JPH0722752B2 - Wafer process wastewater treatment method - Google Patents
Wafer process wastewater treatment methodInfo
- Publication number
- JPH0722752B2 JPH0722752B2 JP62107048A JP10704887A JPH0722752B2 JP H0722752 B2 JPH0722752 B2 JP H0722752B2 JP 62107048 A JP62107048 A JP 62107048A JP 10704887 A JP10704887 A JP 10704887A JP H0722752 B2 JPH0722752 B2 JP H0722752B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- tank
- wafer process
- wastewater
- catalase
- 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.)
- Expired - Fee Related
Links
Landscapes
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Weting (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は半導体工業より排出されるウエーハプロセス排
水の処理方法に関する。The present invention relates to a method for treating wafer process wastewater discharged from the semiconductor industry.
一般に、半導体工場の廃水は、排水源より分類すると、
ウエーハプロセス廃水、廃ガス処理装置廃水、空
調設備廃水、超純水製造装置廃水、生活廃水に分類
される。Generally, the wastewater of semiconductor factories is
Wafer process wastewater, waste gas treatment equipment wastewater, air conditioning equipment wastewater, ultrapure water production equipment wastewater, and domestic wastewater.
これらの中で一番処理がむづかしいのがウエーハプロセ
ス廃水で、この廃水は水量が多く、フッ酸、塩酸、硝
酸、りん酸、酢酸、フッ化アンモニウム、過酸化水素な
どを含んでいる。The most difficult of these treatments is wafer process wastewater, which contains a large amount of water and contains hydrofluoric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid, ammonium fluoride, hydrogen peroxide and the like.
ウエーハプロセス廃水の処理として、消石灰などのアル
カリ性カルシウム塩を添加することにより、pHを中性域
とし、フッ素を難溶性フッ化カルシウムとして沈殿分離
するか、あるいはアルカリ性のアルミニウム塩または、
マグネシウム塩を添加することにより、フッ素を吸着さ
せ沈殿分離したのち上澄水を生物処理し、排出する方法
が一般的である。しかしながら廃水中に過酸化水素を含
有すると、フッ素を沈殿分離する際、沈殿物と過酸化水
素が反応し、フロック中に気泡を抱き込み、沈殿分離に
不具合を生じるので、重亜硫酸ソーダを添加して、過酸
化水素を分解していた。しかしながら、重亜硫酸ソーダ
による過酸化水素の分解法には、 （イ）過酸化水素と重亜硫酸ソーダが反応する際、pHが
下がり、亜硫酸ガスを発生し、周囲の環境に悪影響を及
ぼす。As a treatment of the wafer process wastewater, by adding an alkaline calcium salt such as slaked lime, the pH is set to a neutral range and fluorine is precipitated and separated as a sparingly soluble calcium fluoride, or an alkaline aluminum salt, or
In general, a method of adsorbing fluorine by adding a magnesium salt to cause precipitation separation and then biologically treating the supernatant water and discharging it. However, if hydrogen peroxide is contained in the wastewater, when the fluorine is precipitated and separated, the precipitate reacts with the hydrogen peroxide, entraps air bubbles in the flocs, and causes a problem in precipitation separation.Therefore, add sodium bisulfite. And decomposed hydrogen peroxide. However, in the method for decomposing hydrogen peroxide with sodium bisulfite, (a) when hydrogen peroxide and sodium bisulfite react, the pH is lowered and sulfurous acid gas is generated, which adversely affects the surrounding environment.
（ロ）過酸化水素と重亜硫酸ソーダは等量反応なので、
過酸化水素濃度が高い場合、重亜硫酸ソーダが大量に必
要となる。(B) Since hydrogen peroxide and sodium bisulfite react in the same amount,
When the hydrogen peroxide concentration is high, a large amount of sodium bisulfite is required.
などの欠点があった。There were drawbacks such as.
本発明は、前述の欠点を解決するため鋭意研究を重ねた
結果、酵素であるカタラーゼの使用が各種の問題点を一
挙に解決することを見出したものである。As a result of intensive studies to solve the above-mentioned drawbacks, the present invention has found that the use of the enzyme catalase solves various problems at once.
カタラーゼは1892年ジャコブソン（Jacobson）が過酸化
水素を特異的に分解する酵素として植物組織中から見出
したものであり、現在では嫌気性菌以外のほとんどすべ
ての生物体に分布しており、動物組織特に肝臓、赤血球
に多く存在し、植物では葉緑体などに存在している。そ
して、カタラーゼは、シアン、アジド、フッ素イオンと
結合し、低濃度でその作用が阻害されるという性質があ
る。Catalase was discovered in plant tissue by Jacobson in 1892 as an enzyme that specifically decomposes hydrogen peroxide, and is now distributed in almost all organisms except anaerobic bacteria. Especially in the liver and red blood cells, in plants, it is found in chloroplasts. Catalase has the property of binding to cyanide, azide, and fluoride ions, and inhibiting its action at low concentrations.
