolving the recovered potassium iodide crystal in a solvent to produce a potassium iodide solution may be provided. In this case, it is preferable to further include a step of filtering impurities precipitated by lowering the saturated solubility in the solvent due to an endothermic reaction by dissolution of the potassium iodide crystal.

혹은 상기 제2처리공정은, 요오드화칼륨 용액에 포함되는 붕소를 칼슘이온과 반응시킴으로써 생성된 붕산칼슘의 침전물을 제거하는 공정을 구비할 수 있다. 이 경우에 상기 제2처리공정은, 요오드화칼륨 용액에 잔류하는 칼슘이온을 탄산이온과 반응시킴으로써 생성된 탄산칼슘의 침전물을 제거하는 공정을 더 구비하는 것이 바람직하다.Alternatively, the second treatment step may include a step of removing a precipitate of calcium borate generated by reacting boron contained in a potassium iodide solution with calcium ions. In this case, the second treatment step preferably further includes a step of removing precipitates of calcium carbonate generated by reacting calcium ions remaining in the potassium iodide solution with carbonate ions.

상기 제1불순물 흡착공정이 이루어지는 요오드화칼륨 용액은, 붕소의 농도가 100∼1000mg/L인 것이 바람직하고, 폴리비닐알코올의 농도가 TOC환산으로 100∼500mg/L인 것이 바람직하다.In the potassium iodide solution in which the first impurity adsorption step is performed, the boron concentration is preferably 100 to 1000 mg/L, and the polyvinyl alcohol concentration is preferably 100 to 500 mg/L in terms of TOC.

또한 본 발명의 상기 목적은, 편광판 제조폐액으로부터 요오드화칼륨을 회수하는 편광판 제조폐액의 처리장치로서, 편광판 제조폐액을 농축한 후에 정석을 함으로써 생성된 석출물을 고액분리하여 붕소 및 폴리비닐알코올을 포함하는 불순물이 저감된 요오드화칼륨 용액을 생성하는 제1처리장치와, 얻어진 요오드화칼륨 용액에 잔존하는 폴리비닐알코올을 폴리비닐알코올 흡착체에 흡착시키는 제1불순물 흡착장치와, 상기 제1불순물 흡착장치를 거친 요오드화칼륨 용액에 잔존하는 붕소를 붕소선택 흡착수지에 흡착시키는 제2불순물 흡착장치를 구비하는 편광판 제조폐액의 처리장치에 의하여 달성된다. 이 편광판 제조폐액의 처리장치는, 상기 제1처리장치에서 얻어진 요오드화칼륨 용액의 상기 불순물을 더 저감하는 제2처리장치를 구비하는 것이 바람직하다.In addition, the above object of the present invention is an apparatus for treating a polarizing plate manufacturing waste solution that recovers potassium iodide from a polarizing plate manufacturing waste solution, which contains boron and polyvinyl alcohol by solid-liquid separating the precipitate produced by crystallizing after concentrating the polarizing plate manufacturing waste solution. A first treatment device for generating a potassium iodide solution with reduced impurities, a first impurity adsorption device for adsorbing the polyvinyl alcohol remaining in the obtained potassium iodide solution on the polyvinyl alcohol adsorbent, and the first impurity adsorption device. This is achieved by a polarizing plate manufacturing waste liquid treatment apparatus having a second impurity adsorption device for adsorbing boron remaining in the potassium iodide solution to the boron-selective adsorption resin. It is preferable that this polarizing plate manufacturing waste treatment apparatus further includes a second treatment apparatus which further reduces the impurities in the potassium iodide solution obtained by the first treatment apparatus.

본 발명에 의하면, 편광판 제조폐액으로부터 고품질의 요오드화칼륨 용액을 효율적으로 회수할 수 있는 편광판 제조폐액의 처리방법 및 처리장치를 제공할 수 있다.Advantageous Effects of Invention According to the present invention, a method and apparatus for treating a polarizing plate manufacturing waste solution capable of efficiently recovering a high-quality potassium iodide solution from a polarizing plate manufacturing waste solution can be provided.

도1은, 본 발명의 1실시형태에 관한 편광판 제조폐액의 처리장치의 블럭도이다.
도2는, 본 발명의 다른 실시형태에 관한 편광판 제조폐액의 처리장치의 블럭도이다.
도3은, 본 발명의 또 다른 실시형태에 관한 편광판 제조폐액의 처리장치의 블럭도이다.1 is a block diagram of an apparatus for treating waste liquid for manufacturing a polarizing plate according to an embodiment of the present invention.
Fig. 2 is a block diagram of an apparatus for treating waste liquid for manufacturing a polarizing plate according to another embodiment of the present invention.
3 is a block diagram of an apparatus for treating waste liquid for manufacturing a polarizing plate according to still another embodiment of the present invention.

