JPH0231887A - Method for removing phenol and aromatic amine from aqueous solution - Google Patents

Method for removing phenol and aromatic amine from aqueous solution

Info

Publication number
JPH0231887A
JPH0231887A JP18150988A JP18150988A JPH0231887A JP H0231887 A JPH0231887 A JP H0231887A JP 18150988 A JP18150988 A JP 18150988A JP 18150988 A JP18150988 A JP 18150988A JP H0231887 A JPH0231887 A JP H0231887A
Authority
JP
Japan
Prior art keywords
phenol
hydrogen peroxide
aqueous solution
peroxidase
amount
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
Application number
JP18150988A
Other languages
Japanese (ja)
Inventor
Shinya Nakamoto
信也 中本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NEC Corp
Original Assignee
NEC Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NEC Corp filed Critical NEC Corp
Priority to JP18150988A priority Critical patent/JPH0231887A/en
Publication of JPH0231887A publication Critical patent/JPH0231887A/en
Pending legal-status Critical Current

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  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

PURPOSE:To economically remove phenols and(or) aromatic amines from the aq. soln. thereof with a small amt. of catalyst by reacting hydrogen peroxide kept at a specified concn. with the org. compds. above-mentioned in the presence of peroxidase as catalyst. CONSTITUTION:The peroxidase is dissolved in a phenol aq. soln. and hydrogen peroxide is added at intervals of fixed time period. Thereby, the concn. of the hydrogen peroxide is constantly kept at 10m mol/l. Thus about 98% of the phenol can be removed in the first period of about 60min from the start if reaction. When >= 98% phenol is removed, it requires about 200,000 purpurogallin units/l expensive peroxidase according to a conventional method, but it can be done with about 150,000 purpurogallin units/l by the present method.

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エーノール類および/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用いて反応させ、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(5cience)誌、第224巻、 460
7号、259〜261頁(1983年)に示されている
。この論文では、特にフェノールの除去について詳しく
検討しており、溶液中のフェノールが0,01〜5g/
Iの濃度範囲でこの方法が有効であり、水溶液中のフェ
ノールの98%が除去できるとしている。
[Prior art] In a method for removing phenols and aromatic amines contained in an aqueous solution, these substances are reacted with hydrogen peroxide using peroxidase as a reaction catalyst, and removed from the aqueous solution as an insoluble polymer. The method of doing this is described in, for example, Science (5science), Vol.
No. 7, pp. 259-261 (1983). This paper specifically examines the removal of phenol in detail, and shows that the amount of phenol in the solution is 0.01 to 5 g/
It is said that this method is effective in the concentration range of I, and that 98% of phenol in an aqueous solution can be removed.

フェノール濃度19/Iの水溶液からフェノールを除去
するのに必要なベルオキシダーセ量は水溶液1ftあた
り20.000プルプロガリン単位、過酸化水素値は水
溶液11あたり20mm0+で、フェノール濃度が0.
01〜5g/!で増減した場合、ペルオキシダーゼおよ
び過酸化水素の必要量はフェノール濃度に比例するよう
に増減する必要がある。例えば、フェノール濃度5g/
!の水溶液の場合、水溶液12につきペルオキシダーゼ
は100.000プルプロガリン単位、過酸化水素は1
00mmo lが除去に必要な壜となる。
The amount of peroxidase required to remove phenol from an aqueous solution with a phenol concentration of 19/I is 20.000 purprogalin units per 1 ft of aqueous solution, the hydrogen peroxide value is 20 mm0+ per 1 ft of aqueous solution, and the phenol concentration is 0.
01~5g/! If the amount of peroxidase and hydrogen peroxide is increased or decreased, the required amounts of peroxidase and hydrogen peroxide will need to be increased or decreased in proportion to the phenol concentration. For example, phenol concentration 5g/
! In the case of an aqueous solution of
00 mmol will be the bottle required for removal.

そのほかのフェノール類やアニリン等の芳香族アミンに
ついて検討した結果は、ジャーナル・オブ・アプライド
・バイオケミストリー(Journalof Appl
ied Biochemistry)誌、第21. 4
14〜421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 aniline are published in the Journal of Applied Biochemistry.
ied Biochemistry), No. 21. 4
14-421 (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 a special method. This is disclosed in Japanese Patent Publication No. 59-213494.

[発明が解決しようとする課題] このような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、除去コス
トであり、そのうちの大きな割合を占めるのがペルオキ
シダーゼのような酵素のコストである。特に、高濃度の
フェノール類および/もしくは芳香族アミン類を含有す
る水溶液を対象とする場合、必要なペルオキシダーゼ量
も多くなって除去コストは真人なものとなり、この方法
の実用面での利用は経済性の点で困難でめった。
[Problems to be Solved by the Invention] A problem with such a method for removing phenols or aromatic amines from an aqueous solution is the removal cost, and a large proportion of this is due to the removal of phenols or aromatic amines from an aqueous solution. This is the cost of the enzyme. In particular, when dealing with aqueous solutions containing high concentrations of phenols and/or aromatic amines, the amount of peroxidase required becomes large and the removal cost becomes substantial, making the practical use of this method economical. Sexually difficult and rare.

本発明は以上述べたような従来の事情に対処してなされ
たもので、ペルオキシダーゼの使用量を大巾に少なく(
)て、実用面での利用を可能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こと
を目的とする。
The present invention has been made in response to the conventional circumstances as described above, and is intended to significantly reduce the amount of peroxidase used (
), it is an object of the present invention to provide a method for removing phenols and aromatic amines from an aqueous solution that can be used practically.

[課題を解決するための手段] 本発明は、水溶液中のフェノール類および/もしくは芳
香族アミン類をペルオキシダーゼの存在下で過酸化水素
と反応させて除去する方法において、水溶液中の過酸化
水素濃度を常に10mmol/、11以下に保持しつつ
反応させてな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である。
[Means for Solving the Problems] The present invention provides a method for removing phenols and/or aromatic amines in an aqueous solution by reacting them with hydrogen peroxide in the presence of peroxidase, in which the concentration of hydrogen peroxide in the aqueous solution is reduced. This is a method for removing phenols and aromatic amines from an aqueous solution, characterized in that the reaction is carried out while always maintaining the amount of phenols and aromatic amines at 10 mmol/11 or less.

[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において、過酸化水素は必須の化
学物質でおるが、水溶液中に高濃度で存在した場合、ペ
ルオキシダーゼを失活させる作用がある。
[Operation] Hydrogen peroxide is an essential chemical substance in the method of removing phenols and/or aromatic amines from an aqueous solution by reacting with hydrogen peroxide using the catalytic action of peroxidase. If present, it has the effect of deactivating peroxidase.

ところが、除去しようとするフェノール類等の濃度が高
くなると、従来技術の項で述べたように、過酸化水素必
要量も多くなり、この量を一度に水溶液に添加すれば、
水溶液中の過酸化水素濃度も高くなり、その濃度が1)
に10mmol/ρより大きくなるとペルオキシダーゼ
の失活は、除去対象物質の除去率の低下をもたらす。そ
こで、所定の除去率を冑ようとすれば、ペルオキシダー
ゼ量を増やざなければならない。
However, as the concentration of phenols, etc. to be removed increases, the amount of hydrogen peroxide required also increases, as described in the prior art section, and if this amount is added to the aqueous solution at once,
The concentration of hydrogen peroxide in the aqueous solution also increases;
When the amount of peroxidase exceeds 10 mmol/ρ, peroxidase deactivation results in a decrease in the removal rate of the substance to be removed. Therefore, in order to achieve a predetermined removal rate, the amount of peroxidase must be increased.

一方、水溶液に添加された過酸化水素濃度は除去反応の
進行に伴い、減少していく。従って、初めに10mno
+/ρ以下の濃度になるように過酸化水素を添加した後
、除去反応の進行に伴って減少した過酸化水素量を補充
するように過酸化水素を徐々に添加していけば、高濃度
の過酸化水素と接触することによるペルオキシダーゼの
失活は最小限にすることができ、除去に必要なペルオキ
シダーゼ量を低減することができる。
On the other hand, the concentration of hydrogen peroxide added to the aqueous solution decreases as the removal reaction progresses. Therefore, initially 10mno
If hydrogen peroxide is added to the concentration below +/ρ and then gradually added to replenish the amount of hydrogen peroxide that has decreased as the removal reaction progresses, the concentration can be increased. The deactivation of peroxidase due to contact with hydrogen peroxide can be minimized, and the amount of peroxidase required for removal can be reduced.

[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.

10g/j!フェノール水溶液12にペルオキシダーゼ
(和光純薬製、100プルプロガリン単位/η標品) 
50mg (5,000プルプロガリン単位)を溶解し
た後、30wt%過酸化水素水0,1mlを30秒おき
にフェノール溶液に添加した。過酸化水素水添加直後、
フェノール水溶液中の過酸化水素濃度は0.98mmo
l/flになり、次の過酸化水素水添加(30秒後)を
行うまでにペルオキシダーゼ反応により0mm01 /
 、1!になった。第1図はフェノール水溶液中のフェ
ノール濃度の経時変化を示したものである。
10g/j! Peroxidase in phenol aqueous solution 12 (manufactured by Wako Pure Chemical Industries, Ltd., 100 purpurogalin units/η standard)
After dissolving 50 mg (5,000 purpurogalin units), 0.1 ml of 30 wt% hydrogen peroxide solution was added to the phenol solution every 30 seconds. Immediately after adding hydrogen peroxide,
The hydrogen peroxide concentration in the phenol aqueous solution is 0.98 mmo
l/fl, and by the time the next addition of hydrogen peroxide solution (after 30 seconds) has occurred, the peroxidase reaction has reduced the concentration to 0 mm01/fl.
, 1! Became. FIG. 1 shows the change in phenol concentration in an aqueous phenol solution over time.

同図かられかるように、反応開始から60分後にフェノ
ール濃度は2001F1g#!になり、はじめに存在し
ていたフェノールの98%が除去された。その間添加さ
れた過酸化水素の総量は約0.12 molであった。
As can be seen from the figure, 60 minutes after the start of the reaction, the phenol concentration was 2001F1g#! 98% of the phenol originally present was removed. The total amount of hydrogen peroxide added during that time was about 0.12 mol.

以上、フェノール水溶液に本発明の方法を適用した一実
施例について述べたが、本発明の方法がフェノール以外
のフェノール類おるいは芳香族アミン類にも適用できる
ことは、ペルオキシダーゼがこれらの物質群を反応基質
とし得ることから容易に類推することができる。
An example in which the method of the present invention was applied to an aqueous phenol solution has been described above, but the fact that the method of the present invention can also be applied to phenols other than phenol or aromatic amines means that peroxidase can react with these substance groups. This can be easily inferred from the fact that it can be used as a reaction substrate.

一方、従来技術の項で述べた文献であるサイエンス(5
cience)誌、第224巻、 4607号、  2
59〜261頁(1983年)によるペルオキシダーゼ
・過酸化水素必要量の締出法を10g/βの濃度のフェ
ノール水溶液にまで外挿すると、98%以上のフェノー
ルを除去するに必要なペルオキシダーゼ量は水溶液1β
あたり200.000プルプロガリン単位、過酸化水素
は0.2m01である。実際に実験をしたところ、過酸
化水素必要量全部を反応開始時に加える方法では、10
9/βのフェノール水溶液から98%のフェノールを除
去するのに必要なペルオキシダーゼ量は水溶液12あた
り、150,000プルプロガリン単位であった。また
、過酸化水素必要量は0.2molであった。
On the other hand, the literature mentioned in the prior art section, Science (5
Science) Magazine, Volume 224, No. 4607, 2
59-261 (1983) is extrapolated to an aqueous phenol solution with a concentration of 10 g/β, the amount of peroxidase required to remove 98% or more of phenol is 1β
per 200.000 purpurogalin units, hydrogen peroxide is 0.2 m01. In actual experiments, we found that adding the entire required amount of hydrogen peroxide at the start of the reaction resulted in a
The amount of peroxidase required to remove 98% of phenol from a 9/β aqueous phenol solution was 150,000 purpurogalin units per 12 aqueous solution. Further, the required amount of hydrogen peroxide was 0.2 mol.

以上のことから、本発明の方法によれば、109/Iの
フェノール水溶液から98%のフェノールを除去するの
に必要なペルオキシダーゼ量は従来法に比べ、ペルオキ
シダーゼ必要量は30分の1、過酸化水素必要量は60
%程度になることがわかる。
From the above, according to the method of the present invention, the amount of peroxidase required to remove 98% of phenol from a 109/I phenol aqueous solution is 1/30th that of the conventional method. The required amount of hydrogen is 60
It can be seen that it is about %.

[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
らフェノール類等を除去するに際し、触媒として用いら
れるペルオキシダーゼの量を従来に比べて大巾に少なく
できると共に、過酸化水素量も少なくすることができる
。このため、除去に要するコストが低減化されるので実
用面で非常に有利である。
[Effects of the Invention] As explained above, according to the method of the present invention, when removing phenols etc. from an aqueous solution, the amount of peroxidase used as a catalyst can be greatly reduced compared to the conventional method, and the amount of peroxidase can be greatly reduced compared to the conventional method. The amount of hydrogen can also be reduced. Therefore, the cost required for removal is reduced, which is very advantageous from a practical point of view.

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

第1図はフェノール水溶液中のフェノール:a度の経時
変化を示す図である。
FIG. 1 is a diagram showing changes over time in phenol: degree a in an aqueous phenol solution.

Claims (1)

【特許請求の範囲】[Claims] (1)水溶液中のフェノール類および/もしくは芳香族
アミン類をペルオキシダーゼの存在下で過酸化水素と反
応させて除去する方法において、水溶液中の過酸化水素
濃度を常に10mmol/l以下に保持しつつ反応させ
てな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 in an aqueous solution by reacting them with hydrogen peroxide in the presence of peroxidase, while always maintaining the hydrogen peroxide concentration in the aqueous solution at 10 mmol/l or less. 1. A method for removing phenols and aromatic amines from an aqueous solution, characterized by carrying out a reaction.
JP18150988A 1988-07-22 1988-07-22 Method for removing phenol and aromatic amine from aqueous solution Pending JPH0231887A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP18150988A JPH0231887A (en) 1988-07-22 1988-07-22 Method for removing phenol and aromatic amine from aqueous solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP18150988A JPH0231887A (en) 1988-07-22 1988-07-22 Method for removing phenol and aromatic amine from aqueous solution

Publications (1)

Publication Number Publication Date
JPH0231887A true JPH0231887A (en) 1990-02-01

Family

ID=16102006

Family Applications (1)

Application Number Title Priority Date Filing Date
JP18150988A Pending JPH0231887A (en) 1988-07-22 1988-07-22 Method for removing phenol and aromatic amine from aqueous solution

Country Status (1)

Country Link
JP (1) JPH0231887A (en)

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