そこで、本発明者等は、廃水中に存在するフッ素イオン
を水に不溶性のフッ化カルシウムにすることにより、カ
タラーゼに対する活性を失わしめた後、カタラーゼの有
効利用をはかったものである。なお、フッ素イオンの10
〜20ppm程度の存在であれば、カタラーゼの利用に支障
はない。Therefore, the present inventors attempted to effectively use catalase after the activity against catalase was lost by converting the fluoride ion existing in the waste water into water-insoluble calcium fluoride. Fluorine ion 10
The presence of about 20 ppm does not hinder the use of catalase.
カタラーゼの添加量は、従来、過酸化水素の分解用に用
いられていた重亜硫酸ソーダが過酸化水素と等モル必要
であったのに較べて極めて少量でその目的を達する。目
安となる使用量は、ほぼつぎのとおりである。Catalase is added in an extremely small amount as compared with the case where sodium bisulfite, which has been conventionally used for decomposing hydrogen peroxide, needs to be equimolar to hydrogen peroxide. The approximate usage amount is as follows.
廃水中の過酸化水素濃度が10〜100mg/lのとき添加量は5
0mg/l 廃水中の過酸化水素濃度が100〜250mg/lのとき添加量は
100mg/l 廃水中の過酸化水素濃度が250〜500mg/lのとき添加量は
150mg/l 廃水中の過酸化水素濃度が500〜1,000mg/lのとき添加量
は200mg/l 廃水中の過酸化水素濃度が1,000〜5,000mg/lのとき添加
量は300mg/l 廃水中の過酸化水素濃度が5,000〜10,000mg/lのとき添
加量は500mg/l 使用時のpHは、５〜９、とくに７〜８において酵素の活
性が最高になるのでもっとも好ましい。When the hydrogen peroxide concentration in the wastewater is 10 to 100 mg / l, the addition amount is 5
0 mg / l When the hydrogen peroxide concentration in the wastewater is 100 to 250 mg / l, the amount added is
When the concentration of hydrogen peroxide in the waste water is 250 to 500 mg / l, the addition amount is 100 mg / l.
150 mg / l When the hydrogen peroxide concentration in the waste water is 500 to 1,000 mg / l, the addition amount is 200 mg / l When the hydrogen peroxide concentration in the waste water is 1,000 to 5,000 mg / l, the addition amount is 300 mg / l In the waste water When the concentration of hydrogen peroxide is 5,000 to 10,000 mg / l, the addition amount is 500 mg / l, and when the pH is 5 to 9, especially 7 to 8, the enzyme activity becomes the highest, and it is most preferable.
処理時の水温は０〜50℃である。The water temperature during the treatment is 0 to 50 ° C.
アルカリ性カルシウム含有化合物としては消石灰、生石
灰等が挙げられる。Examples of the alkaline calcium-containing compound include slaked lime and quick lime.
凝集剤としては、ノニオンまたはアニオン性の高分子凝
集剤が挙げられ、例えばポリアクリルアミド、ポリアク
リル酸ソーダ、ポリアクリルアミド部分加水分解物など
が使用できる。Examples of the aggregating agent include nonionic or anionic polymer aggregating agents, and for example, polyacrylamide, sodium polyacrylate, polyacrylamide partial hydrolyzate and the like can be used.
以下に実験例、実施例を示して説明する。 Experimental examples and examples will be described below.
実験例１ ウエーハプロセス廃水（pH2.0,H2O2200ppm）に水酸化カ
ルシウムを添加して系中のフッ素イオンを水不溶性のCa
F2に変化させ、ついで水酸化ナトリウム水溶液を加えpH
を７に微調整したのち、所定濃度になるようにカタラー
ゼを添加し、機械的に20分間攪拌する。カタラーゼ添加
前後の過酸化水素濃度およびpHを測定した。Experimental Example 1 Calcium hydroxide was added to the wafer process wastewater (pH 2.0, H 2 O 2 200 ppm) to remove fluorine ions in the system from water-insoluble Ca.
Change to F 2 , then add aqueous sodium hydroxide solution to
After finely adjusting to 7, catalase was added to a predetermined concentration and mechanically stirred for 20 minutes. The hydrogen peroxide concentration and pH were measured before and after the addition of catalase.
結果を第１表に示す。The results are shown in Table 1.
