JPS6022934A - Regeneration of resin for selective adsorption of boron - Google Patents

Abstract

PURPOSE:To enable stable adsorption treatment of boron by allowing resin for selective adsorption of boron which has been converted to free amine form by the regeneration with alkali soln. to contact with soln. of neutral salt, and converting the free amine part of the resin having function for decomposing neutral salt to a salt loaded form. CONSTITUTION:Mother body of resin obtd. by haloalkylating styrenic copolymer is aminated with an amine expressed by the formula {wherein (n) is an integer 1-6; R is -CH2-[CH(OH)]m-CH2OH or alkyl group; (m) is zero or an integer <=6} to obtain resin for selective adsorption for boron; boron in the soln. is adsorbed with the abovedescribed resin. In this process, the resin is regenerated to the free amine form using alkali soln. and the free amine from resin is allowed to contact with soln. of neutral salt to convert the free amine form part of the resin to the form loaded with the neutral salt, which is used for the adsorption treatment. As the result, blocking of hardness component or heavy metal component contained in the soln. due to formation of hydroxides, or elevation of pH of the treated liquid is prevented enabling stable operation of adsorption.

Description

【発明の詳細な説明】 本発明はスチレン系共重合体を樹脂母体とするホウ素選
択吸着樹脂を用いて、硬度成分および／又は重金属成分
全含有する溶液中のホウ素の吸着処理或は高温溶液中の
ホウ素の吸着処理などにおいて、安定した処理操作ケ行
うための該樹脂の再生方法に関するものである。Detailed Description of the Invention The present invention uses a boron selective adsorption resin having a styrene copolymer as a resin matrix to adsorb boron in a solution containing all hardness components and/or heavy metal components or in a high temperature solution. The present invention relates to a method for regenerating the resin for stable processing operations such as boron adsorption treatment.

ホウ素は天然に広く分布し、植物の成育にとって必須の
元素であるが、これが過剰に存在すると徊、物の成長に
悪影曽を及ぼずことが知られてｂる。従ってホウ素を含
有する地下水や地熱水、石炭火力発電所からの廃水等を
かんがい用水として利用する場合には極力ホウ素濃度を
低く抑える必要がある。また海水中に溶存するマグネシ
ウムを原料とするマグネシウム製錬分野においてもそこ
に存在するホウ素は製品に対し種々の悪影Ｉ＃を及埋ず
ためマグネシウム溶液中のホウ素除去も必要である。Boron is widely distributed in nature and is an essential element for the growth of plants, but it is known that if it exists in excess, it will wander and have a negative impact on the growth of plants. Therefore, when using boron-containing groundwater, geothermal water, wastewater from coal-fired power plants, etc. as irrigation water, it is necessary to keep the boron concentration as low as possible. In addition, in the field of magnesium smelting using magnesium dissolved in seawater as a raw material, it is necessary to remove boron from the magnesium solution because the boron present there does not have various negative effects on the product.

こり、らの塩類が共存する溶液とかアルカリ性溶液から
のホウ素の吸着処理においては、一般に用すられてｂる
強塩基性および弱増基性のアニオン交換樹脂ではホウ素
に対する選択吸着能が乏しく実用に耐え得ない。In the adsorption treatment of boron from solutions in which salts such as salts coexist or alkaline solutions, the generally used strongly basic and weakly base-enhancing anion exchange resins have poor selective adsorption ability for boron, making them impractical. I can't stand it.

近年、これらの溶液からホウ素を選択的に吸着処理する
目的で、スチレン系共重合体の樹脂母体に下記一般式（
１）で表わされるアミンにより官能基を導入したホウ素
選択吸着樹脂が式中、ｎ＝／〜６（！Ｉ数）。In recent years, in order to selectively adsorb boron from these solutions, the following general formula (
A boron selective adsorption resin into which a functional group is introduced with an amine represented by the formula 1) has n=/~6 (!I number).

ＲＦｉ−（Ｊ２ｆＯＨ（ＯＨ）ｉｏ馬０１１又はアルキ
ル基を表わす。但し、ｍ＝０〜ｇ （整数）である。RFi-(J2fOH(OH)io represents an alkyl group. However, m=0 to g (integer).

