JPH0712476B2 - Treatment method of fluorine-containing wastewater - Google Patents
Treatment method of fluorine-containing wastewaterInfo
- Publication number
- JPH0712476B2 JPH0712476B2 JP2160587A JP2160587A JPH0712476B2 JP H0712476 B2 JPH0712476 B2 JP H0712476B2 JP 2160587 A JP2160587 A JP 2160587A JP 2160587 A JP2160587 A JP 2160587A JP H0712476 B2 JPH0712476 B2 JP H0712476B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- added
- ferric
- wastewater
- hydrogen peroxide
- 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
- Removal Of Specific Substances (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、過酸化水素を含むフッ素含有廃水の処理方法
に関する。TECHNICAL FIELD The present invention relates to a method for treating fluorine-containing wastewater containing hydrogen peroxide.
廃水中に含まれるフッ素を除去する方法としては、従
来、カルシウム塩を用いるフッ化カルシウム沈殿法が一
般に行われている。また、フッ化カルシウムを沈殿させ
る際に、第二鉄塩を添加して水酸化第二鉄の沈殿とフッ
化カルシウムを共沈させることも知られている。この方
法では、原水を鉱酸でpH4以下に調整した後、第二鉄塩
及びカルシウム塩を添加し、次いで、アルカリ剤を添加
してpH7〜８に調整し、凝集剤を添加し、固液分離す
る。As a method for removing fluorine contained in wastewater, a calcium fluoride precipitation method using a calcium salt has been generally performed conventionally. It is also known to add a ferric salt to coprecipitate the precipitation of ferric hydroxide and calcium fluoride when precipitating calcium fluoride. In this method, the raw water is adjusted to pH 4 or less with a mineral acid, ferric salt and calcium salt are added, then an alkaline agent is added to adjust the pH to 7 to 8, a flocculant is added, and a solid-liquid mixture is added. To separate.
しかしながら、この処理方法において、廃水中に過酸化
水素が混入してくると、過酸化水素が第二鉄塩に対して
還元剤として作用し、添加した第二鉄イオン（Fe3+）が
第一鉄イオン（Fe2+）に還元されて、第一鉄イオンが処
理水中に混入する。このFe2+のため、処理水が着色する
と同時に水酸化第二鉄の生成が阻害される結果、処理水
のフッ素濃度も高くなる。However, in this treatment method, when hydrogen peroxide is mixed in the wastewater, the hydrogen peroxide acts as a reducing agent for the ferric salt, and the added ferric ion (Fe 3+ ) becomes It is reduced to ferrous ions (Fe 2+ ), and ferrous ions are mixed in the treated water. Due to this Fe 2+ , the treated water is colored and the production of ferric hydroxide is inhibited at the same time, and as a result, the fluorine concentration of the treated water also increases.
従って、本発明は、前記の従来技術の欠点を解消し、フ
ッ素含有廃水中に過酸化水素が混入していても、廃水中
のフッ素を効果的に除去することができるフッ素含有廃
水の処理方法を提供することを目的とする。Therefore, the present invention solves the above-mentioned drawbacks of the prior art, and even if hydrogen peroxide is mixed in the fluorine-containing waste water, it is possible to effectively remove the fluorine in the waste water, and a method for treating fluorine-containing waste water. The purpose is to provide.
本発明は、廃水に第二鉄塩及びカルシウム塩を添加した
後、アルカリ剤をpH9以上になるまで添加することによ
って前記の問題点を解決したものである。The present invention solves the above-mentioned problems by adding a ferric salt and a calcium salt to wastewater and then adding an alkaline agent until the pH reaches 9 or more.
即ち、本発明方法は、過酸化水素及びフッ素を含む廃水
にpH4以下でカルシウム塩及び第二鉄塩を添加し、その
後、アルカリ剤を添加して廃水のpHを９以上に調整した
後、中性〜アルカリ性で沈殿物を生成させることを特徴
とする。That is, according to the method of the present invention, calcium salt and ferric salt are added to a wastewater containing hydrogen peroxide and fluorine at a pH of 4 or lower, and then an alkaline agent is added to adjust the pH of the wastewater to 9 or higher. It is characterized in that it forms a precipitate in a neutral to alkaline manner.