이하에서, 본 발명의 1실시형태에 대하여 첨부도면을 참조하여 설명한다. 도1은, 본 발명의 1실시형태에 관한 편광판 제조폐액(偏光板 製造廢液)의 처리장치(處理裝置)의 블럭도이다. 도1에 나타나는 바와 같이 편광판 제조폐액의 처리장치(1)는, 제1처리장치(第1處理裝置)(10), 제1불순물 흡착장치(第1不純物 吸着裝置)(30) 및 제2불순물 흡착장치(第2不純物 吸着裝置)(40)를 구비하고 있고, 또한 제1필터장치(第1filter裝置)(50), 제2필터장치(第2filter裝置)(52) 및 제3필터장치(第3filter裝置)(54)를 구비하고 있다. 이 편광판 제조폐액의 처리장치(1)는, 액정 디스플레이(液晶 display) 등에 사용되는 편광판의 제조공정(製造工程)에서 발생하는 편광판 제조폐액을 처리한다. 편광판의 제조공정에 있어서는 일반적으로, 폴리비닐알코올(PVA)로 이루어지는 필름(film)을 요오드화칼륨(KI) 용액에 침지(沈漬)시킨 후에, 붕산(H3BO3)수용액 중에서 연신(延伸)시켜, 수세(水洗) 및 건조(乾燥)를 거쳐서 편광판이 제조된다. 이 때문에 편광판 제조폐액에는, PVA가 포함되어 있고 또한 KI나 붕산 등이 주로 이온의 상태로 포함되어 있다.Hereinafter, one embodiment of the present invention will be described with reference to the accompanying drawings. 1 is a block diagram of a treatment apparatus for a polarizing plate manufacturing waste liquid according to an embodiment of the present invention. As shown in Fig. 1, the polarizing plate manufacturing waste liquid treatment apparatus 1 includes a first treatment device 10, a first impurity adsorption device 30, and a second impurity. It is provided with an adsorption device 40, and is provided with a first filter device 50, a second filter device 52, and a third filter device. It is equipped with a 3 filter device (54). This polarizing plate manufacturing waste liquid treatment apparatus 1 treats the polarizing plate manufacturing waste liquid generated in the manufacturing process of a polarizing plate used for a liquid crystal display or the like. In the manufacturing process of a polarizing plate, generally, a film made of polyvinyl alcohol (PVA) is immersed in a potassium iodide (KI) solution and then stretched in an aqueous solution of boric acid (H 3 BO 3 ). Then, a polarizing plate is manufactured through washing with water and drying (乾燥). For this reason, PVA is contained in the polarizing plate manufacturing waste liquid, and KI, boric acid, etc. are mainly contained in an ion state.

제1처리장치(10)는, 증발농축장치(蒸發濃縮裝置)(11), 냉각정석장치(冷却晶析裝置)(12) 및 제1고액분리장치(第1固液分離裝置)(13)를 구비하고 있고, 편광판 제조폐액에 포함되는 붕소(硼素)나 PVA 등의 대부분을 제거함으로써 붕소 및 PVA를 포함하는 불순물이 저감된 KI용액(KI溶液)을 생성한다.The first treatment device 10 includes an evaporation and concentration device 11, a cooling and crystallization device 12, and a first solid-liquid separation device (13). A KI solution (KI溶液) in which impurities including boron and PVA are reduced by removing most of boron and PVA contained in the polarizing plate manufacturing waste solution is produced.

증발농축장치(11)는 편광판 제조폐액을 증발농축한다. 이에 따라, 편광판 제조폐액에 포함되어 있던 붕산 및 PVA의 대부분은 과포화 조건(過飽和 條件)으로 됨으로써 슬러지(sludge)가 되고, 이들을 포함하는 석출물(析出物)이 편광판 제조폐액 중에 생성된다. 석출물에는, 붕산 및 PVA 이외의 불순물이 포함되어 있어도 좋다. 증발농축장치(11)의 구성은, 편광판 제조폐액을 농축할 수 있다면 특별하게 한정되지 않지만, 예를 들면 히트펌프형(heat pump型), 이젝터 구동형(ejector 驅動型), 스팀형(steam型), 플래시형(flash型) 등의 공지의 증발농축장치를 들 수 있고, 이들을 1종 또는 2종 이상을 사용하여 구성할 수 있다. 예를 들면 히트펌프형의 농축장치를 전단(前段)에 배치하고, 이 장치에서 생성된 편광판 제조폐액의 농축액을 더 증발농축하는 플래시형의 농축장치를 후단(後段)에 배치하여 증발농축장치(11)를 구성할 수 있다.The evaporation and concentration device 11 evaporates and concentrates the polarizing plate manufacturing waste liquid. Accordingly, most of the boric acid and PVA contained in the polarizing plate manufacturing waste liquid becomes sludge by being subjected to supersaturation conditions, and a precipitate containing them is generated in the polarizing plate manufacturing waste liquid. Impurities other than boric acid and PVA may be contained in the precipitate. The configuration of the evaporation and concentration device 11 is not particularly limited as long as it can concentrate the manufacturing waste liquid of the polarizing plate, but, for example, a heat pump type, an ejector drive type, and a steam type. ), a flash-type, or the like, and one or two or more of them can be used. For example, a heat pump-type concentrator is placed at the front end, and a flash-type concentrator that further evaporates and concentrates the concentrated solution of the polarizing plate manufacturing waste produced by this unit is disposed at the rear end. 11) can be configured.

냉각정석장치(12)는, 편광판 제조폐액에 포함되는 붕산을 정석함으로써 편광판 제조폐액으로부터 석출물을 더 생성한다. 냉각정석장치(12)의 구성은, 예를 들면 재킷식(jacket式)이나 진공식(眞空式) 등 공지의 구성을 들 수 있고, 편광판 제조폐액을, 45도 이하(예를 들면 40∼45℃)까지 냉각하는 것이 바람직하고, 상온(구체적인 예로서는 30℃ 이하)까지 냉각하는 것이 더 바람직하다. 편광판 제조폐액의 정석방법(晶析方法)은, 붕산 등의 불순물의 양호한 저감효과를 얻기 위하여, 본 실시형태와 같이 냉각정석장치(12)에 의한 냉각정석이 바람직하지만, 결정(結晶)을 석출시키는 다른 조작이어도 좋다.The cooling and crystallization apparatus 12 further generates a precipitate from the polarizing plate manufacturing waste liquid by crystallizing boric acid contained in the polarizing plate manufacturing waste liquid. The configuration of the cooling and crystallization device 12 may be a known configuration such as a jacket type or a vacuum type, and the polarizing plate manufacturing waste liquid is adjusted to 45 degrees or less (for example, 40 to 45 degrees). °C), and more preferably cooling to room temperature (30 °C or less as a specific example). In the polarizing plate manufacturing waste liquid crystallization method, in order to obtain a good reduction effect of impurities such as boric acid, cooling crystallization using the cooling crystallization device 12 is preferable as in the present embodiment, but crystals are deposited. Other operations to be made may be used.

제1고액분리장치(13)는, 편광판 제조폐액 중의 석출물을 고액분리한다. 제1고액분리장치(13)의 구성은, 예를 들면 가압여과(加壓濾過)(필터프레스(filter press)), 진공여과(眞空濾過), 원심여과(遠心濾過) 등의 각종 여과장치나, 디캔터형(decanter型)과 같은 원심분리장치 등 공지의 구성을 들 수 있다.The first solid-liquid separation device 13 solid-liquid separates the precipitate in the polarizing plate manufacturing waste liquid. The configuration of the first solid-liquid separation device 13 is, for example, various filtration devices such as pressure filtration (filter press), vacuum filtration, centrifugal filtration, etc. , And a known configuration such as a centrifugal separator such as a decanter type.

제1불순물 흡착장치(30)는, 폴리비닐알코올 흡착체(PVA흡착체)를 구비하고 있고, 제1처리장치(10)로부터 공급된 KI용액을 PVA흡착체로 흐르게 함으로써 KI용액에 약간 잔존하는 PVA를 흡착제거한다. PVA흡착체는, 표면에 PVA를 흡착할 수 있는 고체상(固體狀)이면 특별하게 한정되지 않고, 입상(粒狀)이나 섬유모양 등의 활성탄 필터(活性炭 filter)를 바람직하게 예시할 수 있지만, 산화티타늄(酸化titanium) 등을 사용할 수도 있다.The first impurity adsorption device 30 is provided with a polyvinyl alcohol adsorbent (PVA adsorbent), and the PVA slightly remaining in the KI solution by flowing the KI solution supplied from the first treatment device 10 to the PVA adsorbent. Adsorbed and removed. The PVA adsorbent is not particularly limited as long as it is a solid form capable of adsorbing PVA on the surface, and activated carbon filters such as granular or fibrous form can be preferably illustrated, but oxidation It is also possible to use titanium or the like.

제2불순물 흡착장치(40)는, 붕소선택 흡착수지(硼素選擇 吸着樹脂)가 충전된 흡착탑(吸着塔)을 구비하고 있고, 제1불순물 흡착장치(30)를 통과한 KI용액을 흡착탑으로 흐르게 함으로써 KI용액에 붕산으로서 약간 잔존하는 붕소를 흡착제거한다. 붕소선택 흡착수지는, 붕소를 선택적으로 흡착할 수 있는 것이면 특별하게 한정되지 않고, 공지의 음이온 교환수지(예를 들면 수산화 세륨/에틸렌 비닐알코올 공중합체, 마이크로 포러스형(micro porous型) 스티렌계·메틸 글루카마인 관능기 등)을 사용할 수 있다.The second impurity adsorption device 40 is provided with an adsorption tower filled with a boron-selective adsorption resin, and allows the KI solution that has passed through the first impurity adsorption device 30 to flow into the adsorption tower. By doing so, boron slightly remaining as boric acid in the KI solution is adsorbed and removed. The boron-selective adsorption resin is not particularly limited as long as it can selectively adsorb boron, and known anion exchange resins (e.g., cerium hydroxide/ethylene vinyl alcohol copolymer, micro porous styrene) Methyl glucamine functional group, etc.) can be used.

제1필터장치(50), 제2필터장치(52) 및 제3필터장치(54)는, 모두 세라믹막 필터(ceramic膜 filter)나 카트리지 필터(cartridge filter) 등의 필터를 구비하고 있고, 제1처리장치(10)와 제1불순물 흡착장치(30)의 사이, 제1불순물 흡착장치(30)와 제2불순물 흡착장치(40)의 사이 및 제2불순물 흡착장치(40)의 후단에 각각 배치되어 있다. 제1필터장치(50)는, 제1처리장치(10)로부터 공급되는 KI용액을 여과함으로써 불순물을 제거한다. 제2필터장치(52)는, 제1불순물 흡착장치(30)를 통과한 KI용액을 여과함으로써 KI용액에 혼입할 우려가 있는 SS성분(예를 들면 활성탄의 부스러기 등)을 제거한다. 제3필터장치(54)는, 제2불순물 흡착장치(40)를 통과한 KI용액을 여과함으로써 KI용액에 혼입할 우려가 있는 SS성분(예를 들면 붕소선택 흡착수지의 부스러기 등)을 제거한다.The first filter device 50, the second filter device 52, and the third filter device 54 are all provided with filters such as a ceramic membrane filter or a cartridge filter. Between the first treatment device 10 and the first impurity adsorption device 30, between the first impurity adsorption device 30 and the second impurity adsorption device 40, and at the rear end of the second impurity adsorption device 40, respectively. It is placed. The first filter device 50 removes impurities by filtering the KI solution supplied from the first treatment device 10. The second filter device 52 filters the KI solution that has passed through the first impurity adsorption device 30 to remove SS components (eg, debris of activated carbon, etc.) that may be mixed in the KI solution. The third filter device 54 filters the KI solution that has passed through the second impurity adsorption device 40 to remove SS components (e.g., debris of boron-selective adsorption resin, etc.) that may be mixed in the KI solution. .

다음에, 상기한 편광판 제조폐액의 처리장치(1)를 사용한 편광판 제조폐액의 처리방법을 설명한다.Next, a method of treating the polarizing plate manufacturing waste liquid using the above-described polarizing plate manufacturing waste liquid processing apparatus 1 will be described.

우선, 편광판 제조폐액을 제1처리장치(10)에 공급한다. 편광판 제조폐액의 pH는, 3.5∼8.0의 범위에 있고, 붕산용액을 포함하기 때문에 보통은 산성이지만, 중성 부근의 편광판 제조폐액이어도 좋다. 또는 수산화나트륨이나 수산화칼륨 등의 pH조정제(pH調整劑)를 편광판 제조폐액에 첨가함으로써 편광판 제조폐액의 pH를 알칼리성(예를 들면 8.5∼11이며, 바람직하게는 8.5∼9.5)으로 조정하여도 좋다.First, the polarizing plate manufacturing waste liquid is supplied to the first treatment device 10. The pH of the polarizing plate manufacturing waste solution is in the range of 3.5 to 8.0, and contains a boric acid solution, so it is usually acidic, but may be a polarizing plate manufacturing waste solution in the vicinity of neutrality. Alternatively, the pH of the polarizing plate manufacturing waste solution may be adjusted to alkalinity (e.g. 8.5 to 11, preferably 8.5 to 9.5) by adding a pH adjuster such as sodium hydroxide or potassium hydroxide to the polarizing plate manufacturing waste solution. .

제1처리장치(10)에 있어서는, 증발농축장치(11)에 의하여 편광판 제조폐액이 농축된 후에, 냉각정석장치(12)에 의하여 냉각되어 냉각정석이 이루어진다. 증발농축장치(11)에서 농축되는 편광판 제조폐액의 pH가 알칼리성으로 조정되는 경우, 농축폐액의 pH를 알칼리성으로 유지하여 냉각정석을 하는 것이 바람직하다. 이 후에 제1고액분리장치(13)에 의하여 석출물이 제거된다. 이렇게 해서, 제1처리장치(10)에 의하여 제1처리공정(第1處理工程)이 이루어지고, 붕소 및 PVA를 포함하는 불순물이 저감된 KI용액이 생성된다.In the first treatment device 10, after the polarizing plate manufacturing waste liquid is concentrated by the evaporation and concentration device 11, it is cooled by the cooling and crystallization device 12 to perform cooling and crystallization. When the pH of the polarizing plate manufacturing waste liquid concentrated in the evaporation and concentration device 11 is adjusted to be alkaline, it is preferable to perform cooling and crystallization by maintaining the pH of the concentrated waste liquid as alkaline. After this, the precipitate is removed by the first solid-liquid separation device 13. In this way, the first treatment step (the first treatment process) is performed by the first treatment device 10, and a KI solution in which impurities including boron and PVA are reduced is produced.

제1처리공정에 의하여 분리된 석출물은, 붕산을 주체(主體)로 하는 결정으로서 PVA가 포함되어 있다. 붕산주체 결정은, 예를 들면 증발농축장치(11)에서 생성된 응축수 등을 이용하여 세정하고 회수함으로써, 예를 들면 반도체나 LED 등의 제조공정에 있어서 재이용할 수 있다. 석출물에는, 붕산 및 PVA 이외에 약간의 KI결정도 포함되어 있기 때문에, 세정 후의 세정폐액을, 후술하는 다른 실시형태에 있어서의 증발정석장치(蒸發晶析裝置)(21)(도2를 참조)에 도입하여도 좋다. 제1처리공정에 있어서의 정석은, KI결정이 석출할 때까지 반복하여 실행하여도 좋고, 불순물로 이루어지는 석출물을 고액분리에 의하여 제거할 수 있다.The precipitate separated by the first treatment step contains PVA as a crystal mainly composed of boric acid. The boric acid-based crystal can be reused in, for example, a manufacturing process such as a semiconductor or LED by washing and recovering it using, for example, condensed water generated in the evaporation and concentration device 11. Since the precipitate contains some KI crystals in addition to boric acid and PVA, the washing waste liquid after washing is transferred to an evaporation and crystallization apparatus 21 (refer to Fig. 2) according to another embodiment described later. You may introduce it. The crystallization in the first treatment step may be repeatedly performed until the KI crystal precipitates, and the precipitate composed of impurities can be removed by solid-liquid separation.

제1불순물 흡착장치(30)에 있어서는, 제1처리공정에서 얻어진 KI용액에 약간 잔존하는 PVA가 PVA흡착체에 의하여 흡착제거되는 제1불순물 흡착공정(第1不純物 吸着工程)이 이루어진다. 이 후에 제2불순물 흡착장치(40)에 있어서는, 제1불순물 흡착공정을 거친 KI용액에 약간 잔존하는 붕소가 붕소선택 흡착수지에 의하여 흡착제거되는 제2불순물 흡착공정(第2不純物 吸着工程)이 이루어진다. 이렇게 해서, KI용액에 약간 포함되어 있는 PVA 및 붕소가, 각각 제1불순물 흡착공정 및 제2불순물 흡착공정에 의하여 제거되기 때문에 편광판 제조폐액으로부터 고품질의 요오드화칼륨 용액을 회수할 수 있다.In the first impurity adsorption device 30, a first impurity adsorption process is performed in which PVA slightly remaining in the KI solution obtained in the first treatment process is adsorbed and removed by the PVA adsorbent. Thereafter, in the second impurity adsorption device 40, a second impurity adsorption process in which boron slightly remaining in the KI solution that has undergone the first impurity adsorption process is adsorbed and removed by the boron-selective adsorption resin. Done. In this way, since PVA and boron slightly contained in the KI solution are removed by the first impurity adsorption process and the second impurity adsorption process, respectively, a high-quality potassium iodide solution can be recovered from the polarizing plate manufacturing waste liquid.

본 발명자들에 의한 KI용액의 고농도시험(高濃度試驗)에 의하면, KI용액의 농도가 포화농도 또는 포화농도에 가까운 농도(예를 들면 약 55%)인 경우, KI용액에 포함되는 PVA가 붕소선택 흡착수지에 의한 붕소의 흡착을 저해하기 때문에, 붕소를 충분히 흡착할 수 없다는 것이 밝혀졌다. 그래서 본 실시형태에 있어서는, 제1불순물 흡착공정에 의하여 KI용액 중의 PVA를 제거한 후에, 제2불순물 흡착공정에 의하여 KI용액 중의 붕소를 제거함으로써 상기와 같은 고농도의 KI용액이어도 붕소를 확실하게 제거할 수 있다.According to the high concentration test of the KI solution by the present inventors, when the concentration of the KI solution is a saturated concentration or a concentration close to the saturated concentration (for example, about 55%), the PVA contained in the KI solution is boron. It has been found that boron cannot be sufficiently adsorbed because it inhibits the adsorption of boron by the selective adsorption resin. Therefore, in the present embodiment, after removing PVA in the KI solution by the first impurity adsorption step, boron in the KI solution is removed by the second impurity adsorption step, so that boron can be reliably removed even with the high concentration KI solution. I can.

제1불순물 흡착장치(30) 및 제2불순물 흡착장치(40)를 통과하는 KI용액은, 제1처리장치(10)에 의하여 붕소 및 PVA가 충분히 저감되어 있기 때문에, 붕소선택 흡착수지나 PVA흡착체의 재생부하(再生負荷)를 대폭적으로 저감 하여 고품질의 요오드화칼륨 용액의 회수를 효율적으로 실행할 수 있다.Since the KI solution passing through the first impurity adsorption device 30 and the second impurity adsorption device 40 is sufficiently reduced in boron and PVA by the first treatment device 10, boron-selective adsorption resin or PVA adsorbent It is possible to efficiently recover a high quality potassium iodide solution by significantly reducing the regeneration load of

이상에서, 본 발명의 1실시형태에 대하여 상세하게 설명하였지만, 본래의 편광판 제조폐액에 포함되는 불순물의 양이 많은 등의 이유로, 제1처리장치(10)에 의하여 붕소 및 PVA를 포함하는 불순물을 충분하게 저감할 수 없는 경우에는, 제1처리장치(10)의 후단에 제2처리장치(第1處理裝置)를 설치하고, 제1처리공정과 제1불순물 흡착공정의 사이에, 요오드화칼륨 용액의 불순물을 더 저감하는 제2처리공정(第2處理工程)을 실행하여도 좋다. 제2처리장치의 구성은 특별하게 한정되지 않지만, 도2 및 도3에 나타내는 구성을 바람직하게 예시할 수 있다. 도2 및 도3에 있어서, 도1과 동일한 구성부분에는 동일한 부호를 붙이고 있다.In the above, one embodiment of the present invention has been described in detail, but for reasons such as a large amount of impurities contained in the original polarizing plate manufacturing waste liquid, impurities including boron and PVA are removed by the first treatment device 10. If it cannot be reduced sufficiently, a second treatment device (第1處理裝置) is installed at the rear end of the first treatment device 10, and between the first treatment step and the first impurity adsorption step, a potassium iodide solution A second treatment step (second treatment process) to further reduce the impurities of may be performed. The configuration of the second processing apparatus is not particularly limited, but configurations shown in Figs. 2 and 3 can be preferably illustrated. In Figs. 2 and 3, the same components as in Fig. 1 are denoted by the same reference numerals.

도2는, 본 발명의 다른 실시형태에 관한 편광판 제조폐액의 처리장치의 블럭도이다. 도2에 나타내는 편광판 제조폐액의 처리장치(1')는, 도1에 나타내는 편광판 제조폐액의 처리장치(1)에 있어서 제1처리장치(10)와 제1필터장치(50)의 사이에 제2처리장치(20)를 배치한 것으로서, 제2처리장치(20) 이외의 구성에 대해서는, 도1에 나타내는 편광판 제조폐액의 처리장치(1)와 동일하다.Fig. 2 is a block diagram of an apparatus for treating waste liquid for manufacturing a polarizing plate according to another embodiment of the present invention. The polarizing plate manufacturing waste liquid treatment apparatus 1 ′ shown in FIG. 2 is provided between the first treatment apparatus 10 and the first filter device 50 in the polarizing plate manufacturing waste liquid treatment apparatus 1 shown in FIG. The second processing apparatus 20 is disposed, and the configurations other than the second processing apparatus 20 are the same as those of the polarizing plate manufacturing waste liquid processing apparatus 1 shown in FIG. 1.

제2처리장치(20)는, 증발정석장치(21), 제2고액분리장치(22) 및 용해탱크(溶解tank)(23)를 구비하고 있다. 증발정석장치(21) 및 제2고액분리장치(22)의 구성은 특별하게 한정되지 않지만, 예를 들면 제1처리장치(10)의 증발농축장치(11) 및 제1고액분리장치(13)와 각각 동일한 구성으로 할 수 있다. 본 실시형태에서는, 증발정석장치(21)로서, 플래시형의 증발장치를 사용한다.The second treatment device 20 includes an evaporation and crystallization device 21, a second solid-liquid separation device 22, and a dissolution tank 23. The configurations of the evaporation and crystallization device 21 and the second solid-liquid separation device 22 are not particularly limited, but, for example, the evaporation and concentration device 11 and the first solid-liquid separation device 13 of the first treatment device 10 Each of these can be configured in the same way. In this embodiment, as the evaporation and crystallization apparatus 21, a flash type evaporation apparatus is used.

증발정석장치(21)는, 제1처리장치(10)에 의하여 농축된 KI용액을 증발시켜서 KI를 과포화로 함으로써 KI결정을 포함하는 석출물을 생성한다. 증발정석의 진행에 따라, KI용액에 KOH를 첨가하는 등을 하여 pH조정을 실행하여도 좋다. 제2고액분리장치(22)는, 증발정석장치(21)에서 생성된 석출물을 고액분리하여 회수한다.The evaporation and crystallization device 21 evaporates the KI solution concentrated by the first treatment device 10 to make the KI supersaturated, thereby generating a precipitate containing KI crystals. As the evaporation and crystallization proceeds, pH adjustment may be performed by adding KOH to the KI solution. The second solid-liquid separation device 22 collects the precipitates generated by the evaporation and crystallization device 21 by solid-liquid separation.

제1처리공정에 의하여 KI용액에 포함되는 붕산 및 PVA의 농도는 저감되어 있기 때문에, 증발정석장치(21)에 의하여 생성되는 석출물은, KI를 주체로 하는 결정이다. 다만, KI의 수율을 올리기 위해서 농축배율을 올리면, 회수 시에 문제가 되기 쉬운 PVA의 혼입량도 증가한다. 그래서 KI결정을 제2고액분리장치(22) 내에서 세정함으로써 KI결정에 부착되는 불순물이 제거된다.Since the concentrations of boric acid and PVA contained in the KI solution are reduced by the first treatment step, the precipitate produced by the evaporation and crystallization device 21 is a crystal mainly composed of KI. However, if the concentration ratio is increased to increase the yield of KI, the amount of PVA mixed, which is likely to be a problem during recovery, also increases. Therefore, impurities adhering to the KI crystal are removed by washing the KI crystal in the second solid-liquid separation device 22.

KI결정의 세정에 사용하는 세정액은, 예를 들면 증발농축장치(11)에서 생성된 응축수를 이용할 수도 있지만, KI의 용해도가 높기 때문에, 용해에 의한 감손(減損)이 크게 된다. 따라서 용해에 의한 감손을 저감하는 것을 목적으로, 이미 회수된 KI의 일부를 이용하는 등을 하여 KI의 포화용액을 생성하고, 이 KI포화용액을 사용하여 KI결정을 세정하는 것이 바람직하다. KI포화용액의 농도는, 반드시 포화농도일 필요는 없고, 포화농도에 가까운 고농도이면 좋다. 고농도의 KI용액을 사용한 세정에 의하여 PVA를 효율적으로 제거할 수 있고, PVA의 혼입이 적은 KI결정을, 필터 등에 의하여 고액분리하여 회수할 수 있다. 세정액은, 탱크 등에 저장하여 순환하여 이용할 수 있다.The cleaning liquid used for cleaning KI crystals may be, for example, condensed water generated by the evaporation and condensing device 11, but since the solubility of KI is high, loss due to dissolution increases. Therefore, in order to reduce the loss due to dissolution, it is preferable to use a part of the already recovered KI to generate a saturated solution of KI, and use this saturated solution to wash the KI crystals. The concentration of the saturated KI solution does not necessarily have to be a saturated concentration, but a high concentration close to the saturated concentration may be sufficient. PVA can be efficiently removed by washing with a high-concentration KI solution, and KI crystals with little incorporation of PVA can be recovered by solid-liquid separation using a filter or the like. The cleaning liquid can be stored in a tank or the like and circulated for use.

회수된 KI결정은, 용해탱크(23)에 있어서 물 등의 용매에 용해됨으로써 불순물이 저감된 KI용액이 생성된다. 용매에 물을 사용한 경우에, KI결정의 물에의 용해는 흡열반응으로서, 예를 들면 20℃의 물에 대하여 KI결정을 55%용액이 되도록 용해시키면, KI용액의 온도는 약 -5℃가 된다. 회수된 KI결정에는, 붕소나 PVA 등의 불순물이 포함되어 있기 때문에, KI결정을 고농도로 용해시킨 용매의 온도가 저하됨으로써 불순물(주로 PVA)의 포화용해도(飽和溶解度)가 저하되어 불순물의 일부 또는 대부분이 석출된다. 이 석출물은 제1필터장치(50)에 의하여 여과된다.The recovered KI crystals are dissolved in a solvent such as water in the dissolution tank 23 to produce a KI solution with reduced impurities. When water is used as a solvent, dissolution of KI crystals in water is an endothermic reaction. For example, when KI crystals are dissolved in a 55% solution in water at 20°C, the temperature of the KI solution is about -5°C. do. Since the recovered KI crystal contains impurities such as boron and PVA, the temperature of the solvent in which the KI crystal is dissolved at a high concentration decreases, thereby lowering the saturated solubility of impurities (mainly PVA), and a part of the impurities or Most are precipitated. This precipitate is filtered by the first filter device 50.

이와 같이 회수된 KI결정을 세정함으로써, 주로 KI결정의 표면에 부착되어 있는 불순물을 저감할 수 있음과 아울러, KI결정의 용해에 의한 흡열반응을 이용하여 KI결정에 포함되어 있는 PVA를 석출시켜서 제거할 수 있기 때문에, PVA가 충분히 저감된 KI용액을 생성할 수 있다. 따라서 제1불순물 흡착장치(30)가 구비하는 PVA흡착체의 부하를 저감할 수 있다.By cleaning the recovered KI crystals, impurities mainly adhering to the surface of the KI crystals can be reduced, and PVA contained in the KI crystals is precipitated and removed using an endothermic reaction by dissolution of the KI crystals. Because it can, it is possible to produce a KI solution in which PVA is sufficiently reduced. Therefore, the load of the PVA adsorbent provided in the first impurity adsorption device 30 can be reduced.

도3은, 본 발명의 또 다른 실시형태에 관한 편광판 제조폐액의 처리장치의 블럭도이다. 도3에 나타내는 편광판 제조폐액의 처리장치(1'')는, 도1에 나타내는 편광판 제조폐액의 처리장치(1)에 있어서 제1처리장치(10)와 제1필터장치(50)의 사이에 제2처리장치(120)를 배치한 것으로서, 제2처리장치(120) 이외의 구성에 대해서는, 도1에 나타내는 편광판 제조폐액의 처리장치(1)와 동일하다.3 is a block diagram of an apparatus for treating waste liquid for manufacturing a polarizing plate according to still another embodiment of the present invention. The polarizing plate manufacturing waste liquid treatment device 1'' shown in Fig. 3 is between the first treatment device 10 and the first filter device 50 in the polarizing plate production waste liquid treatment device 1 shown in FIG. The second treatment device 120 is disposed, and the configuration other than the second treatment device 120 is the same as that of the polarizing plate manufacturing waste liquid treatment device 1 shown in FIG. 1.

도3에 나타내는 제2처리장치(120)는, 제1처리장치(10)에서 불순물이 저감된 KI용액에 칼슘이온(calcium ion)을 공급하여 생성된 침전물을 제거하는 제1반응장치(第1反應裝置)(121)와, 제1반응장치(121)를 거친 KI용액에 탄산이온(炭酸ion)을 공급하여 생성된 침전물을 제거하는 제2반응장치(第2反應裝置)(122)를 구비하고 있다.The second treatment device 120 shown in FIG. 3 is a first reaction device (No. 1) for supplying calcium ions to a KI solution having reduced impurities in the first treatment device 10 to remove the generated precipitate. Equipped with a reaction device 121 and a second reaction device 122 to remove precipitates generated by supplying carbonate ions to the KI solution that has passed through the first reaction device 121 Are doing.

제1반응장치(121)는, KI용액에 약간 잔존하는 붕소를 수산화칼슘의 첨가에 의하여 칼슘이온과 반응시켜서 붕산칼슘의 침전물을 생성하고, 이 침전물을 필터 등으로 제거함으로써 KI용액에 포함되는 붕소를 더 저감한다. 제1반응장치(121)에 공급되는 KI용액은, 제1처리공정에 의하여 농축되어 있기 때문에, 수산화칼슘을 공급하기 전에 증류수 등을 첨가함으로써 KI용액의 농도를 적절한 농도(예를 들면 15∼30%)로 희석하여도 좋다.The first reaction device 121 reacts with calcium ions slightly remaining in the KI solution by adding calcium hydroxide to generate a precipitate of calcium borate, and removes the precipitate with a filter to remove boron contained in the KI solution. Further reduce. Since the KI solution supplied to the first reaction device 121 is concentrated by the first treatment step, distilled water or the like is added before supplying calcium hydroxide to adjust the concentration of the KI solution to an appropriate concentration (for example, 15 to 30%). ) May be diluted.

제2반응장치(122)는, 제1반응장치(121)를 거친 KI용액에 탄산이온을 공급한다. 이에 따라, KI용액에 잔류하는 칼슘이온이 탄산이온과 반응하여 탄산칼슘의 침전물이 생성되고, 이 침전물을 필터 등으로 제거함으로써 KI용액으로부터 칼슘이온을 제거할 수 있다. 탄산이온의 공급은, KI용액에 불순물이 증가하는 것을 억제하기 위하여, 탄산칼륨 또는 이산화탄소의 첨가에 의하여 실행하는 것이 바람직하다. 이렇게 해서, 제2처리장치(120)에 의한 제2처리공정을 실행하여, KI용액의 불순물을 더 저감할 수 있다.The second reaction device 122 supplies carbonate ions to the KI solution that has passed through the first reaction device 121. Accordingly, calcium ions remaining in the KI solution react with carbonate ions to form a precipitate of calcium carbonate, and calcium ions can be removed from the KI solution by removing the precipitate with a filter or the like. The supply of carbonate ions is preferably performed by addition of potassium carbonate or carbon dioxide in order to suppress the increase of impurities in the KI solution. In this way, by executing the second treatment step by the second treatment device 120, impurities in the KI solution can be further reduced.

도1부터 도3의 구성에 있어서, 제1불순물 흡착장치(30)에 도입되는 KI용액의 붕소 및 PVA의 농도는, 특별하게 한정되는 것은 아니지만, 지나치게 높으면 붕소선택 흡착수지나 PVA흡착체의 교환 또는 재생의 빈도가 높아져 실용적으로 사용하기 어려워진다. 구체적으로는, 붕소농도가 100∼1000mg/L인 것이 바람직하고, 폴리비닐알코올의 농도가, TOC환산으로 100∼500mg/L인 것이 바람직하다. KI용액의 붕소농도 및 PVA농도는, 그 후의 제1불순물 흡착공정 및 제2불순물 흡착공정에 의하여 최종적으로는 수 mg/L까지 저감할 수 있다.In the configurations of FIGS. 1 to 3, the concentration of boron and PVA in the KI solution introduced into the first impurity adsorption device 30 is not particularly limited, but if it is too high, the boron-selective adsorption resin or the PVA adsorbent may be exchanged or The frequency of regeneration increases, making it difficult to use practically. Specifically, the boron concentration is preferably 100 to 1000 mg/L, and the polyvinyl alcohol concentration is preferably 100 to 500 mg/L in terms of TOC. The boron concentration and PVA concentration of the KI solution can be finally reduced to several mg/L by the subsequent first impurity adsorption process and the second impurity adsorption process.

1 편광판 제조폐액의 처리장치
10 제1처리장치
11 증발농축장치
12 냉각정석장치
13 제1고액분리장치
20 제2처리장치
21 증발정석장치
22 제2고액분리장치
23 용해탱크
30 제1불순물 흡착장치
40 제2불순물 흡착장치
50 제1필터장치
52 제2필터장치
54 제3필터장치
120 제2처리장치
121 제1반응장치
122 제2반응장치1 Polarizing plate manufacturing waste liquid treatment device
10 First treatment device
11 evaporative concentration device
12 Cooling and crystallization device
13 The first solid-liquid separation device
20 Second processing device
21 evaporation and crystallization device
22 Second solid-liquid separation device
23 Melting tank
30 First impurity adsorption device
40 Second impurity adsorption device
50 First filter device
52 Second filter device
54 Third filter device
120 Second processing unit
121 First reaction device
122 Second reaction device

Claims (9)

편광판 제조폐액(偏光板 製造廢液)으로부터 요오드화칼륨(KI)을 회수하는 편광판 제조폐액의 처리방법(處理方法)으로서,
편광판 제조폐액을 농축(濃縮)한 후에 정석(晶析)을 함으로써 생성된 석출물(析出物)을 고액분리(固液分離)하여 붕소(硼素) 및 폴리비닐알코올을 포함하는 불순물이 저감된 요오드화칼륨 용액을 생성하는 제1처리공정(第1處理工程)과,
상기 제1처리공정에서 얻어진 요오드화칼륨 용액에 잔존하는 폴리비닐알코올을 폴리비닐알코올 흡착체에 흡착시키는 제1불순물 흡착공정(第1不純物 吸着裝置)과,
상기 제1불순물 흡착공정에서 폴리비닐알코올이 흡착되어 제거된 요오드화칼륨 용액에 잔존하는 붕소를 붕소선택 흡착수지(硼素選擇 吸着樹脂)에 흡착시키는 제2불순물흡착공정(第2不純物 吸着裝置)을
구비하는 편광판 제조폐액의 처리방법.
As a treatment method of the polarizing plate manufacturing waste solution for recovering potassium iodide (KI) from the polarizing plate manufacturing waste solution,
Potassium iodide in which impurities including boron and polyvinyl alcohol are reduced by solid-liquid separation of precipitates generated by crystallization after concentrating the polarizing plate manufacturing waste solution. A first treatment step (第1處理工程) to generate a solution, and
A first impurity adsorption step of adsorbing polyvinyl alcohol remaining in the potassium iodide solution obtained in the first treatment step to the polyvinyl alcohol adsorbent; and
In the first impurity adsorption process, a second impurity adsorption process in which boron remaining in the potassium iodide solution removed by polyvinyl alcohol adsorption is adsorbed to a boron selective adsorption resin
A method of treating a waste liquid for manufacturing a polarizing plate provided.
 제1항에 있어서,
상기 제1처리공정과 상기 제1불순물 흡착공정의 사이에, 상기 제1처리공정에서 얻어진 요오드화칼륨 용액의 상기 불순물을 더 저감하는 제2처리공정(第2處理工程)을 구비하는 편광판 제조폐액의 처리방법.
The method of claim 1,
Between the first treatment step and the first impurity adsorption step, a polarizing plate manufacturing waste liquid having a second treatment step (second treatment) for further reducing the impurities in the potassium iodide solution obtained in the first treatment step Treatment method.
 제2항에 있어서,
상기 제2처리공정은, 상기 제1처리공정에서 얻어진 요오드화칼륨 용액을 더 농축하여 요오드화칼륨 결정을 석출시키는 공정과,
석출된 요오드화칼륨 결정을 고액분리하는 공정과,
고액분리된 요오드화칼륨 결정을 세정하여 불순물이 제거된 요오드화칼륨 결정을 회수하는 공정과,
회수한 요오드화칼륨 결정을 용매에 용해시켜서 요오드화칼륨 용액을 생성하는 공정을
구비하는 편광판 제조폐액의 처리방법.
The method of claim 2,
The second treatment step includes a step of further concentrating the potassium iodide solution obtained in the first treatment step to precipitate potassium iodide crystals,
A process of solid-liquid separation of the precipitated potassium iodide crystals,
A step of recovering the potassium iodide crystal from which impurities have been removed by washing the solid-liquid separated potassium iodide crystal;
The process of dissolving the recovered potassium iodide crystals in a solvent to produce a potassium iodide solution
A method of treating a waste liquid for manufacturing a polarizing plate provided.
 제3항에 있어서,
요오드화칼륨 결정의 용해에 의한 흡열반응에 의하여 포화용해도(飽和溶解度)가 저하되어 석출되는 불순물을 여과하는 공정을 더 구비하는 편광판 제조폐액의 처리방법.
The method of claim 3,
A method of treating waste liquid for manufacturing a polarizing plate, further comprising a step of filtering impurities precipitated due to a decrease in saturated solubility due to an endothermic reaction by dissolution of potassium iodide crystals.
 제2항에 있어서,
상기 제2처리공정은, 요오드화칼륨 용액에 포함되는 붕소를 칼슘이온(calcium ion)과 반응시킴으로써 생성된 붕산칼슘의 침전물을 제거하는 공정을 구비하는 편광판 제조폐액의 처리방법.
The method of claim 2,
The second treatment step includes a step of removing a precipitate of calcium borate generated by reacting boron contained in a potassium iodide solution with calcium ions.
 제5항에 있어서,
상기 제2처리공정은, 요오드화칼륨 용액에 잔류하는 칼슘이온을 탄산이온(炭酸ion)과 반응시킴으로써 생성된 탄산칼슘의 침전물을 제거하는 공정을 더 구비하는 편광판 제조폐액의 처리방법.
The method of claim 5,
The second treatment step further comprises a step of removing precipitates of calcium carbonate generated by reacting calcium ions remaining in the potassium iodide solution with carbonate ions.
 제1항 내지 제6항 중 어느 하나의 항에 있어서,
상기 제1불순물 흡착공정이 이루어지는 요오드화칼륨 용액은, 붕소의 농도가 100∼1000mg/L이며, 폴리비닐알코올의 농도가 TOC환산으로 100∼500mg/L인 편광판 제조폐액의 처리방법.
The method according to any one of claims 1 to 6,
The potassium iodide solution in which the first impurity adsorption step is performed has a boron concentration of 100 to 1000 mg/L and a polyvinyl alcohol concentration of 100 to 500 mg/L in terms of TOC.
 편광판 제조폐액으로부터 요오드화칼륨을 회수하는 편광판 제조폐액의 처리장치(處理裝置)로서,
편광판 제조폐액을 농축한 후에 정석을 함으로써 생성된 석출물을 고액분리하여 붕소 및 폴리비닐알코올을 포함하는 불순물이 저감된 요오드화칼륨 용액을 생성하는 제1처리장치(第1處理裝置)와,
상기 제1처리장치에서 얻어진 요오드화칼륨 용액에 잔존하는 폴리비닐알코올을 폴리비닐알코올 흡착체에 흡착시키는 제1불순물 흡착장치(第1不純物 吸着裝置)와,
상기 제1불순물 흡착장치에서 폴리비닐알코올이 흡착되어 제거된 요오드화칼륨 용액에 잔존하는 붕소를 붕소선택 흡착수지에 흡착시키는 제2불순물 흡착장치(第2不純物 吸着裝置)를
구비하는 편광판 제조폐액의 처리장치.

As a polarizing plate manufacturing waste liquid treatment device that recovers potassium iodide from the polarizing plate manufacturing waste liquid,
A first treatment device (第1處理裝置) for producing a potassium iodide solution with reduced impurities including boron and polyvinyl alcohol by solid-liquid separating the precipitate produced by performing crystallization after concentrating the polarizing plate manufacturing waste liquid;
A first impurity adsorption device for adsorbing the polyvinyl alcohol remaining in the potassium iodide solution obtained in the first treatment device to the polyvinyl alcohol adsorbent;
A second impurity adsorption device for adsorbing boron remaining in the potassium iodide solution removed by adsorbing polyvinyl alcohol in the first impurity adsorption device to the boron-selective adsorption resin.
A polarizing plate manufacturing waste liquid treatment device provided.

 제8항에 있어서,
상기 제1처리장치에서 얻어진 요오드화칼륨 용액의 상기 불순물을 더 저감하는 제2처리장치(第2處理裝置)를 구비하는 편광판 제조폐액의 처리장치.The method of claim 8,
A polarizing plate manufacturing waste liquid treatment apparatus comprising a second treatment device (second treatment device) for further reducing the impurities in the potassium iodide solution obtained by the first treatment device.
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