開発され、これまでにとの種のものとしてダイヤイオン
０ＲＢ−０２（三菱化成工業作製、商品名）、アンバー
ライトエＲＡ−７４ｔ３（ロームアンドハース社製、商
品名）等が市販されている、これらは何れもホウ素に対
し、極めて秀れた逸択吸着能を示す樹脂であるが１石炭
火力発電所の廃水や海水から採取した塩化マグネシウム
溶液中に含まれるホウ素除去のように、溶液中に共存壌
メして力にシウムやマグネシウム等の硬度成分および／
又は鉄、ニッケル等の庫金槁成分が存在する場合に、こ
れらの樹脂を・アルカリ溶液で再生して遊離アミン形と
して用いると。It has been developed, and so far, Diaion 0RB-02 (manufactured by Mitsubishi Chemical Industries, trade name), Amberlite RA-74t3 (manufactured by Rohm and Haas, trade name), etc. are commercially available. All of these resins exhibit extremely excellent selective adsorption ability for boron. Hardness components such as sium and magnesium and/or
Or, if metal components such as iron and nickel are present, these resins can be regenerated with an alkaline solution and used in the free amine form.

硬度成分等の水酸化物の沈澱ケ生じ、樹脂性能を低下さ
せた）、樹脂層がブロッキングして固まるという問題が
ある。更にこれらの樹脂を用いて、地熱発電所排水の如
き、高温のホウ素含有液を処理すると官能遅・の熱劣化
が起シ、吸豹性能が経時的に低下するという問題もある
、本発明者＠−は、このようなスチレン系共重合体の樹
脂母体に上記の一般式（１）で表わさｉするアミンによ
り官能基アミンを導入して得られるべく鋭意検討した結
果、上記ホウ素選択吸着樹脂の官能基アミンの中に５樹
脂量体にアミンを反応させる過程で生ずるゆ茅度の高い
、中性塩分解能を示す部分が存在し、これが硬度成分お
よび／又は重金属成分を含む溶液中のホウ素吸着処理の
際にこれらの水酸化物沈澱生成に関与していることを見
い出し走。すなわち該樹脂を用いて溶液中のホウ素吸着
処理を行うに除し、アルカリ溶液で再生して樹脂の官能
み−アミン全遊離形とし、次いで塩化ナトリウム等の中
性塩溶液を該樹脂と接触させて、該樹脂の官能基アミン
中の塩基度の高い中性塩分解能を示す部分を墳負荷形と
してから、硬度成分および／又は重金属成分を含有する
溶液中のホウ素吸着処理に供するならば、硬度成分等の
水酸化物の生成がなく安定したホウ素吸着処理が行なえ
ることが判明した。更に該樹脂中の官能基アミン中の塩
基度の高い中性地分麟能を示す部分と塩基度の低い酸吸
着能しか示さない部分は、遊離アミン形に於て熱安定性
に差があり、地表゛度の高い部分はり０℃以上で実質的
に熱分Ｍが起こる一方、塩基度の低す部分は／θθ℃ｖ
上でも安定である。ところが熔基度の高い１部分子廓化
ナトビ リウム等の中性塩溶液ｆ接触させて堵負荷形とすると熱
安定性が向上し、７００℃以上でも実質的に使用に耐、
えることも判明した、本発明は、か＼る新規な知ｙ、に
み・ついて珈ｈＷ。There are problems such as precipitation of hydroxides such as hardness components, which deteriorates resin performance), and blocking and hardening of the resin layer. Furthermore, when these resins are used to treat high-temperature boron-containing liquids such as wastewater from geothermal power plants, there is a problem that thermal deterioration of the organoleptic slowness occurs, and the leopard absorption performance deteriorates over time. As a result of intensive study to introduce a functional amine into the resin matrix of such a styrene-based copolymer using the amine represented by the general formula (1), we found that Among the functional amines, there is a part that exhibits a high degree of permeability and neutral salt decomposition ability, which is generated in the process of reacting the amine with the pentamer, and this part is used for boron adsorption in solutions containing hardness components and/or heavy metal components. It was discovered that these hydroxides are involved in the formation of precipitates during processing. That is, the resin is used to adsorb boron in a solution, regenerated with an alkaline solution to make the resin into a completely free form of functional amines, and then brought into contact with the resin with a neutral salt solution such as sodium chloride. If the part of the resin that exhibits the ability to decompose neutral salts with high basicity in the amine functional group is made into a mound-loaded form and then subjected to boron adsorption treatment in a solution containing hardness components and/or heavy metal components, the hardness It has been found that stable boron adsorption treatment can be performed without the formation of hydroxides such as components. Furthermore, there is a difference in thermal stability between the free amine form of the functional amine in the resin, the part that has a high basicity and shows neutral ionizing ability, and the part that has a low basicity and only shows an acid adsorption ability. , heat content M occurs substantially above 0℃ in areas with high surface basicity, while /θθ℃v in areas with low basicity.
It is stable even at the top. However, when it is brought into contact with a neutral salt solution such as one-part molecularly decomposed natobilium having a high degree of melting, the thermal stability improves, and it can withstand use even at temperatures above 700°C.
It has also been found that the present invention provides new knowledge and knowledge.

さり、たものであシ、スチレン系共重合体を樹脂ＩＵ：
体とするホウ素選択吸洛朔刀斤による溶液中のホウ素の
吸着処理の安定（また処ｊ７Ｎ操作倉行う方法を提供す
るものである。Resin IU using styrenic copolymer:
The present invention provides a method for stabilizing the adsorption treatment of boron in a solution using a selective boron adsorption method (and a method for performing the treatment using a selective boron adsorption method).

本発明について詳細に説明する。The present invention will be explained in detail.

本発明で用いられるホウ素選択吸着樹脂とは、スチレン
をジビニルベンゼン等の架橋剤で共地合させたものをク
ロロメチルメチルエーテル等でハロメチル化した樹脂母
体？、下記一般式（１）で示される二級アミンで７ミノ
化して得らｉ−Ｌるものである。か＼る二級アミンとし
ては、Ｎ−メチル−Ｄ−グルカミン、Ｎ−予チルーＤ−
グルカミン、Ｎ−メチル−Ｄ−ガラクタミン、Ｎ−メチ
ル−Ｄ−マンノサミン、ジー１−アラピチルアミン等が
挙げられる。The boron selective adsorption resin used in the present invention is a resin matrix obtained by co-forming styrene with a crosslinking agent such as divinylbenzene and halomethylating it with chloromethyl methyl ether. , which is obtained by 7-mination with a secondary amine represented by the following general formula (1). Such secondary amines include N-methyl-D-glucamine, N-premethyl-D-
Examples include glucamine, N-methyl-D-galactamine, N-methyl-D-mannosamine, di-1-arapitylamine, and the like.

ｎ＝／〜６（整数）、 Ｒは一〇Ｈ，Ｉ（−Ｃ町ＯＨ）洩ＯＨ，ＯＨ又はアルキ
ル基を表わす。但し、ｍ＝θ〜６（整釦） アミン反応は１通常実施されている方法によシ行われる
。例えば、ハ日メデル化した樹脂母体をジオキサン、ア
セトン、メチルエチルケトン、クロロホルム、ジクロル
エタン等の７４　当な溶媒の存在下−０〜１００℃の温
度で２〜２０時間アミンと反応させれば良い。又スチレ
ン系共重合体から成る樹脂母体はｂわゆるゲル型でもハ
イポーラス型でも良い。n=/~6 (integer), R represents 10H, I (-C OH) OH, OH or an alkyl group. However, m=θ~6 (setting button) The amine reaction is carried out by a commonly used method. For example, it is sufficient to react a resin matrix which has been converted into a resin with an amine at a temperature of -0 to 100°C for 2 to 20 hours in the presence of a suitable solvent such as dioxane, acetone, methyl ethyl ketone, chloroform, dichloroethane, etc. Further, the resin matrix made of a styrene copolymer may be of a so-called gel type or a highly porous type.

