JPH04110093A - Method for removing phenols and aromatic amines from aqueous solution - Google Patents
Method for removing phenols and aromatic amines from aqueous solutionInfo
- Publication number
- JPH04110093A JPH04110093A JP23208590A JP23208590A JPH04110093A JP H04110093 A JPH04110093 A JP H04110093A JP 23208590 A JP23208590 A JP 23208590A JP 23208590 A JP23208590 A JP 23208590A JP H04110093 A JPH04110093 A JP H04110093A
- Authority
- JP
- Japan
- Prior art keywords
- peroxidase
- aqueous solution
- aromatic amines
- hydrogen peroxide
- phenol
- 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.)
- Granted
Links
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 11
- 150000002989 phenols Chemical class 0.000 title claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 14
- 102000003992 Peroxidases Human genes 0.000 claims abstract description 42
- 108040007629 peroxidase activity proteins Proteins 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000009849 deactivation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 description 1
- 108010025188 Alcohol oxidase Proteins 0.000 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 108010015776 Glucose oxidase Proteins 0.000 description 1
- 239000004366 Glucose oxidase Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- CDZHZLQKNAKKEC-UHFFFAOYSA-N [bis(hydroxymethylamino)methylamino]methanol Chemical compound OCNC(NCO)NCO CDZHZLQKNAKKEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 229940116332 glucose oxidase Drugs 0.000 description 1
- 235000019420 glucose oxidase Nutrition 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は水溶液からのフェノール類および芳香族アミン
類の除去方法に関し、さらに詳しくはペルオキシダーゼ
の触媒作用によりフェノール類および／もしくは芳香族
アミン類を過酸化水素と反応させて除去する方法に関す
る。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for removing phenols and aromatic amines from an aqueous solution, and more specifically, the present invention relates to a method for removing phenols and/or aromatic amines from an aqueous solution. It relates to a method of removing hydrogen peroxide by reacting with it.
（従来の技術）
水溶液中に含まれるフェノール類、芳香族アミン類の除
去方法において、これらの物質と過酸化水素とをペルオ
キシダーゼを反応触媒として反応させて、不溶性の重合
物として水溶液中から除去する方法は、例えば、サイエ
ンス（Ｓｃｉｅｎｃｅ）誌、第２２４巻、４６０７号２
５９〜２６１頁（１９８１年）に示されている。(Prior art) In a method for removing phenols and aromatic amines contained in an aqueous solution, these substances and hydrogen peroxide are reacted with peroxidase as a reaction catalyst to remove them from the aqueous solution as an insoluble polymer. The method is described, for example, in Science, Vol. 224, No. 46072.
59-261 (1981).
そのほかのフェノール類やアニソノなどの芳香族アミン
について検討を加えた結果は、ジャーナル・オブ・アプ
ライド・バイオケミストリー（Ｊｏｕｒｎａｌ ｏｆＡ
ｐｐｌｉｅｄ Ｂｉｏｃｈｅｍｉｓｔｒｙ）誌、第２巻
、４１４〜４２１頁（１９８０年）にみることができる
。また、過酸化水素そのものを水溶液に添加するのでは
なく、グルコースオキシダーゼやアルコールオキシダー
ゼのように、反応生成物として過酸化水素を生じる酵素
とその基質とをペルオキシダーゼとともに水溶液に添加
する方法も、特開昭５９−２１３４９４号公報に示され
ている。The results of studies on other phenols and aromatic amines such as anisono are published in the Journal of Applied Biochemistry.
Biochemistry, Vol. 2, pp. 414-421 (1980). In addition, instead of adding hydrogen peroxide itself to an aqueous solution, a method in which an enzyme that produces hydrogen peroxide as a reaction product, such as glucose oxidase or alcohol oxidase, and its substrate are added to an aqueous solution together with peroxidase is also disclosed in Japanese Patent Publication No. It is shown in Publication No. 59-213494.
（発明が解決しようとする課題）
このようなペルオキシダーゼを反応触媒とした、水溶液
中からのフェノール類もしくは芳香族アミン類の除去方
法において問題となるのは、ペルオキシダーゼの価格で
ある。現在、市販されているペルオキシダーゼは西洋わ
さびから抽出されており、フェノール処理時に、フェノ
ール重合生成物へ吸着されるペルオキシダーゼを補うた
めにペルオキシダーゼを再添加することは、コストの面
で実用的ではない。(Problems to be Solved by the Invention) A problem with this method of removing phenols or aromatic amines from an aqueous solution using peroxidase as a reaction catalyst is the price of peroxidase. Currently, commercially available peroxidase is extracted from horseradish, and it is not practical in terms of cost to re-add peroxidase to supplement the peroxidase adsorbed to the phenol polymerization product during phenol treatment.
また、反応液中にゼラチンを加えることで吸着を防げる
が、ゼラチンが水溶性でないため、添加する際に加熱溶
解する必要があり、コストや操作上問題がある。Further, adsorption can be prevented by adding gelatin to the reaction solution, but since gelatin is not water-soluble, it is necessary to heat and dissolve it when adding it, which poses problems in terms of cost and operation.
（課題を解決するための手段）
本発明は、上記の問題点を解決するための手段として、
水溶液からペルオキシダーゼの触媒作用によりフェノー
ル類およびｌもしくは芳香族アミン類を過酸化水素と反
応させて除去する方法において、親水性ポリマーを添加
することを特徴とする水溶液からのフェノール類および
芳香族アミン類の除去方法を提供するものである。(Means for Solving the Problems) The present invention provides, as means for solving the above problems,
A method for removing phenols and aromatic amines from an aqueous solution by reacting with hydrogen peroxide through the catalytic action of peroxidase, the method comprising adding a hydrophilic polymer. This provides a method for removing.
（作用）
水溶液からペルオキシダーゼの触媒作用によりフェノー
ル類および／もしくは芳香族アミン類を過酸化水素と反
応させて除去する方法では、除去反応の進行にともない
、ペルオキシダーゼの触媒活性が水溶液中から失われる
ことが指摘されていた（サイエンス（Ｓｃｉｅｎｃｅ）
誌、第２２４巻、４６０７号２５９〜２９１頁（１９８
３年））。これは、除去反応の中間生成物である芳香族
ラジカルがペルオキシダーゼの活性中心に結合し、ペル
オキシダーゼが失活するためと考えられていた。(Function) In the method of removing phenols and/or aromatic amines from an aqueous solution by reacting them with hydrogen peroxide using the catalytic action of peroxidase, the catalytic activity of peroxidase is lost from the aqueous solution as the removal reaction progresses. It was pointed out that (Science)
Magazine, Vol. 224, No. 4607, pp. 259-291 (198
3 years)). This was thought to be because aromatic radicals, which are intermediate products of the removal reaction, bind to the active center of peroxidase, deactivating peroxidase.
しかし、発明者が検討したところでは、反応の進行とと
もに水溶液中のペルオキシダーゼ活性は減少するが、そ
れとともにペルオキシダーゼ自体も失われていくことが
判明した。ペルオキシダーゼ活性の減少量とベルオキシ
ダイーゼ自体の減少量がほぼ比例することからみて、ペ
ルオキシダーゼ活性の消失の原因は、ペルオキシダーゼ
除去反応によって生じたフェノール重合生成物に吸着し
、反応液から除去されてしまうことにあると考えられた
。発明者はこのようなベルオキシダイーゼの吸着を抑制
する作用を持つ添加物を検討したところ、ポリエチレン
グリコールやポリビニルアルコールのような親水性のポ
リマーがペルオキシダーゼの吸着抑制に有効であること
が判明した。However, the inventor's studies revealed that as the reaction progresses, the peroxidase activity in the aqueous solution decreases, but at the same time, the peroxidase itself also disappears. Considering that the amount of decrease in peroxidase activity is almost proportional to the amount of decrease in peroxidase itself, the reason for the loss of peroxidase activity is that it is adsorbed to the phenol polymerization product generated by the peroxidase removal reaction and removed from the reaction solution. It was thought that there was a particular reason. The inventor investigated additives that have the effect of suppressing the adsorption of peroxidase, and found that hydrophilic polymers such as polyethylene glycol and polyvinyl alcohol are effective in suppressing the adsorption of peroxidase.
（実施例） 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
以下の実施例で使用したペルオキシダーゼは和光純薬製
で、その比活性は、１００プルプロガリン単位／ｍｇ標
品であった。ポリエチレングリコールの分子量は、平均
分子量で表わした。過酸化水素水は、３０ｗｔ％を用い
た
フェノール水溶液は、１０ｍＭＧＴＡ緩衝液（β：β−
ジメチルグルタル酸、トリス（ヒドロキシメチルアミノ
）メタン、２−アミノ−２−メチル−１：３−プロパン
ジオールを２０ｍＭを含む）にフェノールを１０ｇ／ｌ
になるように溶解しｐＨ６，０になるように塩酸で調整
したものと ｆ−
また、水溶液中のフェノール濃度は工業用水試験方法、
ＪＩＳ Ｋ ０１０１によって測定した。全有機炭素濃
度はＴＯＣメーター（島津製作所製）で測定した。The peroxidase used in the following examples was manufactured by Wako Pure Chemical Industries, Ltd., and its specific activity was 100 purpurogalin units/mg standard. The molecular weight of polyethylene glycol was expressed as an average molecular weight. The hydrogen peroxide solution used was 30 wt%.The phenol aqueous solution was prepared using 10mM GTA buffer (β:β-
10 g/l of phenol (containing 20 mM dimethylglutaric acid, tris(hydroxymethylamino)methane, 2-amino-2-methyl-1:3-propanediol)
The phenol concentration in the aqueous solution was determined by the industrial water test method.
Measured according to JIS K 0101. The total organic carbon concentration was measured with a TOC meter (manufactured by Shimadzu Corporation).
まずフェノール水溶液を５０ｍ１にポリエチレングリコ
ール（平均分子量６０００）を０．５．１．２．３ｇ／
ｌになるように添加し、過酸化水素水を１８□１／ｍｉ
ｎで連続添加し、計２５０μｍ添加した。添加終了時に
水溶液から試料を採取し、上清中のペルオキシダーゼ活
性を測定した。第１図に、ポリエチレングリコール添加
濃度とペルオキシダーゼ残存活性（過酸化水素水添加前
のペルオキシダーゼ活性を１００％として表わした）の
関係を示した。この図からポリエチレングリコールの添
加がペルオキシダーゼ吸着の抑制に有効であることがわ
かる。First, add 0.5, 1, 2.3 g of polyethylene glycol (average molecular weight 6000) to 50 ml of phenol aqueous solution.
Add hydrogen peroxide solution to 18□1/mi.
It was added continuously at 250 μm in total. At the end of the addition, a sample was taken from the aqueous solution and the peroxidase activity in the supernatant was measured. FIG. 1 shows the relationship between the concentration of polyethylene glycol added and the residual peroxidase activity (peroxidase activity before addition of hydrogen peroxide solution is expressed as 100%). This figure shows that the addition of polyethylene glycol is effective in suppressing peroxidase adsorption.
次にフェノール水溶液を５０ｍ１にペルオキシダーゼを
２ｇ／ｌ、分子量の異なるポリエチレングリコール（平
均分子量２００．３００．４００．６００．１０００．
７５００）を３ｇ／ｌの濃度で添加した。このフェノー
ル水溶液に、過酸化水素水を１８βｍｉｎで連続添加し
、計２５０ｐ１加えた。添加終了時に水溶液の一部を採
り、上溝中のペルオキシダーゼ活性を測定した。結果は
第１表に示したように、平均分子量６００以上のポリエ
チレングリコールを添加した際には、ペルオキシダーゼ
残存活性（ポリエチレングリコール添加前を１００％と
した）が高かった。Next, add 50ml of phenol aqueous solution, 2g/l of peroxidase, and polyethylene glycols with different molecular weights (average molecular weight: 200.300.400.600.1000.
7500) was added at a concentration of 3 g/l. To this aqueous phenol solution, hydrogen peroxide solution was continuously added at 18 β min, and a total of 250 p1 was added. At the end of the addition, a portion of the aqueous solution was taken and the peroxidase activity in the upper groove was measured. The results are shown in Table 1, when polyethylene glycol having an average molecular weight of 600 or more was added, the peroxidase residual activity (before addition of polyethylene glycol was taken as 100%) was high.
第１表
次に、フェノール水溶液を５０ｍ１に、ペルオキシダー
ゼを０．０１ｇ／ｌの濃度で添加し、ポリエチレングリ
コール（平均分子量１０００）、ポリビニルアルコール
（重合度的２０００）のいずれかを３ｇ／ｌになるよう
に加え、過酸化水素水を１８μｌ／ｍｉｎで連続で計５
４０，１まで添加した。第２表に示したように、ポリエ
チレングツコール、ポリビニルアルコールを添加した場
合、何も添加しなかった場合に比較し、高いフェノール
除去率を示した。Table 1 Next, add peroxidase to 50ml of phenol aqueous solution at a concentration of 0.01g/l, and add either polyethylene glycol (average molecular weight 1000) or polyvinyl alcohol (degree of polymerization 2000) to 3g/l. Add hydrogen peroxide solution continuously at 18 μl/min for a total of 5 times.
40.1 was added. As shown in Table 2, when polyethylene gutucol and polyvinyl alcohol were added, a higher phenol removal rate was shown than when nothing was added.
第２表
（発明の効果）
以上説明したように、本発明の方法によれば水溶液中か
らフェノール類などを除去するに際し、親水性ポリマー
を反応液に加えることで、触媒として用いられるペルオ
キシダーゼのフェノール重合生成物への吸着を抑制し、
ペルオキシダーゼの使用量を従来に比べて少なくできる
。このため、除去に要するコストが低減されるので実用
面で非常に有利である。また他の親水性ポリマーも効果
は異なるが使用可能である。Table 2 (Effects of the Invention) As explained above, according to the method of the present invention, when removing phenols etc. from an aqueous solution, by adding a hydrophilic polymer to the reaction solution, the phenol of peroxidase used as a catalyst can be removed. Suppresses adsorption to polymerization products,
The amount of peroxidase used can be reduced compared to conventional methods. Therefore, the cost required for removal is reduced, which is very advantageous from a practical point of view. Other hydrophilic polymers can also be used, although the effects may vary.
第１図は、ポリエチレングリコールの添加量とペルオキ
シダーゼ残存活性の関係を示す図である。FIG. 1 is a diagram showing the relationship between the amount of polyethylene glycol added and the residual peroxidase activity.
Claims (1)
ェノール類および／もしくは芳香族アミン類を過酸化水
素と反応させて除去する方法において、前記水溶液に親
水性ポリマーを添加することを特徴とする水溶液からの
フェノール類および芳香族アミン類の除去方法。(1) A method for removing phenols and/or aromatic amines from an aqueous solution by reacting them with hydrogen peroxide through the catalytic action of peroxidase, which comprises adding a hydrophilic polymer to the aqueous solution. and aromatic amines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2232085A JP2591288B2 (en) | 1990-08-31 | 1990-08-31 | Method for removing phenols and aromatic amines from aqueous solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2232085A JP2591288B2 (en) | 1990-08-31 | 1990-08-31 | Method for removing phenols and aromatic amines from aqueous solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04110093A true JPH04110093A (en) | 1992-04-10 |
| JP2591288B2 JP2591288B2 (en) | 1997-03-19 |
Family
ID=16933765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2232085A Expired - Lifetime JP2591288B2 (en) | 1990-08-31 | 1990-08-31 | Method for removing phenols and aromatic amines from aqueous solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2591288B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214419A (en) * | 1988-06-30 | 1990-01-18 | Mitsubishi Electric Corp | Rotary head assembly for magnetic recording and reproducing device |
-
1990
- 1990-08-31 JP JP2232085A patent/JP2591288B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214419A (en) * | 1988-06-30 | 1990-01-18 | Mitsubishi Electric Corp | Rotary head assembly for magnetic recording and reproducing device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2591288B2 (en) | 1997-03-19 |
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