詳述すれば、本発明方法においては、まず、廃水のpHを
４以下に調整する。廃水のpHが４を越えると、第二鉄塩
を添加したときに、第二鉄塩が水酸化第二鉄として単独
で沈殿してしまうので、この段階では好ましくない。More specifically, in the method of the present invention, first, the pH of the wastewater is adjusted to 4 or less. If the pH of the wastewater exceeds 4, when the ferric salt is added, the ferric salt will precipitate as ferric hydroxide alone, which is not preferable at this stage.
pH調整後、カルシウム塩及び第二鉄塩を添加する。カル
シウム塩としては、塩化カルシウム、硫酸カルシウム、
炭酸カルシウム等を使用することができる。カルシウム
塩の添加量は、フッ素に対して１〜２反応当量であるの
が好ましい。第二鉄塩としては、塩化第二鉄、硫酸第二
鉄等を使用することができる。第二鉄塩の添加量は、25
〜300mg/lである。After adjusting the pH, calcium salt and ferric salt are added. As calcium salts, calcium chloride, calcium sulfate,
Calcium carbonate or the like can be used. The amount of calcium salt added is preferably 1-2 reaction equivalents with respect to fluorine. As the ferric salt, ferric chloride, ferric sulfate or the like can be used. The amount of ferric salt added is 25
~ 300 mg / l.
カルシウム塩及び第二鉄塩を添加した後、直ぐにアルカ
リ剤を加えてpHを９以上に調整して沈殿物を生成させ
る。中性付近では、過酸化水素が第二鉄イオンを還元し
て第一鉄イオンにしてしまうので、pH9以上として過酸
化水素を分解する。即ち、ここで、CaF2及びFe（OH）３
が沈殿すると同時に過酸化水素が分解する。CaF2の粒子
は、Fe（OH）３に吸着され、共沈する。Immediately after adding the calcium salt and ferric salt, an alkaline agent is added to adjust the pH to 9 or more to form a precipitate. In the vicinity of neutrality, hydrogen peroxide reduces ferric ions to ferrous ions, so that hydrogen peroxide is decomposed at pH 9 or higher. That is, here, CaF 2 and Fe (OH) 3
Hydrogen peroxide is decomposed at the same time that the hydrogen peroxide precipitates. The CaF 2 particles are adsorbed on Fe (OH) 3 and coprecipitate.
生成した沈殿物を常法で固液分離することができる。分
離液は、必要に応じて中性にした後、放流することがで
きる。また、一旦、廃水のpHを９以上にして過酸化水素
を分解させた後、酸を加えて中性付近で沈殿物の生成及
び固液分離処理を行ってもよい。The formed precipitate can be solid-liquid separated by a conventional method. The separated liquid can be discharged after neutralizing it if necessary. Alternatively, the pH of the waste water may be once adjusted to 9 or higher to decompose the hydrogen peroxide, and then an acid may be added to perform precipitation and solid-liquid separation treatment in the vicinity of neutrality.
カルシウム塩及び第二鉄塩を添加した後、アルカリ剤を
加えてpHを９以上に調整すると、廃水中に含まれている
過酸化水素が分解され、第二鉄イオンの還元は起こらな
いので、CaF2の粒子は、Fe（OH）３に吸着され、共沈す
る。After adding the calcium salt and ferric salt and adjusting the pH to 9 or more by adding an alkaline agent, hydrogen peroxide contained in the wastewater is decomposed and the reduction of ferric ion does not occur. The CaF 2 particles are adsorbed on Fe (OH) 3 and coprecipitate.
次に、実施例に基づいて本発明を詳述するが、本発明は
これに限定されるものではない。Next, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
実施例１ 原水としてフッ素濃度243mg/l、過酸化水素濃度36mg/
l、pH2.5の廃水を使用した。この原水に塩化第二鉄をFe
3+として100mg/l添加し、更に、フッ素に対して反応当
量＝２の塩化カルシウムを添加した。その後、水酸化カ
ルシウムを添加して廃水のpHを10とし、数分間攪拌し
た。その後、高分子凝集剤を添加して、沈殿物を凝集さ
せ、固液分離した。Example 1 As raw water, fluorine concentration 243 mg / l, hydrogen peroxide concentration 36 mg /
Waste water of pH 2.5 was used. Add ferric chloride to this raw water
100 mg / l was added as 3+ , and further calcium chloride having a reaction equivalent of 2 with respect to fluorine was added. Then, calcium hydroxide was added to adjust the pH of the wastewater to 10, and the mixture was stirred for several minutes. Then, a polymer flocculant was added to flocculate the precipitate, and solid-liquid separation was performed.
得られた処理水中のフッ素濃度は、8mg/lとなった。The fluorine concentration in the obtained treated water was 8 mg / l.
上記の実験において、塩化第二鉄及び塩化カルシウムを
添加した後、廃水のpHを種々に変えて実験し、得られた
処理水のフッ素濃度を測定し、結果を第１図に示す。In the above experiment, after adding ferric chloride and calcium chloride, the pH of the waste water was changed variously, the fluorine concentration of the obtained treated water was measured, and the result is shown in FIG.
第１図から判るように、従来法として、pH7で実施した
場合には、Ｆ＝40mg/lであり、pH8で実施した場合に
は、Ｆ＝18mg/lであった。これに対し、本発明方法によ
りpH9以上で実施すると、Ｆ＝8mg/lとなり、本発明によ
れば良好な結果が得られた。As can be seen from FIG. 1, when the conventional method was carried out at pH 7, F = 40 mg / l, and when it was carried out at pH 8, F = 18 mg / l. On the other hand, when the method of the present invention was carried out at pH 9 or higher, F = 8 mg / l, and the present invention provided good results.
本発明方法によれば、フッ素含有廃水中に過酸化水素が
混入していても、廃水中のフッ素を効率良く除去するこ
とができる。According to the method of the present invention, even if hydrogen peroxide is mixed in the waste water containing fluorine, the fluorine in the waste water can be efficiently removed.
第１図は、沈殿物生成時のpHと処理水のフッ素濃度との
関係を示すグラフである。FIG. 1 is a graph showing the relationship between pH at the time of deposit formation and the fluorine concentration of treated water.
Claims (1)
下でカルシウム塩及び第二鉄塩を添加し、その後、アル
カリ剤を添加して廃水のpHを９以上に調整した後、中性
〜アルカリ性で沈殿物を生成させることを特徴とするフ
ッ素含有廃水の処理方法。1. A calcium hydroxide and a ferric salt are added to a wastewater containing hydrogen peroxide and fluorine at a pH of 4 or less, and then an alkaline agent is added to adjust the pH of the wastewater to 9 or more, and then neutrality A method for treating fluorine-containing wastewater, which is characterized in that an alkaline precipitate is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160587A JPH0712476B2 (en) | 1987-01-30 | 1987-01-30 | Treatment method of fluorine-containing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160587A JPH0712476B2 (en) | 1987-01-30 | 1987-01-30 | Treatment method of fluorine-containing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63190695A JPS63190695A (en) | 1988-08-08 |
| JPH0712476B2 true JPH0712476B2 (en) | 1995-02-15 |
Family
ID=12059666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2160587A Expired - Fee Related JPH0712476B2 (en) | 1987-01-30 | 1987-01-30 | Treatment method of fluorine-containing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0712476B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4132851B2 (en) * | 2002-02-06 | 2008-08-13 | オルガノ株式会社 | Method for treating wastewater containing fluorine and hydrogen peroxide |
| JP4879575B2 (en) * | 2005-12-21 | 2012-02-22 | コスモ工機株式会社 | Detaching method of pipe connecting member |
| CN117819696A (en) * | 2024-01-29 | 2024-04-05 | 东晟环保科技集团(安徽)股份有限公司 | A pretreatment method for strongly acidic fluorine-containing organic wastewater |
-
1987
- 1987-01-30 JP JP2160587A patent/JPH0712476B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63190695A (en) | 1988-08-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |