JPH10225644A - Method for regenerating strongly basic anion-exchange resin - Google Patents
Method for regenerating strongly basic anion-exchange resinInfo
- Publication number
- JPH10225644A JPH10225644A JP9044802A JP4480297A JPH10225644A JP H10225644 A JPH10225644 A JP H10225644A JP 9044802 A JP9044802 A JP 9044802A JP 4480297 A JP4480297 A JP 4480297A JP H10225644 A JPH10225644 A JP H10225644A
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- anion exchange
- basic anion
- strongly basic
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、強塩基性アニオン
交換樹脂の回生方法に関し、詳しくは、脱塩処理に供し
て有機物を吸着した強塩基性アニオン交換樹脂の回生方
法において、特定の強塩基性アニオン交換樹脂の使用に
より、比較的高い温度における有効な回生を行なうこと
が出来る強塩基性アニオン交換樹脂の回生方法の改良に
関する。TECHNICAL FIELD The present invention relates to a method for regenerating a strongly basic anion exchange resin, and more particularly, to a method for regenerating a strongly basic anion exchange resin which has been subjected to a desalting treatment to adsorb organic substances. The present invention relates to an improvement in a method for regenerating a strongly basic anion exchange resin, which enables effective regeneration at a relatively high temperature by using a basic anion exchange resin.
【0002】[0002]
【従来の技術】純水の製造には、河川水、工業用水、上
水などの原水中に含まれる不純物を除去するため、イオ
ン交換方法が広く採用されている。2. Description of the Related Art In the production of pure water, an ion exchange method is widely used to remove impurities contained in raw water such as river water, industrial water, and tap water.
【0003】強塩基性アニオン交換樹脂は、原水中に含
まれる無機質イオン、有機物などの不純物を吸着する。
吸着された有機物のうちフミン質などの一部の有機物
は、強塩基性アニオン交換樹脂に不可逆的に吸着され、
通常の再生剤である水酸化ナトリウムでは脱着されずに
通水サイクルの増加と共に徐々に蓄積され、いわゆる有
機物汚染障害を受けたといわれる状態になり、アニオン
交換能力の低下を引き起こす。[0003] A strongly basic anion exchange resin adsorbs impurities such as inorganic ions and organic substances contained in raw water.
Some organic substances such as humic substances among the adsorbed organic substances are irreversibly adsorbed on the strongly basic anion exchange resin,
Sodium hydroxide, which is a usual regenerant, is not desorbed but is gradually accumulated with an increase in the water-flow cycle, so that it is said that it has suffered a so-called organic contamination obstacle, and causes a decrease in anion exchange capacity.
【0004】そこで、有機物汚染障害を受けた強塩基性
アニオン交換樹脂と回生剤を接触させて吸着された有機
物を脱着させる方法が種々提案されている。回生剤とし
ては、例えば、塩化ナトリウム等の無機塩水溶液、無機
塩と水酸化ナトリウム等の苛性アルカリとの混合水溶
液、塩酸などの無機酸水溶液、次亜塩素酸ナトリウム等
の酸化剤の水溶液などが使用されている。しかしなが
ら、前記の方法では、樹脂粒子表層面付近に吸着された
有機物は比較的容易に脱着されるが、樹脂粒子の内部細
孔に吸着された有機物は脱着し難い。[0004] Therefore, various methods have been proposed for desorbing the adsorbed organic substances by contacting the regenerant with a strongly basic anion exchange resin which has been damaged by organic substances. Examples of the regenerative agent include an aqueous solution of an inorganic salt such as sodium chloride, a mixed aqueous solution of an inorganic salt and a caustic alkali such as sodium hydroxide, an aqueous solution of an inorganic acid such as hydrochloric acid, and an aqueous solution of an oxidizing agent such as sodium hypochlorite. It is used. However, in the above method, organic substances adsorbed in the vicinity of the surface of the resin particles are relatively easily desorbed, but organic substances adsorbed in the internal pores of the resin particles are not easily desorbed.
【0005】そのため、樹脂粒子の内部細孔に吸着され
た有機物を効率よく脱着させるため、回生剤を加温して
接触させる方法も提案されている。しかしながら、前記
の方法では、加温した回生剤が強塩基性アニオン交換樹
脂の交換基を熱分解させる恐れがある。しかも、従来、
大部分の強塩基性アニオン交換樹脂では、仮に、50℃
前後に加温された回生剤を使用しても有機物の一部が樹
脂粒子の内部細孔に残留してアニオン交換能力を十分に
回復させることが出来ない。そこで、有機物汚染を受け
た強塩基性アニオン交換樹脂について、簡便で効果的な
回生方法が求められていた。[0005] Therefore, a method has been proposed in which a regenerative agent is heated and brought into contact with the regenerative agent in order to efficiently desorb organic substances adsorbed in the internal pores of the resin particles. However, in the above method, the heated regenerative agent may thermally decompose the exchange group of the strongly basic anion exchange resin. Moreover, conventionally,
For most strongly basic anion exchange resins, if at 50 ° C.
Even if a regenerative agent heated before and after is used, part of the organic matter remains in the internal pores of the resin particles, and the anion exchange ability cannot be sufficiently restored. Therefore, a simple and effective regenerative method has been required for a strongly basic anion exchange resin contaminated with organic substances.
【0006】[0006]
【発明が解決しようとする課題】本発明は、上記の実情
に鑑みなされたものであり、その目的は、強塩基性アニ
オン交換樹脂における有機物除去のための回生方法であ
って、有機物の脱着率にすぐれた強塩基性イオン交換樹
脂の回生方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a regenerating method for removing an organic substance from a strongly basic anion exchange resin, the method comprising the steps of: An object of the present invention is to provide a method for regenerating a strongly basic ion exchange resin which is excellent in the above.
【0007】[0007]
【課題を解決するための手段】本発明者らは、上記の目
的を達成すべく種々検討を重ねた結果、ある特定の強塩
基性アニオン交換樹脂は、50℃以上に加温された塩化
ナトリウム水溶液により回生を行うならば樹脂内部細孔
内に有機物の残留が少ないと言う意外な特性を備えてい
ることを見出し、本発明の完成に至った。Means for Solving the Problems The present inventors have made various studies to achieve the above object, and as a result, a specific strong basic anion exchange resin was obtained by heating sodium chloride heated to 50 ° C. or more. It has been found that if the regeneration is carried out with an aqueous solution, the resin has an unexpected characteristic that the amount of organic substances remaining in the internal pores of the resin is small, and the present invention has been completed.
【0008】すなわち、本発明の要旨は、脱塩処理に供
して有機物を吸着した、下記一般式(I)で表される4
級アンモニウム塩基を有する構造単位および不飽和炭化
水素基含有架橋性モノマーから誘導される構造単位を含
有する強塩基性アニオン交換樹脂の回生方法であって、
当該強塩基性アニオン交換樹脂に50℃以上に加温した
塩化ナトリウム水溶液を接触させて吸着された有機物を
脱着させることを特徴とする強塩基性アニオン交換樹脂
の回生方法に存する。[0008] That is, the gist of the present invention is to provide a compound represented by the following general formula (I), which is subjected to desalting treatment to adsorb organic substances.
A method for regenerating a strongly basic anion exchange resin containing a structural unit having a quaternary ammonium base and a structural unit derived from an unsaturated hydrocarbon group-containing crosslinkable monomer,
A method for regenerating a strongly basic anion exchange resin, comprising contacting an aqueous solution of sodium chloride heated to 50 ° C. or higher with the strongly basic anion exchange resin to desorb adsorbed organic substances.
【0009】[0009]
【発明の実施の形態】以下、本発明を詳細に説明する。
先ず、本発明で使用される強塩基性アニオン交換樹脂に
ついて説明する。上記のアニオン交換樹脂は、請求項1
に記載の一般式(I)で表される4級アンモニウム塩基
を有する構造単位および不飽和炭化水素基含有架橋性モ
ノマーから誘導される構造単位を含有する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the strongly basic anion exchange resin used in the present invention will be described. The anion exchange resin according to claim 1
And a structural unit having a quaternary ammonium salt group represented by the general formula (I) and a structural unit derived from an unsaturated hydrocarbon group-containing crosslinkable monomer.
【0010】一般式(I)において、Aは炭素数3〜8
の直鎖状アルキレン基または炭素数4〜9のアルコキシ
メチレン基を表すが、上記の直鎖状アルキレン基として
は、例えば、プロピレン基、ブチレン基、ペンチレン
基、ヘキシレン基などが挙げられ、上記のアルコキシ基
としては、ブトキシメチレン基、ペントキシメチレン基
などが挙げられる。In the general formula (I), A represents 3 to 8 carbon atoms.
Represents a linear alkylene group or an alkoxymethylene group having 4 to 9 carbon atoms. Examples of the linear alkylene group include a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the alkoxy group include a butoxymethylene group and a pentoxymethylene group.
【0011】一般式(I)において、R1は水酸基で置
換されていてもよい炭素数1〜4のアルキル基、R2及
びR3は炭素数1〜4の炭化水素基を表すが、これらの
アルキル基としては、メチル基、エチル基、プロピレン
基、ブチレン基などが挙げられる。In the general formula (I), R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group, and R 2 and R 3 represent a hydrocarbon group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propylene group, and a butylene group.
【0012】一般式(I)において、X-はアンモニウ
ム基に配位した対イオンを表すが、その具体例として
は、Cl-、Br-、I-等のハロゲンイオン、硫酸イオ
ン、NO 3 -、OH-、p−トルエンスルホン酸イオン
等のアニオンが挙げられる。そして、アニオンが硫酸イ
オンの様に2価である場合には、一般式(I)で表され
る構造単位2分子に対してアニオン1分子が結合する。
また、ベンゼン環の置換基のアルキル基としては、メチ
ル基、エチル基などが挙げられ、ハロゲン原子として
は、塩素、臭素、沃素などが挙げられる。In the general formula (I), X-Is Ammoniu
Represents a counter ion coordinated to the
Is Cl-, Br-, I-Halogen ions, sulfate ions, etc.
No, NO Three -, OH-, P-toluenesulfonic acid ion
And the like. And the anion is sulfated
When it is divalent, such as on, it is represented by the general formula (I)
One molecule of an anion binds to two molecules of the structural unit.
In addition, as the alkyl group of the substituent on the benzene ring, methyl
And a halogen atom.
Represents chlorine, bromine, iodine and the like.
【0013】一般式(I)において、R2及びR3はメチ
ル基が好ましく、更には、R1がメチル基であるトリメ
チルアンモニウム塩基(I型強塩基性樹脂)又はR1が
ヒドロキシエチル基であるジメチルヒドロキシエチルア
ンモニウム塩基(II型強塩基性樹脂)が好ましい。In the general formula (I), R 2 and R 3 are preferably a methyl group. Further, R 1 is a methyl group, such as a trimethylammonium base (type I strong basic resin) or R 1 is a hydroxyethyl group. Certain dimethylhydroxyethylammonium bases (type II strongly basic resins) are preferred.
【0014】不飽和炭化水素基含有架橋性モノマーとし
ては、通常、ジビニルベンゼン、トリビニルベンゼン、
ジビニルトルエン、ジビニルナフタレン、ジビニルキシ
レン、エチレングリコールジメタクリレート、ジエチレ
ングリコールジメタクリレート、トリメチロールプロパ
ントリメタクリレート等が挙げられる。これらの中では
ジビニルベンゼンが好ましい。As the unsaturated hydrocarbon group-containing crosslinking monomer, divinylbenzene, trivinylbenzene,
Examples thereof include divinyltoluene, divinylnaphthalene, divinylxylene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate. Of these, divinylbenzene is preferred.
【0015】上記の強塩基性アニオン交換樹脂において
は、全アニオン交換基に対する一般式(I)で表される
4級アンモニウム基の割合は90%以上であることが好
ましく、全アニオン交換基の実質的全量が一般式(I)
で表される4級アンモニウム基であることが特に好まし
い。In the above strongly basic anion exchange resin, the ratio of the quaternary ammonium group represented by the general formula (I) to all anion exchange groups is preferably at least 90%, The total amount is the general formula (I)
Particularly preferred is a quaternary ammonium group represented by
【0016】上記の強塩基性アニオン交換樹脂は、例え
ば、グリニヤール法によりクロルメチルスチレンに炭素
数3〜8のポリメチレン基を有するポリアルキレンジハ
ライドを反応させて得たモノマー又はビニルベンジルア
ルコールと1,ω−ジハロゲノアルカンとの反応によっ
て得られるアルコキシメチレン基を有するモノマー(ω
−ハロゲノメチルスチレン)と架橋剤としてのジビニル
ベンゼンとの共重合によって製造することが出来る。The strongly basic anion exchange resin is, for example, a monomer obtained by reacting chloromethylstyrene with a polyalkylene dihalide having a polymethylene group having 3 to 8 carbon atoms by the Grignard method or vinylbenzyl alcohol with 1,1 a monomer having an alkoxymethylene group obtained by reaction with an ω-dihalogenoalkane (ω
-Halogenomethylstyrene) and divinylbenzene as a crosslinking agent.
【0017】上記の強塩基性アニオン交換樹脂は、例え
ば、特開平4−349941号公報や特開平7−289
921号公報に記載されて公知である。しかしながら、
上記の公報には、当該強塩基性アニオン交換樹脂が吸着
した有機物を脱着させるための回生方法については記載
されていない。The above-mentioned strongly basic anion exchange resin is disclosed, for example, in JP-A-4-349951 and JP-A-7-289.
921 is well known. However,
The above publication does not disclose a regeneration method for desorbing the organic substance adsorbed by the strongly basic anion exchange resin.
【0018】次いで、有機物を吸着した強塩基性アニオ
ン交換樹脂に塩化ナトリウム水溶液を接触させる本発明
の回生方法について説明する。上記の強塩基性アニオン
交換樹脂は、イオン交換塔に充填され、原水を通水さ
れ、無機質イオン、有機物などを吸着し、脱塩処理が行
なわれる。原水の所定量の通液が終了すると、吸着した
無機質イオンと有機物の大部分を脱着するため、通常、
強塩基性アニオン交換樹脂は再生剤である水酸化ナトリ
ウム水溶液を使用して再生工程にかけられる。Next, the regeneration method of the present invention in which an aqueous solution of sodium chloride is brought into contact with a strongly basic anion exchange resin having adsorbed an organic substance will be described. The above-mentioned strong basic anion exchange resin is packed in an ion exchange tower, passed through raw water, adsorbs inorganic ions, organic substances, etc., and is subjected to a desalination treatment. When the passage of a predetermined amount of raw water is completed, most of the adsorbed inorganic ions and organic substances are desorbed.
The strongly basic anion exchange resin is subjected to a regeneration step using an aqueous sodium hydroxide solution as a regenerant.
【0019】原水による通水工程と水酸化ナトリウム水
溶液による再生工程とのサイクルを繰り返すと、脱着さ
れないフミン質、例えば、フミン酸、フルボ酸などの一
部の有機物が強塩基性アニオン交換樹脂内部の細孔に徐
々に蓄積され、処理水純度の低下、採水量の極端な減少
などのアニオン交換障害が引き起こされる。By repeating the cycle of the step of passing water with raw water and the step of regenerating with an aqueous solution of sodium hydroxide, some organic substances such as humic substances that are not desorbed, for example, humic acid and fulvic acid, are removed from the strongly basic anion exchange resin. It gradually accumulates in the pores and causes anion exchange disorders such as a decrease in the purity of the treated water and an extreme decrease in the amount of water taken.
【0020】本発明の回生方法は、有機物が吸着された
強塩基性アニオン交換樹脂に塩化ナトリウム水溶液を5
0℃以上に加温して接触させることを必須の要件とす
る。すなわち、本発明で採用する強塩基性アニオン交換
樹脂に吸着された有機物の脱着効果は、塩化ナトリウム
水溶液の温度が50℃未満では小さく、50℃以上では
増大する。塩化ナトリウム水溶液の上限温度は、特に制
限されないが、97.5℃を目安とする。The regenerating method of the present invention comprises the steps of adding an aqueous solution of sodium chloride to a strongly basic anion exchange resin on which an organic substance is adsorbed.
It is an essential requirement that the contact be made by heating to 0 ° C. or higher. That is, the desorption effect of the organic substance adsorbed on the strongly basic anion exchange resin employed in the present invention is small when the temperature of the aqueous sodium chloride solution is lower than 50 ° C, and increases when the temperature of the aqueous sodium chloride solution is 50 ° C or higher. Although the upper limit temperature of the aqueous sodium chloride solution is not particularly limited, 97.5 ° C. is a standard.
【0021】塩化ナトリウム水溶液は、強塩基性アニオ
ン交換樹脂に対して選択性の大きな塩素イオンを対立イ
オンとして有し、イオン交換塔内部で不溶性の沈殿を生
成せず、汎用的で安価なことにより使用される。塩化ナ
トリウム水溶液濃度は、特に制限されないが、2〜15
重量%の範囲が好ましい。The aqueous sodium chloride solution has a chloride ion having a high selectivity for a strongly basic anion exchange resin as an allion, does not generate an insoluble precipitate inside the ion exchange column, and is versatile and inexpensive. used. The concentration of the aqueous sodium chloride solution is not particularly limited, but may be 2 to 15%.
A range of weight% is preferred.
【0022】なお、塩化ナトリウム水溶液は、通常は塩
化ナトリウム単独の水溶液でよいが、他に、有機物汚染
の程度または有機物の性質によって、塩化ナトリウムに
水酸化ナトリウム及び水溶性有機溶媒(メタノール、エ
タノール、イソプロピルアルコール等)から選ばれる1
種以上を加えて混合水溶液を使用してもよく、汚染した
有機物の解離度を大きくして脱着するので好ましい。塩
化ナトリウムと水酸化ナトリウム、水溶性有機溶媒など
の混合比は、対象とする有機汚染の程度または有機物の
性質により適宜調製される。The aqueous sodium chloride solution may be usually an aqueous solution of sodium chloride alone. However, depending on the degree of contamination of organic substances or the nature of organic substances, sodium chloride and water-soluble organic solvents (methanol, ethanol, 1 selected from isopropyl alcohol)
A mixed aqueous solution may be used by adding more than one species, which is preferable because the dissociation degree of the contaminated organic matter is increased and the organic matter is desorbed. The mixing ratio of sodium chloride to sodium hydroxide, a water-soluble organic solvent, and the like is appropriately adjusted depending on the degree of the target organic contamination or the nature of the organic substance.
【0023】前記強塩基性アニオン交換樹脂のイオン交
換塔への充填方式は、単独でアニオン交換塔に充填する
単床方式、弱塩基性アニオン交換樹脂と強塩基性アニオ
ン交換樹脂を積層させて充填する複層床方式、強酸性カ
チオン交換樹脂と強塩基性アニオン交換樹脂とを混合状
態で収容した充填塔を使用する混床方式などが適宜採用
される。The method of filling the ion exchange tower with the strong basic anion exchange resin is a single bed method in which the anion exchange tower is filled alone, or the weak basic anion exchange resin and the strong basic anion exchange resin are stacked and charged. And a mixed bed method using a packed tower containing a strongly acidic cation exchange resin and a strongly basic anion exchange resin in a mixed state.
【0024】本発明における回生操作は、原水による通
水工程と水酸化ナトリウム水溶液による再生工程とのサ
イクルを繰り返して有機物汚染に起因すると思われるア
ニオン交換障害が発生した際に行ってもよいが、定期
的、例えば、数回の通水工程の終了後に行なってもよ
い。The regenerative operation in the present invention may be performed when an anion exchange failure which is considered to be caused by organic matter contamination occurs by repeating a cycle of a water passing process using raw water and a regeneration process using an aqueous sodium hydroxide solution. It may be performed periodically, for example, after several water passing steps are completed.
【0025】上記の回生操作を施された強塩基性アニオ
ン交換樹脂は、水酸化ナトリウム水溶液などの再生剤を
使用した再生工程により、アニオン交換基を水酸イオン
型に交換後、再び純水の製造に供される。The strongly basic anion exchange resin subjected to the regenerating operation described above is subjected to a regeneration step using a regenerant such as an aqueous sodium hydroxide solution to exchange an anion exchange group into a hydroxyl ion type, and then to pure water again. Provided for manufacturing.
【0026】上述の通り、本発明の回生方法は、有機物
を吸着した特定の構造を有する強塩基性アニオン交換樹
脂に上記のような極めて簡単な回生工程を適用すること
により、有機物を取り除くことが出来るため、河川水、
工業用水、上水などの原水からボイラー用水、電子材料
洗浄用水、医薬製造用水、化粧品製造用水、飲料・食品
製造用水などの純水を効率よく製造することが出来る。As described above, the regeneration method of the present invention can remove organic substances by applying the above-mentioned extremely simple regeneration step to a strongly basic anion exchange resin having a specific structure to which organic substances are adsorbed. River water,
It is possible to efficiently produce pure water such as boiler water, water for washing electronic materials, water for producing pharmaceuticals, water for producing cosmetics, and water for producing beverages and foods from raw water such as industrial water and clean water.
【0027】[0027]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明は、その要旨を超えない限り、以下の実
施例に限定されない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
【0028】製造例 <4−ブロモブチルスチレンの合成>窒素置換したジエ
チルエーテル中、クロルメチルスチレン100重量部と
金属マグネシウム16.5重量部とを10℃で3時間攪
拌し、マグネシウム複合体を得た。次いで、窒素置換テ
トラヒドロフランで溶媒置換した後、15℃の条件下、
1,3−ジブロモプロパン463重量部およびLi2C
uCl4 4.4重量部を含むテトラヒドロフラン14
42重量部中にマグネシウム複合体を滴下し、15℃で
5時間反応を行った。Production Example <Synthesis of 4-bromobutylstyrene> In nitrogen-substituted diethyl ether, 100 parts by weight of chloromethylstyrene and 16.5 parts by weight of metallic magnesium were stirred at 10 ° C. for 3 hours to obtain a magnesium complex. Was. Next, after solvent replacement with nitrogen-substituted tetrahydrofuran, at 15 ° C.
463 parts by weight of 1,3-dibromopropane and Li 2 C
Tetrahydrofuran 14 containing 4.4 parts by weight of uCl 4
The magnesium complex was dropped into 42 parts by weight, and the reaction was performed at 15 ° C. for 5 hours.
【0029】次いで、得られた反応液を0.3Tor
r、120℃の条件下に蒸留し、4−ブロモブチルスチ
レン55重量部を得た。4−ブロモブチルスチレンの同
定は、「ジャーナル・オブ・ポリマー・サイエンス・ポ
リマー・ケミストリー・エディション,20巻,198
2年,3015ページ」に記載のNMR法によって行っ
た。Next, the obtained reaction solution was added to 0.3 Torr.
Distillation was carried out at 120 ° C. to obtain 55 parts by weight of 4-bromobutylstyrene. The identification of 4-bromobutylstyrene is described in "Journal of Polymer Science Polymer Chemistry Edition, Vol. 20, 198.
2 years, p. 3015 ".
【0030】<4−ブロモブチルスチレン架橋共重合体
の合成>上記の4−ブロモブチルスチレン93.5重量
部と純度80重量%のジビニルベンゼン(残部主成分は
エチルビニルベンゼン)6.5重量部に1.0重量部の
アゾビスイソブチロニトリルを加え、窒素雰囲気下、7
0℃で18時間懸濁重合を行い、4−ブロモブチルスチ
レン架橋共重合体の粒状物を90重量%の収率で得た。<Synthesis of Crosslinked 4-Bromobutylstyrene Copolymer> 93.5 parts by weight of the above 4-bromobutylstyrene and 6.5 parts by weight of divinylbenzene having a purity of 80% by weight (the remaining main component is ethylvinylbenzene). Azobisisobutyronitrile (1.0 parts by weight) was added to
Suspension polymerization was performed at 0 ° C. for 18 hours to obtain a 4-bromobutylstyrene crosslinked copolymer granular material in a yield of 90% by weight.
【0031】<強塩基性アニオン交換樹脂の合成>上記
の4−ブロモブチルスチレン架橋共重合体100重量部
をジオキサン300重量部中に2時間攪拌懸濁させて膨
潤させた後、ブロモ基に対して3モル当量の30重量%
トリメチルアミン水溶液を滴下し、50℃で10時間反
応を続行し、強塩基性アニオン交換樹脂を得た。得られ
た強塩基性アニオン交換樹脂を脱塩水で十分に洗浄した
後、その塩型をクロル型に交換した。この様にして得ら
れた強塩基性アニオン交換樹脂の一般性能を測定した結
果、中性塩分解容量は1.27meq/m1、3.33
meq/g、水分は45.7重量%であった。<Synthesis of Strongly Basic Anion Exchange Resin> 100 parts by weight of the above crosslinked 4-bromobutylstyrene copolymer was stirred and suspended in 300 parts by weight of dioxane for 2 hours to swell. 30% by weight of 3 molar equivalents
An aqueous solution of trimethylamine was added dropwise, and the reaction was continued at 50 ° C. for 10 hours to obtain a strongly basic anion exchange resin. After sufficiently washing the obtained strongly basic anion exchange resin with demineralized water, the salt form was exchanged for a chlor form. As a result of measuring the general performance of the thus obtained strongly basic anion exchange resin, the neutral salt decomposition capacity was 1.27 meq / m1, 3.33.
meq / g and water content was 45.7% by weight.
【0032】実施例1 <強塩基性アニオン交換樹脂の再生>上記の製造例で得
られた強塩基性アニオン交換樹脂25mlを内径14m
m、長さ30cmのガラスカラムに充填後、4重量%N
aOH水溶液600mlを通液して再生を行った。次い
で、脱塩水で十分水洗後、ガラスカラムから取り出し、
遠心分離機を使用して付着水分を除いた。Example 1 <Regeneration of Strongly Basic Anion Exchange Resin> 25 ml of the strongly basic anion exchange resin obtained in the above-mentioned preparation example was treated with an inner diameter of 14 m.
m, 4 wt% N after filling into a glass column 30 cm long
Regeneration was performed by passing 600 ml of an aOH aqueous solution. Then, after thoroughly washing with demineralized water, take out from the glass column,
Adhered water was removed using a centrifuge.
【0033】<フミン酸水溶液の調製>試薬フミン酸
(和光純薬工業(株)製)100mgに4重量%NaO
H水溶液100mlを加え、30分間攪拌した。次い
で、予め再生して水素イオン型に交換した強酸性カチオ
ン交換樹脂(三菱化学(株)製 商品「ダイヤイオンS
KIB」)150mlを充填した内径33mm、長さ2
5cmのガラスカラムに上記水溶液を200ml/hの
流速で通液し、さらに、300mlの脱塩水で押出しを
行った後、カラム流出液に1100mlの脱塩水を加え
て全量を1500mlとし、254nm、10mmセル
における吸光度を測定した。<Preparation of aqueous solution of humic acid> 100 mg of reagent humic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 4% by weight of NaO
100 ml of H aqueous solution was added and stirred for 30 minutes. Then, a strongly acidic cation exchange resin that has been previously regenerated and exchanged into a hydrogen ion type (“Diaion S” manufactured by Mitsubishi Chemical Corporation)
KIB ") Inner diameter of 33 mm, length 2 filled with 150 ml
The aqueous solution was passed through a 5 cm glass column at a flow rate of 200 ml / h, and was further extruded with 300 ml of demineralized water. The absorbance in the cell was measured.
【0034】<強塩基性アニオン交換樹脂によるフミン
酸の吸着>1リットルの三角フラスコに、上記の方法で
調製したフミン酸水溶液400ml及び上記の方法で製
造し再生した強塩基性アニオン交換樹脂20mlを加
え、20℃、80rpmの条件で24時間振盪し、強塩
基性アニオン交換樹脂にフミン酸を吸着させた。次い
で、No.5Cのろ紙で当強塩基性アニオン交換樹脂を
ろ別後、ろ液の254nm、10mmセルにおける吸光
度を測定した。吸着操作前後のろ液の吸光度差に液量4
00mlを乗じ、樹脂量20mlで除することにより、
単位樹脂量当たりの見掛けのフミン酸吸着量を求めた。<Adsorption of Humic Acid by Strongly Basic Anion Exchange Resin> 400 ml of the aqueous humic acid solution prepared by the above method and 20 ml of the strongly basic anion exchange resin produced and regenerated by the above method are placed in a 1-liter Erlenmeyer flask. In addition, the mixture was shaken under the conditions of 20 ° C. and 80 rpm for 24 hours to adsorb humic acid to the strongly basic anion exchange resin. Then, No. After the strong basic anion exchange resin was filtered off with a 5C filter paper, the absorbance of the filtrate in a 254 nm, 10 mm cell was measured. The difference between the absorbance of the filtrate before and after the adsorption operation is 4
By multiplying by 00 ml and dividing by 20 ml of resin,
The apparent humic acid adsorption amount per unit resin amount was determined.
【0035】<吸着されたフミン酸の脱着>上記の方法
によりフミン酸を吸着させた強塩基性アニオン交換樹脂
全量を脱塩水で十分水洗後、遠心分離機を使用して付着
水分を除去した。次いで、300mlの三角フラスコ4
個に各々樹脂5mlを分取し、さらに、回生剤として1
0重量%NaCl水溶液100mlを加えた。20℃、
40℃、60℃又は80℃に温度設定された恒温振盪機
に各々の三角フラスコをセットし、80rpmの条件で
24時間振盪し、強塩基性アニオン交換樹脂からフミン
酸を脱着させた。次いで、No.5Cのろ紙で強塩基性
アニオン交換樹脂をろ別後、ろ液の254nm、10m
mセルにおける吸光度を測定した。得られた吸光度に回
生剤量100mlを乗じ、樹脂量5mlで除することに
より、単位樹脂量当たりの見掛けの脱着量を得た。得ら
れた見掛けの脱着量を、先に求めた見掛けの吸着量で除
することにより、各温度におけるフミン酸の脱着率を求
めた。脱着率を図1に示す。<Desorption of Adsorbed Humic Acid> The entire amount of the strongly basic anion exchange resin on which humic acid was adsorbed by the above method was thoroughly washed with demineralized water, and then adhering water was removed using a centrifuge. Next, a 300 ml Erlenmeyer flask 4
5 ml of the resin was separately collected into individual pieces, and 1
100 ml of a 0 wt% NaCl aqueous solution was added. 20 ° C,
Each Erlenmeyer flask was set on a constant temperature shaker set to 40 ° C., 60 ° C., or 80 ° C., and shaken at 80 rpm for 24 hours to desorb humic acid from the strongly basic anion exchange resin. Then, No. After filtering off the strongly basic anion exchange resin with a 5C filter paper, the filtrate was 254 nm, 10 m
The absorbance in the m cell was measured. The apparent absorbance per unit resin amount was obtained by multiplying the obtained absorbance by 100 ml of the regenerating agent and dividing by 5 ml of the resin amount. By dividing the obtained apparent desorption amount by the apparent adsorption amount obtained above, the desorption ratio of humic acid at each temperature was obtained. The desorption rate is shown in FIG.
【0036】比較例1 実施例1において、強塩基性アニオン交換樹脂(三菱化
学(株)製 商品「ダイヤイオンSA10A」)を使用
した以外は、実施例1と同一の操作を行ないフミン酸の
脱着率を求めた。脱着率を図1に示す。COMPARATIVE EXAMPLE 1 Desorption of humic acid was carried out in the same manner as in Example 1 except that a strong basic anion exchange resin (manufactured by Mitsubishi Chemical Corporation, "Diaion SA10A") was used. The rate was determined. The desorption rate is shown in FIG.
【0037】[0037]
【発明の効果】本発明の回生方法は、特定の強塩基性ア
ニオン交換樹脂に特定の回生方法を組み合わせることに
より、有機物を吸着した強塩基性アニオン交換樹脂から
極めて簡便な方法により有機物を脱着させることが出来
るので、効率よく純水を製造することが出来る。According to the regenerating method of the present invention, an organic substance is desorbed from a strongly basic anion exchange resin adsorbed with an organic substance by a very simple method by combining a specific regenerating method with a specific strongly basic anion exchange resin. Therefore, pure water can be efficiently produced.
【図1】強塩基性アニオン交換樹脂の回生温度とフミン
酸の脱着率との関係を示すグラフFIG. 1 is a graph showing the relationship between the regeneration temperature of a strongly basic anion exchange resin and the desorption rate of humic acid.
Claims (3)
記一般式(I)で表される4級アンモニウム塩基を有す
る構造単位および不飽和炭化水素基含有架橋性モノマー
から誘導される構造単位を含有する強塩基性アニオン交
換樹脂の回生方法であって、当該強塩基性アニオン交換
樹脂に50℃以上に加温した塩化ナトリウム水溶液を接
触させて吸着された有機物を脱着させることを特徴とす
る強塩基性アニオン交換樹脂の回生方法。 【化1】 (一般式(I)中、Aは炭素数3〜8の直鎖状アルキレ
ン基または炭素数4〜9のアルコキシメチレン基を表
し、R1は水酸基で置換されていてもよい炭素数1〜4
のアルキル基、R2及びR3は炭素数1〜4の炭化水素
基、X-はアンモニウム基に配位した対イオンを表し又
はベンゼン環はアルキル基またはハロゲン原子で置換さ
れていてもよい。)1. A structural unit having a quaternary ammonium group represented by the following general formula (I) and a structural unit derived from an unsaturated hydrocarbon group-containing crosslinkable monomer, which has been subjected to a desalting treatment to adsorb an organic substance. A method for regenerating a strongly basic anion exchange resin, comprising contacting an aqueous solution of sodium chloride heated to 50 ° C. or more with the strongly basic anion exchange resin to desorb adsorbed organic substances. A method for regenerating a strongly basic anion exchange resin. Embedded image (In the general formula (I), A represents a linear alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 9 carbon atoms, and R 1 has 1 to 4 carbon atoms which may be substituted with a hydroxyl group.
R 2 and R 3 represent a hydrocarbon group having 1 to 4 carbon atoms; X − represents a counter ion coordinated to an ammonium group; or the benzene ring may be substituted with an alkyl group or a halogen atom. )
で表される4級アンモニウム基の割合が90%以上であ
る強塩基性アニオン交換樹脂を使用する請求項1に記載
の回生方法。2. Formula (I) for all anion exchange groups
The regeneration method according to claim 1, wherein a strongly basic anion exchange resin having a quaternary ammonium group ratio of 90% or more is used.
に水酸化ナトリウム及び水溶性有機溶媒から選ばれる1
種以上を加えた混合水溶液である請求項1記載の回生方
法。3. An aqueous solution of sodium chloride, wherein the aqueous solution of sodium chloride is selected from sodium hydroxide and a water-soluble organic solvent.
The regenerating method according to claim 1, wherein the regenerating method is a mixed aqueous solution to which seeds or more are added.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9044802A JPH10225644A (en) | 1997-02-13 | 1997-02-13 | Method for regenerating strongly basic anion-exchange resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9044802A JPH10225644A (en) | 1997-02-13 | 1997-02-13 | Method for regenerating strongly basic anion-exchange resin |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10225644A true JPH10225644A (en) | 1998-08-25 |
Family
ID=12701564
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9044802A Pending JPH10225644A (en) | 1997-02-13 | 1997-02-13 | Method for regenerating strongly basic anion-exchange resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH10225644A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002062284A (en) * | 2000-08-23 | 2002-02-28 | Japan Organo Co Ltd | Impurity extracting method from ion exchange resin and ion exchange resin evaluating method |
WO2003047754A1 (en) * | 2001-12-06 | 2003-06-12 | Organo Corporation | Method for recovering activity of ion exchanger and agent for use in recovering activity of anion exchanger |
CN1326622C (en) * | 2005-05-27 | 2007-07-18 | 哈尔滨工业大学 | Process for reactivating gel type strong base negative resin of polluted in industrial water treatment |
-
1997
- 1997-02-13 JP JP9044802A patent/JPH10225644A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002062284A (en) * | 2000-08-23 | 2002-02-28 | Japan Organo Co Ltd | Impurity extracting method from ion exchange resin and ion exchange resin evaluating method |
WO2003047754A1 (en) * | 2001-12-06 | 2003-06-12 | Organo Corporation | Method for recovering activity of ion exchanger and agent for use in recovering activity of anion exchanger |
CN1326622C (en) * | 2005-05-27 | 2007-07-18 | 哈尔滨工业大学 | Process for reactivating gel type strong base negative resin of polluted in industrial water treatment |
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