比較実験例１ 従来法と比較のため、34％重亜硫酸ソーダを所定量添加
して同様の実験を行なった。Comparative Experimental Example 1 For comparison with the conventional method, the same experiment was conducted by adding a predetermined amount of 34% sodium bisulfite.
結果を第１表に示す。The results are shown in Table 1.
実験例２ ウエーハプロセス廃水（pH1.5,H2O21000ppm）に水酸化
カルシウムを加えて系中のフッ素イオンを水不溶性のCa
F2に変化させ、さらに水酸化ナトリウム水溶液を加え、
pHを７に微調整したのち、所定濃度になるようにカタラ
ーゼを添加し、機械的に20分間攪拌する。カタラーゼ添
加前後の過酸化水素濃度およびpHを測定した。 Experimental Example 2 Calcium hydroxide was added to the wafer process wastewater (pH 1.5, H 2 O 2 1000 ppm) to remove fluorine ions in the system from water-insoluble Ca.
Change to F 2 , add more aqueous sodium hydroxide,
After finely adjusting the pH to 7, catalase is added to a predetermined concentration and mechanically stirred for 20 minutes. The hydrogen peroxide concentration and pH were measured before and after the addition of catalase.
結果を第２表に示す。The results are shown in Table 2.
比較実験例２ 従来法と比較のため、34％重亜硫酸ソーダを所定量添加
して同様の実験を行なった。Comparative Experimental Example 2 For comparison with the conventional method, the same experiment was conducted by adding a predetermined amount of 34% sodium bisulfite.
結果を第２表に示す。The results are shown in Table 2.
実施例１ 図面に示すウエーハプロセス排水処理設備を使用した。
５m3容量のＡ槽に排水を15m3/hrの割合で供給し、消石
灰を約５％水性スラリーとして、500l/hrの割合で加え
た。また、35％塩酸を添加して、pHを６〜７に調整し
た。 Example 1 A wafer process wastewater treatment facility shown in the drawings was used.
Waste water was supplied to a 5 m 3 tank A at a rate of 15 m 3 / hr, and slaked lime was added as an about 5% aqueous slurry at a rate of 500 l / hr. Further, the pH was adjusted to 6 to 7 by adding 35% hydrochloric acid.
Ａ槽からＢ槽、Ｂ槽から沈殿槽への排水の移送は、オバ
ーフロー方式により行なった。Ｂ槽もＡ槽と同一容量の
槽であり、ここでは25％水酸化ナトリウム溶液を添加し
てpHを７に微調整した。カタラーゼは、Ａ槽から送られ
てくる処理水量に対し、50ppmになるように、Ｂ槽に連
続添加した。The waste water was transferred from the A tank to the B tank and from the B tank to the precipitation tank by an overflow method. The tank B has the same capacity as the tank A. Here, the pH was finely adjusted to 7 by adding a 25% sodium hydroxide solution. Catalase was continuously added to the B tank so as to be 50 ppm with respect to the amount of treated water sent from the A tank.
Ｂ槽の滞留時間は約20分間である。Ｂ槽に流入する排水
中の過酸化水素濃度は平均値で150ppmであった。Ｂ槽で
処理された排水は、沈殿槽に送られるが、このとき凝集
剤としてポリアクリルアミド系のクリフロック pA 362
（栗田工業株式会社商標）を約1ppm加えることにより、
沈殿を促進する。沈殿槽の有効容積は約76m3のものを使
用した。沈殿槽から気泡の発生はみられなかった。試験
の結果、沈殿槽における過酸化水素濃度は、10ppm以下
となり、フッ化カルシウムフロックの浮上は認められな
かった。The residence time in tank B is about 20 minutes. Drainage flowing into tank B
The average hydrogen peroxide concentration was 150 ppm. In tank B
The treated wastewater is sent to a settling tank, where it is condensed.
Polyacrylamide Cliflock as an agent pA 362
By adding about 1 ppm (trademark of Kurita Water Industries Ltd.),
Promotes precipitation. The effective volume of the sedimentation tank is about 76 m3Use one
I used it. No bubbles were found in the settling tank. test
As a result, the hydrogen peroxide concentration in the settling tank was 10 ppm or less.
Therefore, the flocculation of calcium fluoride was not observed.
won.
本発明の効果は、次の通りである。 The effects of the present invention are as follows.
（１）重亜硫酸ソーダを使用するときのように反応によ
りpHがさがることもなく、又亜硫酸ガスのような有毒ガ
スを発生することがないので、二次公害の心配もない。(1) Since the pH does not decrease due to the reaction unlike the case of using sodium bisulfite and a toxic gas such as sulfurous acid gas is not generated, there is no fear of secondary pollution.
（２）カタラーゼは触媒的に働くので、使用量が極めて
少い。(2) Catalase acts catalytically, so the amount used is extremely small.
第１図は、本発明の１実施例を示す。 Ａ槽、フッ素イオン除去のための槽であり、Ｂ槽はカタ
ラーゼを用いた過酸化水素分解槽、Ｃ槽は沈殿槽であ
る。 1:消石灰スリラー貯槽、2:カタラーゼ水溶液貯槽 3:凝集剤貯槽、4:攪拌機 5:ウエーハプロセス排水供給パイプ ６〜7:移送パイプ 8:処理済排水の排出用パイプFIG. 1 shows an embodiment of the present invention. A tank is a tank for removing fluorine ions, a B tank is a hydrogen peroxide decomposition tank using catalase, and a C tank is a precipitation tank. 1: Slaked lime chiller storage tank, 2: Catalase aqueous solution storage tank 3: Flocculant storage tank, 4: Stirrer 5: Wafer process wastewater supply pipe 6 to 7: Transfer pipe 8: Treated wastewater discharge pipe
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 21/304 ３４１ Ｚ 21/306 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location H01L 21/304 341 Z 21/306
Claims (1)
ルシウム含有化合物を添加し、排水中のフッ素イオンを
フッ化カルシウムにした後、pH5〜９において、カタラ
ーゼを添加し、過酸化水素を分解し、ついで、固液分離
することを特徴とするウエーハプロセス排水の処理方
法。1. An alkaline calcium-containing compound is added to wafer process wastewater to convert the fluoride ions in the wastewater into calcium fluoride, and then catalase is added at pH 5 to 9 to decompose hydrogen peroxide, and then, A method for treating wafer process wastewater, which comprises solid-liquid separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62107048A JPH0722752B2 (en) | 1987-04-30 | 1987-04-30 | Wafer process wastewater treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62107048A JPH0722752B2 (en) | 1987-04-30 | 1987-04-30 | Wafer process wastewater treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63270595A JPS63270595A (en) | 1988-11-08 |
| JPH0722752B2 true JPH0722752B2 (en) | 1995-03-15 |
Family
ID=14449195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62107048A Expired - Fee Related JPH0722752B2 (en) | 1987-04-30 | 1987-04-30 | Wafer process wastewater treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0722752B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01297198A (en) * | 1988-05-26 | 1989-11-30 | Nec Corp | Treatment of waste water |
| US9254400B2 (en) * | 2010-03-02 | 2016-02-09 | Ecolab Usa Inc. | Method for processing peroxygen solutions |
| WO2017221944A1 (en) * | 2016-06-21 | 2017-12-28 | パナソニックヘルスケアホールディングス株式会社 | Catalase inhibitor and method for measuring analyte using catalase inhibitor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS556606A (en) * | 1978-06-29 | 1980-01-18 | Toshiba Corp | Priority change system |
| JPS586299A (en) * | 1981-06-30 | 1983-01-13 | リガツツオ・ピエ−ル・ジオルジオ | Purification of water containing organic pollutants |
| EP0134766A1 (en) * | 1983-08-10 | 1985-03-20 | Purac Aktiebolag | Method of treating peroxide-containing wastewater |
| JPS60175504A (en) * | 1984-02-22 | 1985-09-09 | Kurita Water Ind Ltd | Method for washing membrane separation apparatus |
| JPS62279885A (en) * | 1986-05-27 | 1987-12-04 | Naigai Kagaku Seihin Kk | Treatment of waste water containing hydrogen peroxide |
-
1987
- 1987-04-30 JP JP62107048A patent/JPH0722752B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS556606A (en) * | 1978-06-29 | 1980-01-18 | Toshiba Corp | Priority change system |
| JPS586299A (en) * | 1981-06-30 | 1983-01-13 | リガツツオ・ピエ−ル・ジオルジオ | Purification of water containing organic pollutants |
| EP0134766A1 (en) * | 1983-08-10 | 1985-03-20 | Purac Aktiebolag | Method of treating peroxide-containing wastewater |
| JPS6058297A (en) * | 1983-08-10 | 1985-04-04 | プラク・アクツエブラ−グ | Method of treating waste water containing peroxide |
| JPS60175504A (en) * | 1984-02-22 | 1985-09-09 | Kurita Water Ind Ltd | Method for washing membrane separation apparatus |
| JPS62279885A (en) * | 1986-05-27 | 1987-12-04 | Naigai Kagaku Seihin Kk | Treatment of waste water containing hydrogen peroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63270595A (en) | 1988-11-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |