JPS6052161B2 - Method for producing chelate resin for mercury removal - Google Patents
Method for producing chelate resin for mercury removalInfo
- Publication number
- JPS6052161B2 JPS6052161B2 JP14498582A JP14498582A JPS6052161B2 JP S6052161 B2 JPS6052161 B2 JP S6052161B2 JP 14498582 A JP14498582 A JP 14498582A JP 14498582 A JP14498582 A JP 14498582A JP S6052161 B2 JPS6052161 B2 JP S6052161B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- chelate resin
- mercury
- chelate
- mercury removal
- 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.)
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Description
【発明の詳細な説明】
本発明は水銀イオンを選択的に吸着する新規なキレー
ト樹脂の製造方法に関するものてある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel chelate resin that selectively adsorbs mercury ions.
更に詳細には、ハロゲン原子を含有する樹脂と、サリチ
ルアミン、または、２−テニルアミンを反応させる事よ
り成る水銀除去用キレート樹脂の製造に関するものであ
る。 従来、水銀法食塩電解工場や金属精錬工場などか
ら排出される。More specifically, the present invention relates to the production of a chelate resin for removing mercury by reacting a resin containing a halogen atom with salicylamine or 2-thenylamine. Traditionally, it is emitted from mercury-method salt electrolysis plants and metal smelting plants.
ごく微量の水銀■イオンを含む廃水の処理には、イオン
交換樹脂、活性炭、ジチオカルバメート基を有するキレ
ート樹脂が用いられてきた。しカルながら、イオン交換
樹脂を用いる方法では、共存塩類のおよぼす影響が大き
く、高濃度の食塩存在下では、水銀イオンの吸着性能が
著しく低下するという欠点をもつ。また、活性炭、ジチ
オカルバメート型キレート樹脂では、水銀イオンのみな
らず他の重金属イオンをも吸着し、選択性に乏しいとい
う欠点を有する。さらに、ジチオカルバメート型キレー
ト樹脂ではジチオカルバメート基が酸化等に弱いという
欠点をもつ。 本発明者らは、既に提案されている水銀
吸着用材料と比較し、共存塩類の影響を受けすに、水銀
イオンのみを選択的に吸着し、かつ化学的に安定なキレ
ート樹脂を開発すべく、鋭意研究を重ねた結果、本発明
を見い出すにいたつた。Ion exchange resins, activated carbon, and chelate resins with dithiocarbamate groups have been used to treat wastewater containing trace amounts of mercury ions. However, the method using an ion exchange resin has the disadvantage that the influence of coexisting salts is large, and the adsorption performance of mercury ions is significantly reduced in the presence of a high concentration of common salt. In addition, activated carbon and dithiocarbamate type chelate resins have the disadvantage that they adsorb not only mercury ions but also other heavy metal ions, resulting in poor selectivity. Furthermore, the dithiocarbamate type chelate resin has the disadvantage that the dithiocarbamate group is susceptible to oxidation. The present inventors aimed to develop a chelate resin that selectively adsorbs only mercury ions and is chemically stable, without being affected by coexisting salts, in comparison with mercury adsorption materials that have already been proposed. As a result of extensive research, we have discovered the present invention.
すなわち、本発明はハロゲン原子を含有する樹脂と、
該樹脂のハロゲンｌｙ原子に対し、ｌｙ分子以上のサリ
チルアミン、または、２−テニルアミンを含む溶液を、
９０〜１１０℃の温度で１時間以上反応せしめることを
特徴とする、水銀除去用キレート樹脂の製造方法である
。That is, the present invention includes a resin containing a halogen atom,
A solution containing more than ly molecules of salicylamine or 2-thenylamine per halogen ly atom of the resin,
This is a method for producing a chelate resin for removing mercury, which is characterized by reacting at a temperature of 90 to 110°C for 1 hour or more.
本発明のキレート樹脂の製造に使用されるハロゲン原
子を含有する樹脂としては、ポリ塩化ビニル、ポリ塩化
ビニリデン等のハロゲン含有樹脂、または、ポリスチレ
ン等をハロゲン化せしめた樹脂があげられる。Examples of the halogen atom-containing resin used for producing the chelate resin of the present invention include halogen-containing resins such as polyvinyl chloride and polyvinylidene chloride, and halogenated resins such as polystyrene.
さらに上記樹脂成分と共重合し得る他のエチレン系不飽
和単量体との共重合体であつてもよい。特に好ましくは
、ゲル型もしくは巨大網目状（ＭＲ型）ポリスチレン−
（１〜２０％）−ジビニルベンゼン共重合体をクロルメ
チル化した樹脂が用いられる。 本発明においてハロゲ
ン原子を含有する樹脂と反応させるアミンとしては、下
図に示すサリチルアミン、２−テニルアミンが用いられ
る。Furthermore, it may be a copolymer with another ethylenically unsaturated monomer that can be copolymerized with the above resin component. Particularly preferably gel type or giant reticulated (MR type) polystyrene
A resin obtained by chloromethylating a (1 to 20%)-divinylbenzene copolymer is used. In the present invention, salicylamine and 2-thenylamine shown in the figure below are used as the amine to be reacted with the resin containing a halogen atom.
これらのアミンは分子内に水銀イオンと安定な錯体を形
成し得るフェノール性水酸基やチオフェン基ならびにア
ミノ基を持つ２座配位子である。ハロゲン原子を含有す
る樹脂と上記アミンとの反応は、該樹脂のハロゲン１ダ
原子に対して１ダ分子以上のアミンを用いればよいが、
反応で生成する塩酸を除去するために、好ましくは２〜
５ｙ分子のアミンが用いられる。These amines are bidentate ligands having a phenolic hydroxyl group, a thiophene group, and an amino group that can form a stable complex with mercury ions in the molecule. For the reaction between the resin containing a halogen atom and the above amine, it is sufficient to use one or more amine molecules per one halogen atom of the resin.
In order to remove hydrochloric acid generated in the reaction, preferably 2 to
A 5y molecule of amine is used.
反応の溶媒としては、水、メチルアルコール、エチルア
ルコール、テトラヒドロフラン、ジオキサン、ベンゼン
、トルエン等が用いられる。好ましくは反応温度との関
係でジオキサンが用いられる。反応温度は９０〜１１０
℃で行われる。As a solvent for the reaction, water, methyl alcohol, ethyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, etc. are used. Preferably, dioxane is used depending on the reaction temperature. Reaction temperature is 90-110
Performed at °C.
上記温度以上ではハロゲン含有樹脂の脱ハロゲン化反応
が起り、また、上記温度以下では反応率が低下し、いず
れの場合も得られた反応生成物の水銀イオン吸着能が低
下するので好ましくない。反応時間は１時間以上でよい
が、反応時間が短いと、反応率が低下するので、好まし
くは１２〜４８時間が適当てある。If the temperature is above the above, dehalogenation reaction of the halogen-containing resin occurs, and if the temperature is below the above, the reaction rate decreases, and in either case, the mercury ion adsorption ability of the obtained reaction product decreases, which is not preferable. The reaction time may be 1 hour or more, but if the reaction time is short, the reaction rate will decrease, so preferably 12 to 48 hours is appropriate.
以上のようにして製造した樹脂は、洗浄乾燥した後、キ
レート樹脂として使用することができる。The resin produced as described above can be used as a chelate resin after being washed and dried.
本発明のキレート樹脂は、銅、ニッケル、亜鉛、コバル
ト等通常の重金属イオンとは安定な錯体をほとんど形成
せず、これらの貴金属イオン共存下においても、選択的
に水銀イオンのみを捕集する。The chelate resin of the present invention hardly forms stable complexes with common heavy metal ions such as copper, nickel, zinc, and cobalt, and selectively collects only mercury ions even in the presence of these noble metal ions.
また、高濃度の共存塩類存在下においても、吸着能力の
低下が見られないという利点を有する。以上本キレート
樹脂について実施例により、更．に詳細に説明する。Furthermore, it has the advantage that no decrease in adsorption capacity is observed even in the presence of high concentrations of coexisting salts. Further details regarding the present chelate resin are provided in Examples. will be explained in detail.
反応に用いたサリチルアミンおよび２−テニルアミンは
、それぞれ公知の方法で合成した。（Ｈ．ＫａｎａｔＯ
ｍｉａｎｄＩ．Ｍｕｒａｓｅ，Ｂｕｌｌ．Ｃｈｅｍ．Ｓ
Ｏｃ．Ｊｐｎ．，４３巻、２２６頁、１９７０年および
Ｈ．Ｄ．ＨａｒｔＯｕｇｈａｎｄＳ．Ｌ．Ｍｅｉｓｅｌ
，Ｊ．Ａｍ．Ｃｈｅｍ．ＳＯｃ．−，７罎、４０１８頁
、１９４詳）高分子母体の樹脂は、スチレンー（１〜２
０％）ージビニルベンゼンのゲル型共重合体、もしくは
、ＭＲ型共重合体であり、おのおの公知の方法で合成し
た。（Ｊ．Ｒ．Ｍｉｌｌａｒ，Ｄ．Ｇ．Ｓｍｉｔｈ，Ｗ
．Ｅ．ＭａｒｒａｎｄＴ．Ｒ．Ｅ．Ｋｒｅｓｓｍａｎ，
Ｊ．Ｃｈｅｍ．ＳＯＯ．，２１８頁、１９６坪およびＲ
．Ｋｕｎｉｎ，Ｅ．Ｆ．ＭｅｉｔｚｎｅｒａｎｄＮ．Ｍ
．ＢＯｒｔｎｉｃｋ，Ｊ．Ａｍ．Ｃｈｅｍ．ＳＯｃ．，
８捲、３０５頁、１９６拝）高分子母体の粒度は３０〜
４００メッシュのものを使用した。クロルメチルポリス
チレンは公知の方法で合成した。（Ｋ．Ｗ．Ｐｅｐｐｅ
ｒ，Ｈ．Ｍ．ＰａｉｓｉｅｙａｎｄＭ．Ａ．ＹＯｌｌｒ
ｌｇ，Ｊ．Ｃｈｅｍ．ＳＯｃ．，４Ｏ９７頁、１９５詳
）２００〜４００メッシュのゲル型スチレンー２％ージ
ビニル・ベンゼン共重合体より得られた、クロルメチル
ポリスチレン樹脂の塩素含有率は、２０．８２％（５．
８ｒｎｍ０１ｅ／ｇ一乾燥樹脂）であつた。この塩素含
有率２０．８２％のゲル型クロルメチルポリスチレンを
出発原料として用いたキレート樹脂の製造方法と性能試
験の実施例を以下に述べる。実施例１
２５０ｍ１のジオキサン中に上記クロルメチルポリスチ
レン（１７．３ｙ）およびサリチルアミン（４９．２ｙ
）を加え、１００℃で４８Ｉ寺間加熱攪拌した。Salicylamine and 2-thenylamine used in the reaction were each synthesized by known methods. (H.KanatO
miandI. Murase, Bull. Chem. S
Oc. Jpn. , vol. 43, p. 226, 1970 and H. D. HartOughandS. L. Meisel
, J. Am. Chem. SOc. -, 7 pages, 4018 pages, 194 details) The polymer matrix resin is styrene (1 to 2
0%)-divinylbenzene gel-type copolymer or MR-type copolymer, each of which was synthesized by a known method. (J.R. Millar, D.G. Smith, W.
．． E. MarrandT. R. E. Kressman,
J. Chem. SOO. , 218 pages, 196 tsubo and R
．． Kunin, E. F. MeitznerandN. M
．． Bortnick, J. Am. Chem. SOc. ，
8 pages, 305 pages, 196 pages) The particle size of the polymer matrix is 30~
A 400 mesh one was used. Chlormethylpolystyrene was synthesized by a known method. (K.W. Peppe
r,H. M. PaisieyandM. A. YOllr
lg, J. Chem. SOc. , 4O p. 97, 195 details) The chlorine content of the chloromethyl polystyrene resin obtained from the 200-400 mesh gel-type styrene-2% divinyl benzene copolymer is 20.82% (5.
8rnm01e/g - dry resin). A method for producing a chelate resin using this gel-type chloromethyl polystyrene with a chlorine content of 20.82% as a starting material and an example of a performance test will be described below. Example 1 The above chloromethyl polystyrene (17.3y) and salicylamine (49.2y) in 250ml dioxane
) was added, and the mixture was heated and stirred at 100° C. for 48 I Terama.
反応生成物を泊過し、水、ジオキサンで充分洗浄し乾燥
した。２１．５ｆの淡黄色樹脂が得られた。（本樹脂を
キレート樹脂Ａと呼ふ。）元素分析値：Ｃｌ８．４４％
、Ｎ３．２％配位子含有率：２．２９ｒｎｍ０Ｉｅ／ｙ
一乾燥樹脂実施例２クロルメチルポリスチレン（１７．
３ｙ）および２−テニルアミン（４５．２９）より、実
施例１と同様の方法により２０．３Ｖの淡黄色樹脂が得
られた。The reaction product was filtered overnight, thoroughly washed with water and dioxane, and dried. A pale yellow resin of 21.5f was obtained. (This resin is called chelate resin A.) Elemental analysis value: Cl8.44%
, N3.2% Ligand content: 2.29rnm0Ie/y
One Dry Resin Example 2 Chlormethylpolystyrene (17.
3y) and 2-thenylamine (45.29), a pale yellow resin of 20.3V was obtained in the same manner as in Example 1.
（本樹脂をキレート樹脂Ｂと呼ぶ。）元素分析値：Ｃｌ
Ｏ．７％、Ｎ４．Ｏ７％配位子含有率：２．９１ｍｍ０
１ｅ／ｙ一乾燥樹脂応用例１実施例１および２で合成し
たキレート樹脂Ａ，またはキレート樹脂Ｂ５ＯＯＴｎ９
を、０．０２Ｍの銅イオンを含む１００ｍ１の水溶液に
加え、所定のＰＨに調整した。(This resin is called chelate resin B.) Elemental analysis value: Cl
O. 7%, N4. O7% ligand content: 2.91mm0
1e/y - Dry resin application example 1 Chelate resin A synthesized in Examples 1 and 2, or chelate resin B5OOTn9
was added to 100 ml of an aqueous solution containing 0.02M copper ions, and the pH was adjusted to a predetermined value.
室温で３時間攪拌した後樹脂を分離し、吸着された銅イ
オンを洲塩酸で溶出した。溶出液中の銅イオンを定量し
、吸着量を求めた。同様にしてニッケル、亜鉛、コバル
トイオンの吸着量を求めた。After stirring for 3 hours at room temperature, the resin was separated and the adsorbed copper ions were eluted with hydrochloric acid. Copper ions in the eluate were quantified to determine the amount of adsorption. In the same manner, adsorption amounts of nickel, zinc, and cobalt ions were determined.
第一表に乾燥樹脂１ｙ当りの最大吸着量（ＭｍＯｌｅ／
ｙ一乾燥樹脂）を示す。応用例２実施例１および２て合
成したキレート樹脂Ａ１または、キレート樹脂ＢｌＯＯ
ｍ９を、種々のＰＨに調整した１０００ｐｐｂの水銀イ
オンを含む溶液５０ｍ１に加え、室温で３時間攪拌した
。Table 1 shows the maximum adsorption amount per y of dry resin (MmOle/
y - dry resin). Application example 2 Chelate resin A1 or chelate resin BlOO synthesized in Examples 1 and 2
m9 was added to 50 ml of a solution containing 1000 ppb mercury ions adjusted to various pH and stirred at room temperature for 3 hours.
溶液中に残留する水銀イオンを定量した除去率を求めた
。除去率とＰＨの関係を第二表に示す。キレート樹脂Ａ
，Ｂとも、強酸性ＰＨ領域できわめて高い除去率を示し
た。応用例３
高濃度の塩化ナトリウム１Ｍを含む１０００ｐｐｂの水
銀イオンを含む溶液を用い、応用例２と同様の方法で、
溶液中に残留する水銀イオンを定量した除去率を求めた
。The removal rate was determined by quantifying the amount of mercury ions remaining in the solution. The relationship between removal rate and PH is shown in Table 2. Chelate resin A
, B both exhibited extremely high removal rates in the strongly acidic PH range. Application Example 3 Using a solution containing 1000 ppb of mercury ions and containing 1 M of highly concentrated sodium chloride, in the same manner as Application Example 2,
The removal rate was determined by quantifying the amount of mercury ions remaining in the solution.
除去率とＰＨの関係を第三表に示す。１Ｍの塩化ナトリ
ウム共存化においても水銀イオンの除去率に著しい低下
は見られなかつた。Table 3 shows the relationship between removal rate and PH. Even in the coexistence of 1M sodium chloride, no significant decrease in the removal rate of mercury ions was observed.
Claims (1)
１ｇ原子に対し、１ｇ分子以上のサリチルアミンまたは
２−テニルアミンを含む溶液を、９０〜１１０℃の温度
で１時間以上反応せしめることを特徴とする水銀除去用
キレート樹脂の製造方法。1. A resin containing a halogen atom is reacted with a solution containing 1 g or more of salicylamine or 2-thenylamine per 1 g of halogen atom of the resin at a temperature of 90 to 110°C for 1 hour or more. A method for producing chelate resin for mercury removal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14498582A JPS6052161B2 (en) | 1982-08-20 | 1982-08-20 | Method for producing chelate resin for mercury removal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14498582A JPS6052161B2 (en) | 1982-08-20 | 1982-08-20 | Method for producing chelate resin for mercury removal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5936103A JPS5936103A (en) | 1984-02-28 |
| JPS6052161B2 true JPS6052161B2 (en) | 1985-11-18 |
Family
ID=15374791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14498582A Expired JPS6052161B2 (en) | 1982-08-20 | 1982-08-20 | Method for producing chelate resin for mercury removal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6052161B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3603515B2 (en) * | 1996-12-24 | 2004-12-22 | ダイヤニトリックス株式会社 | Polymer having thiourea group and heavy metal scavenger comprising the same |
-
1982
- 1982-08-20 JP JP14498582A patent/JPS6052161B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5936103A (en) | 1984-02-28 |
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