これらのホウ素選択吸着樹脂の塩基度の高いアミン部分
を部分的に塩負荷形にすることが必要であるが１部分的
塩負荷方法としては、ホウ素吸着処理を終了した樹脂に
塩酸、硫酸等の酸溶液を接触させて、樹脂に吸添してい
るホウ素を溶離した後、苛性ソーダ、アンモニア智のア
ルカリ性溶液で再生し７て樹脂の官能基アミンを遊離形
とし５次いでｎｔ化ナナトリウム増化カリ、硫酸ナトリ
ウム、硫酸アンモニウム等の中性塩溶液を樹脂と接触さ
せて、樹脂の′自能都アミン中の堵基度の高い中性地分
解能葡有するｉ’Ａｓ分に丸＋ｊ　Ｊ３荷を行なう。塩
負荷を行なう際に用いられる中性塩溶液の温度は、／〜
１０Ｍ＊５６の範囲で選定されれば良く、号た使用する
量は樹脂官能基アミンの中性塩分解容量を予め測定し、
その側：の７〜７０倍量の範囲で、ホウ素含有溶液中に
共存する他の硬度成分等の濃度、処理流速、処理温度等
全考慮して適宜選定される。このようにして部分塩負荷
を施した樹脂は１次いで原液中のホウ素の吸着処理に用
いらｈる。It is necessary to partially salt-load the highly basic amine part of these boron selective adsorption resins. One partial salt-loading method is to apply hydrochloric acid, sulfuric acid, etc. to the resin that has undergone boron adsorption treatment. After contacting with an acid solution to elute the boron adsorbed to the resin, it is regenerated with an alkaline solution of caustic soda and ammonia, and the functional amine of the resin is converted into a free form. A neutral salt solution such as sodium sulfate or ammonium sulfate is brought into contact with the resin to carry out round +j J3 loading on the i'As portion of the resin which has a high degree of neutral base decomposition in the amine. The temperature of the neutral salt solution used during salt loading is /~
The amount should be selected within the range of 10M*56, and the amount to be used should be determined by measuring the neutral salt decomposition capacity of the resin functional amine in advance.
The amount on that side is appropriately selected in the range of 7 to 70 times the amount on that side, taking into account the concentration of other hardness components coexisting in the boron-containing solution, processing flow rate, processing temperature, etc. The resin partially salt-loaded in this way is then used for adsorption treatment of boron in the stock solution.

本発明方法により部分的に塩魚荷処理’を飾した樹脂に
よりホウ素含有溶液を処理すれば、溶液中に共存する硬
度成分や重金属成分の水酸化物生成によるブロッキング
と力）、処理液のｐＨ上昇などを生ずることなく安定し
た操作を行うことが出来、しかも比較的高し温度の溶液
も処理出来るのである。更に又１本発明方法で処理すれ
は、吸着したホウ素の溶離に使用する酸の量全低減する
ことが出来、また、再生速度も早められるので、ｍ脂を
繰返し使用することを考慮すｈば本発明方法は工業的に
極めて有用な方法である。If a boron-containing solution is treated with a resin partially decorated with salt fish treatment according to the method of the present invention, the blocking effect due to the formation of hydroxides of hardness components and heavy metal components coexisting in the solution, and the pH of the treatment solution. It is possible to perform stable operations without causing temperature rise, and it is also possible to process solutions at relatively high temperatures. Furthermore, when the method of the present invention is used, the amount of acid used to elute the adsorbed boron can be completely reduced, and the regeneration rate can be accelerated, so it is possible to reduce the amount of acid used to elute the adsorbed boron. The method of the present invention is industrially extremely useful.

次に、本発明方法？実施例によシ更に詳細にｎＲ明する
が１本発明はその要旨を超えない飼り、以下の実施例に
画定されるものではない。Next, the method of the present invention? The present invention will be explained in more detail with reference to Examples, but the present invention does not go beyond the gist thereof and is not limited to the following Examples.

実ガロ例／ ホウ素選択吸着樹脂ダイヤイオン（ＪＲＢＯコ（三菱化
成工業■製、商品名）を遊離形で／！θ−採シ、これを
内径２０　ＩＩＩ　４２１長さ！ＯＯ關ｌのジャケット
付ガラス製カラムに充填し、これに！％塩酸／！θＮｆ
ｆＢＶ２で流し１次いで脱廖水で押出水浄後、！九奇性
ソーダ／　！　ＯｍｅをＥＩＶｊで流して再生する。次
いで、説地水で押出水洗を行なった後、　ｊ　ｗｔ、％
　ｆ％：化ナトリウム水溶液２００ｄｆＢＶ２で流し勝
増水で水洗し。Actual example: Boron selective adsorption resin Diamond Ion (JRBO Co., Ltd. (Mitsubishi Chemical Industries, Ltd., product name) is used in free form/!θ-sampling, and this is used as a jacketed glass with an inner diameter of 20 III and a length of 421 and 421 mm. !% hydrochloric acid/!θNf
After purifying the extruded water in the sink with fBV2 and then with de-liquid water,! Kyushu Soda/! Play Ome on EIVj. Next, after extrusion washing with local water, j wt,%
f%: Nagashi with aqueous sodium chloride solution 200dfBV2 and washed with water.

次いでカラムジャケットに６θ℃の温水を循環してカラ
ム内温度を６０℃に保、Ｓ）た。これにホウ酸へコタｙ
７ｔ　（コ２！酵：ｂ換鎧、）堵化ナトリ　ラム　／、
３１／ｌ、硫酸す　ト　リ　ウ　ムθ、タ　２／ｌ。Next, hot water at 6θ°C was circulated through the column jacket to maintain the column internal temperature at 60°C. Add boric acid to this
7t (Ko2! Fermentation: b replacement armor,) Toka Natori Ram /,
31/l, sodium sulfate θ, ta 2/l.

フッ化ナトリウムθ、θ５ｙ７ｔ、硫酸マグネシウム０
．１ｆ／ｌ、環化カルシウム３．３ｆ　／　ｔを含むｐ
Ｈ４，θの溶液′ｌｒｋ速ＥＶ／ｊで通液してホウ素の
吸着処理を行なった。この時カラムから流出する処理液
中のホウ素嬢度全カーミン＾ν比色法で測定した所、処
理液量／　７　Ｂｅｄ　Ｖｏｌｕｎ＋８（以下ＢＶと略
す）までは処理液中のホウ素濃度はθ、／ｐＰＩ（Ｂ換
算）以下でその後徐々にホウ素の漏出が起こシ、処理液
中のホウ素濃度が／解（Ｂ換算）までの処理液量は／ｒ
ＢＶであった。この時の処理液のｐＨとホウ素の（Ｊ８
！過曲線を図１に示す。処理液のｐＨけり前後に保た）
１゜硬度成分の水酸化物による沈澱はみられなかった。Sodium fluoride θ, θ5y7t, magnesium sulfate 0
．． 1f/l, p containing 3.3f/t of calcium cyclide
Boron adsorption treatment was carried out by passing a solution of H4, θ at a speed of 'lrk EV/j. At this time, the boron concentration in the treatment liquid flowing out from the column was measured by the total carmine ^ν colorimetric method, and the boron concentration in the treatment liquid was θ, / Boron gradually leaks out below pPI (B conversion), and the amount of processing liquid until the boron concentration in the treatment liquid reaches / solution (B conversion) is /r.
It was BV. At this time, the pH of the treatment solution and the concentration of boron (J8
! The overcurve is shown in Figure 1. (The pH of the processing solution was maintained around the same level)
No precipitation due to hydroxide of the 1° hardness component was observed.

処理液中のホウ素濃度／θｐｐｎ（Ｂ換算）に達した時
点で通液を停止し、吸着したホウ素の溶離、再生：塩負
荷を樅なって再び原液を流し６てホウ素の吸着処理を行
なった。以上の工程を内での硬度成分の水酸化物沈澱は
Ｖられず、安定した処理ができた。When the concentration of boron in the treatment solution / θppn (converted to B) was reached, the flow of the solution was stopped, and the adsorbed boron was eluted and regenerated: the salt load was removed and the stock solution was flowed again to perform the boron adsorption treatment. . The hydroxide precipitation of the hardness component did not occur during the above steps, and stable processing was possible.

実施例λ 実施例／の試験が終了した樹脂とカラムをそのまま周込
て、実施例／と同様の方法で樹脂を部分地負荷形とし、
カラムジャケットに？θ℃の温水を通してカラム内温度
を？θ℃に保ち。Example λ The resin for which the test of Example/ has been completed and the column are wrapped as they are, and the resin is partially ground-loaded in the same manner as Example/.
Column jacket? The temperature inside the column is measured by passing hot water at θ℃? Keep at θ℃.

これにホウ酸θ、５７ｙ７ｔ（／θＯｐＨｌｌ　；　Ｂ
換算）、塩化ナトリウムθ、コｒ／１．ｈ’ｃ酸ナトリ
ウム０．３ｆ　／　ｔ　’に含ｔｒ　ｐＨｊ、０１）ｍ
液’ｃ流ｈ　ＥＶ、２０で通液してホウ素の吸着処理全
行なった。この時カラムから流出する処理液中のホウ素
の分析は実施例／と同様の方法で行なった所、処理液量
２　ｊ、２Ｂ　Ｙまでは処理液中のホウ素濃度はＯ９／
ｐＩｌｌｌ（Ｂ換算）以下でその抜栓々にホウ素の漏出
が起こり、処理液中のホウ素濃度が／Ｐ（Ｂ換ｑ、）ま
での処理液ｉ１．２　／、、ＯＢ　Ｖ　テ；９　ツ７’
ｃ。To this, boric acid θ, 57y7t (/θOpHll; B
(conversion), sodium chloride θ, co r/1. Sodium h'c acid 0.3f/t' contains tr pHj, 01)m
The entire boron adsorption process was carried out by passing the solution at a flow rate h EV of 20. At this time, analysis of boron in the treated liquid flowing out from the column was carried out in the same manner as in Example 1. Up to the treated liquid volumes 2j and 2B Y, the boron concentration in the treated liquid was O9/
When the boron concentration in the treatment liquid reaches /P (B conversion q,), boron leaks from the plugs below pIllll (B conversion).
c.

処理液中のホウ素濃度が／θｐｐｍ　（’Ｂ換算）に達
した時点で通液を停止し、吸着したホウ素の酸による溶
離、アルカリによる再生、中性地溶液による部分塩負荷
を行なった後、朽ひ原液ケ流してホウ素の吸着処理！を
行なった。この工程１５０回繰り返しても樹脂のホウ素
の吸着能力に伺らの変化もなく安定して処理ができた。When the boron concentration in the treatment solution reached /θppm ('B conversion), the flow of the solution was stopped, and the adsorbed boron was eluted with acid, regenerated with alkali, and partially salted with a neutral ground solution. Boron adsorption treatment by draining the rotting solution! I did this. Even after repeating this process 150 times, there was no change in the boron adsorption ability of the resin, and the treatment was stable.

比較例／ 実施例−でホウ素の吸着処理ケ終えた褌１脂をそのまま
用すて同一カラム内で、夕％鳩酸／！θ１ｎｌを８Ｖ２
で流し成鳥しているホウ素を溶離し、次いで脱塩水で押
出水洗を行なって妙）Ｃ−！％苛性ソーダ／Δ゛θゴを
ｓｖ−！で流し再生し、脱ね１・水で押出水洗全行なっ
た。Comparative Example/ The loincloth fat that had been subjected to the boron adsorption treatment in Example - was used as it was, and in the same column, % pig acid/! θ1nl to 8V2
The mature boron was eluted with water, and then the extrusion was washed with demineralized water. % caustic soda/Δ゛θgo sv-! I washed it with water and regenerated it, and I did all the extrusion washing with water.

次いで、実軸例／と同一のホウ累含鳴溶液をに０℃で、
ＢＶ／！でカラムに供給し、ホウ素の吸着処理をした。Next, the same borosilicate solution as in the real axis example was added at 0°C.
BV/! was supplied to the column and subjected to boron adsorption treatment.

この時の処理液のｐＨとホウ素破過の様子を図／に破線
で示す。この場合通液開始当初処理液ｐＨが７２となυ
、原液の硬度成分に由来する水酸化物の白色沈澱が処理
液中にみられた。次いで吸着処理を終了した後、カラム
内の樹脂を取シ出した所、４ＩＮ脂に同様の水酸化物の
沈澱が付着し、樹脂がこれによってブロッキングして固
まっていた。The pH of the treatment solution and the state of boron breakthrough at this time are shown by broken lines in the figure. In this case, the pH of the treated solution is 72 at the beginning of the flow.
A white precipitate of hydroxide derived from the hardness component of the stock solution was observed in the treatment solution. After the adsorption treatment was completed, the resin in the column was taken out and found that similar hydroxide precipitates had adhered to the 4IN resin, blocking the resin and solidifying it.

比較例コ 実施例／−で用いたカラムにダイヤイオン０ＲＢＯ２（
三菱化成工業■製、商品名）奮遊離形で／　ｊ　Ｏｄ充
填し、これに！九塩酸／！θｄをｅＶ、２で流し１次い
で脱塩水で押出水洗し、次にｔ％苛性ソーダ／！θｄを
ＢＶコで流し脱塩水で押出・水洗音して実施例コと同一
のホウ素含有原液全と０℃でＳＶコθで通液してホウ素
吸看処理をした。カラムからの処理液中のホウ素濃度が
１０ｐｐ（Ｂ換算）となった時点で、通液を停止し、酸
によるホウ酸の溶離とアルカリによる再生を行なって再
び原液を通してホウ素の吸着処理を行なうという工程を
！θ回繰り返して行なった。この方法では樹脂中のアミ
ンの塩基度の高い熱安定性に乏しい部分がアルカリ溶液
で完全に再生されて遊離形となるために出ｙが／屏（ｐ
換ｑ：）と々るま、での処刑１７伐・肪で比較すると！
θ回目のそれは／回目と比較シて／θ、２タロの低下で
あった。Diaion 0RBO2 (
Manufactured by Mitsubishi Kasei ■, product name) in a free form / j Od filled, this! Nine hydrochloric acid/! θd at eV, 2, then extrusion washing with demineralized water, then t% caustic soda/! θd was flushed with BV, extruded and rinsed with demineralized water, and the same boron-containing stock solution as in Example 1 was passed through SV at θ at 0° C. for boron absorption treatment. When the boron concentration in the treated solution from the column reaches 10 pp (B equivalent), the flow of the solution is stopped, the boric acid is eluted with an acid, the boron is regenerated with an alkali, and the raw solution is passed through the column again for boron adsorption treatment. The process! This was repeated θ times. In this method, the part of the amine in the resin with high basicity and poor thermal stability is completely regenerated with an alkaline solution and becomes a free form, so that the output is
Comparison q:) Comparing the 17 executions and fats in Totoruma!
The θth one was a decrease of 2 taros compared to the /θth time.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は、ホウ素選択吸着樹脂によるポウ素吸着如理に
おける処理液のｐＨ値とホウ素の破ｊ尚曲線奮示９′も
のてあシ、横引１１は、外１理液景（ＢＶ）（ｒ、に、
軸（右）は処理（え液のｐ）Ｉ値全、同（左）は処ｖ）
１液のホウ素濃度（胴；Ｂ換１１）を表わす。 出　願　人　三菱化成工業株式会社 代　理　人　５Ｔ’理士　要否用　− （は力）７名）Figure 1 shows the pH value of the treatment solution and the breakdown of boron in the case of boron adsorption using a boron selective adsorption resin. (r, to,
The axis (right) is the total I value of the treatment (p) of the liquid, and the axis (left) is the treatment (p)
It represents the boron concentration of 1 liquid (body; B exchange 11). Applicant: Mitsubishi Chemical Industries, Ltd. Agent: 5T' Physician (Required or not) (7 people)

Claims (2)

【特許請求の範囲】[Claims] （１）スチレン系共重合体をハロアルキル化した樹脂母
体を下記一般式（１） 式中、ｎ＝／〜ｇ（整数）、Ｒは 一０Ｒ２ｆＯＨ（ＯＨ）％０Ｈ２０Ｈ又はアルキル基を
表わす。但し、ｎ−０〜ｇ（整数）である。 で表わされるアミンでアミノ化して得られるホウ素選択
吸着樹脂を使用して溶液中のホウ素を吸着処理するに際
し、アルカリ溶液で再生して遊離アミン形とした該樹脂
を中性塩溶液と接触させ、該樹脂の中性塩分解能を有す
るアミン部分を塩負荷形として吸着処理に供することを
特徴とするホウ素選択吸着樹脂の再生ｍｐ方法。(1) A resin base obtained by haloalkylating a styrene copolymer is expressed by the following general formula (1). In the formula, n=/~g (integer), and R represents 10R2fOH(OH)%0H20H or an alkyl group. However, it is n-0 to g (integer). When adsorbing boron in a solution using a boron selective adsorption resin obtained by amination with an amine represented by, the resin is regenerated into a free amine form with an alkaline solution and brought into contact with a neutral salt solution, 1. A method for regenerating a boron selective adsorption resin, characterized in that an amine portion of the resin having a neutral salt decomposition ability is subjected to an adsorption treatment in a salt-loaded form. （２）　ホウ素と硬度成分及び／又は重金属成分を（３
）　ホウ素を含む溶液の温度がり０℃以上であることを
ｑ！！徴とする特許請求の範囲第１項記載の方法。(2) Boron and hardness components and/or heavy metal components (3
) The temperature of the solution containing boron is 0℃ or higher! ! The method according to claim 1, characterized in that: