JPH06170366A - Method for treating waste cleaning liquid - Google Patents
Method for treating waste cleaning liquidInfo
- Publication number
- JPH06170366A JPH06170366A JP35015092A JP35015092A JPH06170366A JP H06170366 A JPH06170366 A JP H06170366A JP 35015092 A JP35015092 A JP 35015092A JP 35015092 A JP35015092 A JP 35015092A JP H06170366 A JPH06170366 A JP H06170366A
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- liquid
- organic acid
- cleaning liquid
- treatment
- 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
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、洗浄廃液の処理方法に
係り、特にボイラ、熱交換器、タンク等の化学洗浄廃液
の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating cleaning waste liquid, and more particularly to a method for treating chemical cleaning waste liquid for boilers, heat exchangers, tanks and the like.
【0002】[0002]
【従来の技術】酸化鉄を主体としたスケールが付着して
いる洗浄対象物を、有機酸で洗浄した後、水洗後、前記
酸洗浄ではほとんど除去できない金属銅を除去し、洗浄
対象物の金属表面を安定化させるため、除銅・防錆処理
を実施する例は多い。洗浄終了後、上記廃液に含有され
るCOD、重金属類及びNH3 を処理しなければならな
いが、近年処理が確実で簡単に行なえる逆浸透膜(以
下、ROという)処理が適用されることが多い。2. Description of the Related Art After cleaning an object to be cleaned, which has scales mainly composed of iron oxide, with an organic acid, it is washed with water and then metal copper, which is hardly removable by the acid cleaning, is removed to remove the metal of the object to be cleaned. In many cases, copper removal and anticorrosion treatment are performed to stabilize the surface. After the cleaning is completed, COD, heavy metals and NH 3 contained in the waste liquid must be treated, but in recent years, a reverse osmosis membrane (hereinafter referred to as RO) treatment, which is reliable and easy to perform, has been applied. Many.
【0003】この場合に、ROの処理効率を上げる目的
で、有機酸洗浄廃液中の低級カルボン酸の解離度を上げ
るために、pHを5〜6、好ましくは5.5〜6に調整
するのであるが、有機酸洗浄廃液と、除銅防錆液を混合
すると、有機酸洗浄液に含まれる還元剤の働きで除銅防
錆液中の銅が遊離するので、両液を別の槽に受けなけれ
ばならなかった。この結果従来の廃液処理では2つの廃
液槽に酸廃液と除銅防錆液を別々に受け入れ、酸廃液は
pHを5〜6に調整し、除銅防錆液は銅が遊離しないよ
うに、キレート剤を添加した後、NH3 の除去効率を上
げるため、同様の理由でpH5〜7に調整しRO処理を
実施しなければならなかった。In this case, the pH is adjusted to 5 to 6, preferably 5.5 to 6 in order to increase the dissociation degree of the lower carboxylic acid in the organic acid cleaning waste liquid for the purpose of increasing the RO treatment efficiency. However, when the organic acid cleaning waste liquid is mixed with the copper removal rust preventive solution, the reducing agent contained in the organic acid cleaning solution releases copper in the copper remover rust preventive solution, so both solutions should be received in separate tanks. I had to. As a result, in the conventional waste liquid treatment, the acid waste liquid and the copper removal anticorrosion liquid are separately received in two waste liquid tanks, the pH of the acid waste liquid is adjusted to 5 to 6, and the copper removal anticorrosion liquid does not release copper. After the addition of the chelating agent, in order to improve the NH 3 removal efficiency, it was necessary to adjust the pH to 5 to 7 and perform the RO treatment for the same reason.
【0004】[0004]
【発明が解決しようとする課題】上記のように、従来技
術では有機酸洗浄廃液と除銅防錆液とは、それぞれ別々
にpH調整してRO処理を実施しなければならなく、不
経済であった。本発明は、前記した従来技術の問題点を
改善し、有機酸洗浄廃液と除銅防錆液とを一緒に混合し
てRO処理できる経済的な方法を提供することを課題と
する。As described above, in the prior art, the organic acid cleaning waste liquid and the copper removal anticorrosion liquid must be separately pH-adjusted for RO treatment, which is uneconomical. there were. SUMMARY OF THE INVENTION It is an object of the present invention to improve the above-mentioned problems of the prior art and provide an economical method capable of performing RO treatment by mixing an organic acid cleaning waste liquid and a copper removal anticorrosive liquid together.
【0005】[0005]
【課題を解決するための手段】上記課題を解決するため
に、本発明では、カルボン酸と洗浄効果を高めるための
還元剤とを含有する有機酸洗浄廃液と、除銅防錆液とを
混合し、pH調整して逆浸透膜処理する洗浄廃液の処理
方法において、前記有機酸洗浄廃液を、又は該有機酸洗
浄廃液と前記除銅防錆液とを混合後に該洗浄廃液を、酸
化することとしたものである。前記方法において、カル
ボン酸はカルボキシル基の解離度が低く、pH4以下で
は半透膜の透過率が高く、RO処理における透過率が5
%を超えるモノカルボン酸又はジカルボン酸を用いるこ
とができる。In order to solve the above problems, in the present invention, an organic acid cleaning waste liquid containing a carboxylic acid and a reducing agent for enhancing the cleaning effect is mixed with a copper removing anticorrosive liquid. In the method for treating a cleaning waste liquid in which the pH is adjusted to perform reverse osmosis membrane treatment, the organic acid cleaning waste liquid, or the cleaning waste liquid after mixing the organic acid cleaning waste liquid and the copper removal anticorrosive liquid, is oxidized. It is what In the above method, the carboxylic acid has a low degree of dissociation of the carboxyl group, has a high permeability of the semipermeable membrane at a pH of 4 or less, and has a permeability of 5 in the RO treatment.
More than% monocarboxylic or dicarboxylic acids can be used.
【0006】上記のように、本発明においては、廃液槽
に酸洗廃液を受け入れた後除銅防錆液を受け入れる前又
は後に廃液中に含有されるFe2+をFe3+に酸化するこ
とによって、1つの廃液槽に両方の廃液を受け入れるこ
とを可能にしたものである。図1に、本発明の工程図を
記載し、これに基づいて説明する。まず、廃液槽に酸洗
浄廃液1を導入し、次いで除銅防錆液2を導入する。こ
の際、酸化処理3、3′は酸洗浄廃液1を導入した後に
行うか、又は除銅防錆液2を流入した後に行うのがよ
い。次いで、pHを5〜6に調整4した後に、RO処理
5することにより廃液処理することができる。As described above, in the present invention, after the pickling waste liquid is received in the waste liquid tank and before or after receiving the copper removal anticorrosive liquid, Fe 2+ contained in the waste liquid is oxidized to Fe 3+. This makes it possible to receive both waste liquids in one waste liquid tank. FIG. 1 shows a process chart of the present invention, and description will be made based on this. First, the acid cleaning waste liquid 1 is introduced into the waste liquid tank, and then the copper removal rust preventive liquid 2 is introduced. At this time, it is preferable that the oxidation treatments 3 and 3'be performed after the acid cleaning waste liquid 1 is introduced or after the copper removal anticorrosive liquid 2 is introduced. Then, the pH is adjusted to 5 to 6 and then the RO treatment 5 is performed to perform the waste liquid treatment.
【0007】[0007]
【作用】本発明においては、酸性の洗浄液とアルカリ性
の除銅防錆液を混合して処理するので、従来各々をpH
調整するのに消費した酸・アルカリがそれぞれ低減され
ることで、余分な塩の注入が少くなるためRO処理での
濃縮率は増大する。また、従来必要とした高価なキレー
ト剤の添加も不要となるので、処理に要する薬品量は少
なくなる。Fe2+をFe3+に酸化する酸化剤は特に限定
される必要はないが、後段のRO処理に負荷を掛けない
ためには、空気、酸素、オゾン、過酸化水素等の塩濃度
を増加しないものが望ましい。In the present invention, since an acidic cleaning solution and an alkaline copper removing anticorrosive solution are mixed and treated, the pH of each is conventionally changed.
By reducing the amount of acid and alkali consumed for adjustment, the injection of extra salt is reduced and the concentration rate in RO treatment is increased. In addition, since it is not necessary to add an expensive chelating agent, which is conventionally required, the amount of chemicals required for the treatment is reduced. The oxidizing agent that oxidizes Fe 2+ to Fe 3+ does not have to be particularly limited, but in order not to impose a load on the subsequent RO treatment, increase the salt concentration of air, oxygen, ozone, hydrogen peroxide, etc. Those that do not do are desirable.
【0008】[0008]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はこれに限定されない。 実施例1 下記表1の組成の酸洗廃液Aと除銅防錆液Bとを混合処
理する実験を行った。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 An experiment was conducted in which a pickling waste liquid A having the composition shown in Table 1 below and a copper removal anticorrosive liquid B were mixed and treated.
【0009】[0009]
【表1】 [Table 1]
【0010】その結果は以下のようであった。 (a)、表1の組成の酸洗廃液(A)と除銅防錆液
(B)(以下(A)液(B)液)を2:1にて混合しp
H5.5〜6に調整を行うと、直ちに銅が遊離した。 (b)、(a)の液を空気酸化により酸化したところ銅
は再び溶解した。 (c)、あらかじめ空気酸化した(A)液を(a)と同
様に操作したところ銅の遊離は起こらなかった。The results were as follows. (A), the pickling waste liquid (A) having the composition shown in Table 1 and the copper removal anticorrosive liquid (B) (hereinafter (A) liquid (B) liquid) are mixed at a ratio of 2: 1 and p
When H5.5 to 6 was adjusted, copper was immediately released. When the liquids of (b) and (a) were oxidized by air oxidation, copper was dissolved again. (C) When liquid (A) which had been air-oxidized in advance was operated in the same manner as in (a), liberation of copper did not occur.
【0011】(d)、(b)(c)の操作をFe2+とエ
リソルビン酸ナトリウムを酸化するのに必要な過酸化水
素水(35%H2 O2 、1.8ml)を用いて同様に行
なったところ銅は溶解した。 (e)、(A)液のpHを、(B)液と混合時にpH
5.5〜6になるようにあらかじめ調整し(b)〜
(d)に示す酸化手段で処理した後、混合したところ銅
は溶解した。 このように酸化処理することにより、銅は溶解した。The operations of (d), (b) and (c) were carried out by using Fe 2+ and hydrogen peroxide solution (35% H 2 O 2 , 1.8 ml) necessary for oxidizing sodium erythorbate. The copper melted as a result. (E), (A) solution pH, when mixed with (B) solution
Adjust in advance so as to be 5.5 to 6 (b) to
After the treatment by the oxidizing means shown in (d), when mixed, copper was dissolved. Copper was dissolved by such an oxidation treatment.
【0012】次に、上記廃液を図1に示すフローに従っ
て以下のように処理した。 A液を空気酸化したのち、B液を混合する。そのと
きの比率はA:B=2:1とした。この液を水酸化ナト
リウムを用いてpH5.5に調整したのち、RO処理を
行った。 比較例として A液,B液をそれぞれ単独にpH調整し、RO処理し
た。この場合、A液はNaOHでpH5.5に調整し、
B液は中和処理する前にキレート剤としてEDTAを銅
イオンに対して少過剰当量の830mg/リットル濃度
になるよう添加したのち、硫酸を用いてpH7.0に調
整し、RO処理した。 それらの結果を表2に示す。Next, the waste liquid was treated as follows according to the flow shown in FIG. After liquid A is air-oxidized, liquid B is mixed. The ratio at that time was A: B = 2: 1. This solution was adjusted to pH 5.5 with sodium hydroxide and then subjected to RO treatment. As a comparative example, solution A and solution B were individually pH-adjusted and subjected to RO treatment. In this case, the solution A is adjusted to pH 5.5 with NaOH,
Before neutralizing the solution B, EDTA was added as a chelating agent to a concentration of 830 mg / liter, which is a slight excess equivalent to copper ions, and then the pH was adjusted to 7.0 with sulfuric acid and subjected to RO treatment. The results are shown in Table 2.
【0013】[0013]
【表2】 [Table 2]
【0014】濃縮率=原水液量/濃縮水液量 より 従来法の濃縮率 : 400+200/54+25=
7.6 本発明の濃縮率 : 600/75=8.0 表2から明らかなように、本発明によるRO処理は従来
法による結果と比べて、透過液の性状は2液を混合して
処理しているにも拘らず、殆んど変化は認められず、ま
た、濃縮率も向上している。Concentration rate = Raw water liquid amount / Concentrated water liquid amount Concentration ratio of the conventional method: 400 + 200/54 + 25 =
7.6 Concentration rate of the present invention: 600/75 = 8.0 As is clear from Table 2, the RO treatment according to the present invention is performed by mixing two liquids in terms of the property of the permeated liquid as compared with the result obtained by the conventional method. Despite this, almost no change was observed and the concentration rate was also improved.
【0015】[0015]
【発明の効果】本発明によれば、廃液受槽を従来の2槽
から1槽にすることができ、またpH調整剤の使用量も
少なくなった。更には、従来必要としたキレート剤の添
加も不要となった。According to the present invention, the waste liquid receiving tank can be changed from the conventional two tanks to one tank, and the amount of the pH adjuster used is reduced. Furthermore, the addition of the chelating agent, which was conventionally required, is no longer necessary.
【図1】本発明の処理方法を示す工程図。FIG. 1 is a process drawing showing a processing method of the present invention.
1:酸洗浄廃液、2:除銅防錆液、3、3′:酸化処
理、4:pH調整、5:RO処理1: Acid cleaning waste liquid, 2: Copper removal rust preventive liquid, 3 ': Oxidation treatment, 4: pH adjustment, 5: RO treatment
Claims (1)
元剤とを含有する有機酸洗浄廃液と、除銅防錆液とを混
合し、pH調整して逆浸透膜処理する洗浄廃液の処理方
法において、前記有機酸洗浄廃液を、又は該有機酸洗浄
廃液と前記除銅防錆液とを混合後に該洗浄廃液を、酸化
することを特徴とする洗浄廃液の処理方法。1. A method for treating a cleaning waste liquid, which comprises mixing an organic acid cleaning waste liquid containing a carboxylic acid and a reducing agent for enhancing the cleaning effect with a copper removal rust preventive solution and adjusting the pH to perform reverse osmosis membrane treatment. 3. The method for treating a cleaning waste liquid, comprising oxidizing the organic acid cleaning waste liquid or the cleaning waste liquid after mixing the organic acid cleaning waste liquid and the copper removal anticorrosive liquid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35015092A JPH06170366A (en) | 1992-12-04 | 1992-12-04 | Method for treating waste cleaning liquid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35015092A JPH06170366A (en) | 1992-12-04 | 1992-12-04 | Method for treating waste cleaning liquid |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06170366A true JPH06170366A (en) | 1994-06-21 |
Family
ID=18408570
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP35015092A Pending JPH06170366A (en) | 1992-12-04 | 1992-12-04 | Method for treating waste cleaning liquid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH06170366A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998041478A1 (en) * | 1997-03-14 | 1998-09-24 | E.I. Du Pont De Nemours And Company | Treatment of effluent streams containing organic acids |
CN106745933A (en) * | 2015-11-23 | 2017-05-31 | 湖南衡阳新澧化工有限公司 | A kind of ferriferous oxide produces the processing method of waste water |
-
1992
- 1992-12-04 JP JP35015092A patent/JPH06170366A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998041478A1 (en) * | 1997-03-14 | 1998-09-24 | E.I. Du Pont De Nemours And Company | Treatment of effluent streams containing organic acids |
CN106745933A (en) * | 2015-11-23 | 2017-05-31 | 湖南衡阳新澧化工有限公司 | A kind of ferriferous oxide produces the processing method of waste water |
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