JP2504039B2 - Treatment method of water containing antimony - Google Patents
Treatment method of water containing antimonyInfo
- Publication number
- JP2504039B2 JP2504039B2 JP62070255A JP7025587A JP2504039B2 JP 2504039 B2 JP2504039 B2 JP 2504039B2 JP 62070255 A JP62070255 A JP 62070255A JP 7025587 A JP7025587 A JP 7025587A JP 2504039 B2 JP2504039 B2 JP 2504039B2
- Authority
- JP
- Japan
- Prior art keywords
- antimony
- water
- containing water
- treatment
- liquid separation
- 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 - Lifetime
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、アンチモン含有水から、アンチモンを高
度かつ効率的に除去することのできる処理方法に関する
ものである。TECHNICAL FIELD The present invention relates to a treatment method capable of highly and efficiently removing antimony from antimony-containing water.
従来のアンチモン含有水の処理方法としては、廃水中
の鉄、銅、亜鉛など共存する他の金属類と共沈させる
か、または塩化鉄、硫酸鉄などを添加して凝集沈殿する
方法、ならびに硫酸バンドによるpH6〜９における凝集
沈殿処理方法などが知られており、鉄を利用する場合は
いずれもアルカリ性特にpH9〜11で処理されている（例
えば特開昭61−291094号）。Conventional antimony-containing water treatment methods include coprecipitation with other coexisting metals such as iron, copper, and zinc in wastewater, or a method of adding iron chloride, iron sulfate, or the like to coagulate and precipitate, and sulfuric acid. A method of coagulating and precipitating with a band at pH 6 to 9 is known, and when iron is used, all are treated with alkalinity, particularly pH 9 to 11 (for example, JP-A-61-291094).
しかしながら、このような従来の処理方法はいずれも
効率的な方法ではなく、薬剤を多量に使用してもアンチ
モンを高度に除去することが困難であり、処理水中のア
ンチモン濃度が高く、そのまま放流できないという問題
点があった。However, none of these conventional treatment methods are efficient methods, and it is difficult to remove antimony to a high degree even if a large amount of a drug is used, and the concentration of antimony in the treated water is high, and it cannot be discharged as it is. There was a problem.
この発明は上記問題点を解決するためのもので、簡単
な操作によりアンチモンを高度かつ効率的に除去できる
アンチモン含有水の処理方法を提案することを目的とし
ている。The present invention is intended to solve the above problems, and an object of the present invention is to propose a method for treating antimony-containing water capable of highly efficiently removing antimony by a simple operation.
この発明は、アンチモン含有水を第二鉄塩の存在下
で、かつpH4〜７に調整して不溶性の沈殿物を生成さ
せ、固液分離することを特徴とするアンチモン含有水の
処理方法である。The present invention is a method for treating antimony-containing water, characterized in that antimony-containing water is adjusted to pH 4 to 7 in the presence of ferric salt to form an insoluble precipitate, and solid-liquid separation is performed. .
本発明において処理の対象となるアンチモン含有水
は、めっき廃水などの３価または５価のアンチモンイオ
ンを含む水であり、鉄イオンその他の金属イオンおよび
有機物を含んでいてもよい。The antimony-containing water to be treated in the present invention is water containing trivalent or pentavalent antimony ions such as plating waste water, and may contain iron ions and other metal ions and organic substances.
水中におけるアンチモンは種々の形態で存在してお
り、アンチモンを安定して除去するためにはアンチモン
含有水を予め前処理しておくのが望ましい。すなわち一
般にアンチモンは５価と３価が存在するが、後述の実施
例からも分かるように、５価の方が３価よりも除去し易
く、第二鉄塩による処理に先立ち曝気等により３価のも
のを５価に酸化しておくのが好ましい。酸化のための曝
気は通常20分〜３時間程度でよい。この曝気による酸化
は処理に先立って前処理として行ってもよいが、第二鉄
塩により処理する反応槽内で撹拌を兼ねて行ってもよ
い。Antimony in water exists in various forms, and it is desirable to pretreat antimony-containing water in advance in order to stably remove antimony. That is, generally, antimony has five valences and three valences, but as will be understood from the examples described later, the five valences are easier to remove than the three valences, and the trivalents are trivalent by aeration or the like prior to the treatment with ferric salt. It is preferable to oxidize the above compound to pentavalent. The aeration for oxidation is usually 20 minutes to 3 hours. This oxidation by aeration may be carried out as a pretreatment prior to the treatment, but it may also be carried out with stirring in the reaction tank treated with the ferric salt.
また、アンチモン含有水に有機物が含まれている場合
には、第二鉄塩による処理の前に生物処理等を行って有
機物を除去しておくのが望ましい。生物処理は通常の活
性汚泥法、接触酸化法など任意の手段が利用できる。生
物処理等により有機物を除去すると、アンチモン除去効
果が安定する。特に有機酸が存在するとアンチモンと有
機酸とが錯塩を形成し、第二鉄塩による処理では除去効
果が悪いが、生物処理により有機酸を除去しておくと処
理効果が向上する。Further, when the antimony-containing water contains organic matter, it is desirable to remove the organic matter by performing biological treatment or the like before the treatment with the ferric salt. For biological treatment, any means such as ordinary activated sludge method and catalytic oxidation method can be used. When organic substances are removed by biological treatment or the like, the antimony removing effect becomes stable. In particular, when an organic acid is present, antimony and an organic acid form a complex salt, and the removal effect is poor with the treatment with ferric salt, but the removal of the organic acid by biological treatment improves the treatment effect.
本発明による処理方法は、まずアンチモン含有水を第
二鉄塩の存在下においてpH4〜７、好ましくはpH4〜６に
調整することにより不溶性の沈殿物を生成させる。In the treatment method according to the present invention, an insoluble precipitate is produced by first adjusting the pH of the antimony-containing water to pH 4 to 7, preferably pH 4 to 6 in the presence of ferric salt.
本発明において使用する第二鉄塩としては、硫酸第二
鉄、塩化第二鉄など任意のものが使用でき、これらは単
独でまたは組合せて使用可能である。また第一鉄塩を添
加して反応槽内で曝気して第二鉄塩としてもよい。第二
鉄塩の添加量は原水および処理水中のアンチモンの濃度
により異なるが、原水中のアンチモン濃度１に対し、重
量比でFe3+として５〜200が目安となり、多い程よい
が、処理水質との兼ねあいで任意に決めてよい。As the ferric salt used in the present invention, any one such as ferric sulfate and ferric chloride can be used, and these can be used alone or in combination. Alternatively, a ferrous salt may be added and aerated in the reaction tank to form a ferric salt. The amount of ferric salt added varies depending on the concentration of antimony in the raw water and the treated water, but 5 to 200 as Fe 3+ in weight ratio to the antimony concentration of 1 in the raw water is a guide, and the higher the better, the better the treated water quality. It may be arbitrarily decided depending on the balance.
pH調整は必要により水酸化ナトリウムなどのアルカリ
剤または塩酸、硫酸などの酸を添加して行う。処理水中
のアンチモン濃度をできるだけ低下させるにはpH4〜７
好ましくはpH4〜６に調節することが望ましい。鉄塩の
添加、ならびにpH調節の順序は特に限定されない。If necessary, pH is adjusted by adding an alkaline agent such as sodium hydroxide or an acid such as hydrochloric acid or sulfuric acid. To reduce the concentration of antimony in treated water as much as possible, pH 4 to 7
It is desirable to adjust the pH to 4-6. The order of adding the iron salt and adjusting the pH is not particularly limited.
以上のようにアンチモン含有水を鉄塩の存在下にpH4
〜７に調節して５〜30分間程度反応させると、アンチモ
ンは不溶性の沈殿物となって析出するので、固液分離に
より固形分を除去する。固液分離の方法としては、沈
殿、濾過、遠心分離、限外濾過、精度濾過など任意のも
のが採用できる。固液分離に際しては、高分子凝集剤を
添加して分離を促進させるのが好ましい。As described above, antimony-containing water was adjusted to pH 4 in the presence of iron salts.
When the reaction is adjusted to -7 and reacted for about 5 to 30 minutes, antimony precipitates as an insoluble precipitate, so the solid content is removed by solid-liquid separation. As the method for solid-liquid separation, any method such as precipitation, filtration, centrifugation, ultrafiltration, precision filtration can be adopted. In solid-liquid separation, it is preferable to add a polymer flocculant to accelerate the separation.
アンチモンが沈殿除去される機構は明確ではないが、
共沈によるものと推測される。この場合アンチモンを含
んだ不溶性の沈殿物が析出し、自然沈殿などによって容
易に固液分離できる。固液分離された固形分は汚泥とし
て濃縮、脱水等の処理をして系外に排出する。The mechanism by which antimony is precipitated and removed is not clear,
It is presumed to be due to coprecipitation. In this case, an insoluble precipitate containing antimony is deposited, and solid-liquid separation can be easily performed by natural precipitation or the like. The solid content separated by solid-liquid separation is concentrated and dehydrated as sludge and discharged to the outside of the system.
第二鉄塩の存在下におけるpH調整による不溶性沈殿物
の生成および固液分離は２段階に行うことができ、これ
によりアンチモンの除去率は向上する。この場合、第１
段階の固液分離した分離液に再度第二鉄塩を添加しpH調
整して沈殿物を生成させ、固液分離を行う。２段階処理
の場合、第２段階の沈殿物を原水に添加して第１段階の
沈殿物の生成を行うと、薬品の添加量を少なくできると
ともに、汚泥の発生量も少なくなる。The formation of an insoluble precipitate and the solid-liquid separation by adjusting the pH in the presence of ferric salt can be performed in two stages, which improves the removal rate of antimony. In this case, the first
Ferric salt is again added to the separated liquid obtained in the step of solid-liquid separation to adjust the pH to form a precipitate, and solid-liquid separation is performed. In the case of the two-stage treatment, when the second-stage precipitate is added to the raw water to generate the first-stage precipitate, the amount of chemicals added can be reduced and the amount of sludge generated is reduced.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
実施例１ 五塩化アンチモン1g（Sbとして）水10に加えて30分
間撹拌した。このアンチモン含有水に塩化第二鉄1000mg
/（Feとして）を添加し、水酸化ナトリウムまたは塩
酸を用いて種々のpHに調整し、５分間撹拌した。次に高
分子凝集剤を1mg/加え、固液分離した。上澄水を濾紙
No.5Aで濾過し、濾液についてアンチモン濃度を測定し
た結果（Ａ）を第１図に示す。また比較のために、塩化
第二鉄の代りに、塩化第一鉄（Ｂ）、硫酸バンド（Ｃ）
および塩化カルシウム（Ｄ）を各々単独で使用した場合
の結果を第１図に併記する。Example 1 1 g of antimony pentachloride (as Sb) was added to water 10 and stirred for 30 minutes. 1000 mg of ferric chloride in this antimony-containing water
/ (As Fe) was added, adjusted to various pHs with sodium hydroxide or hydrochloric acid and stirred for 5 minutes. Next, 1 mg / polymeric flocculant was added and solid-liquid separation was performed. Clear water with filter paper
FIG. 1 shows the result (A) obtained by measuring the antimony concentration of the filtrate after filtration with No. 5A. Also, for comparison, instead of ferric chloride, ferrous chloride (B), sulfuric acid band (C)
The results when calcium chloride (D) and calcium chloride (D) are used alone are also shown in FIG.
実施例２ 実施例１において五塩化アンチモンの代りに三塩化ア
ンチモンを使用した以外は実施例１と同様に試験した結
果を第２図に示す。Example 2 The results of the same test as in Example 1 except that antimony trichloride was used instead of antimony pentachloride in Example 1 are shown in FIG.
実施例３ 実施例２において、予めアンチモン含有水を２時間空
気曝気した後同様の処理を行った結果（Ｅ）、および曝
気を行わなかった結果（Ｆ）を第３図に示す。Example 3 FIG. 3 shows the result (E) of the same treatment as in Example 2 in which the antimony-containing water was previously aerated with air for 2 hours and the result (F) without the aeration.
実施例４ 五塩化アンチモン0.1g（Sbとして）および乳酸5gを水
10に加え、pH4に調整して撹拌し、アンチモン含有水
とした。この水に活性汚泥を約200mg/、栄養剤として
硫酸アンモニウム25mg/（Ｎとして）、およびリン酸
カリウム5mg/（Ｐとして）をそれぞれ添加し、空気曝
気して24時間生物処理を行った。この生物処理水を遠心
分離し、その上澄水に硫酸第二鉄の種々の量で添加し、
pH5に調整して５分間撹拌した。次に、高分子凝集剤を1
mg/添加して沈殿、濾過した。濾過水のアンチモンを
測定した結果（Ｇ）を第４図に示す。第４図には生物処
理しなかった場合の結果（Ｈ）を併記する。Example 4 Antimony pentachloride 0.1 g (as Sb) and lactic acid 5 g in water
In addition to 10, the pH was adjusted to 4 and stirred to obtain antimony-containing water. Activated sludge of about 200 mg /, ammonium sulfate of 25 mg / (as N) and potassium phosphate of 5 mg / (as P) were added to this water, respectively, and aerated with air for biological treatment for 24 hours. The biologically treated water was centrifuged, and various amounts of ferric sulfate were added to the supernatant water,
The pH was adjusted to 5 and stirred for 5 minutes. Next, add 1
mg / added to precipitate and filter. The result (G) of measuring antimony of the filtered water is shown in FIG. FIG. 4 also shows the result (H) when the biological treatment was not performed.
以上の結果より、第二鉄塩の存在下でpH4〜７に調整
した場合は他の場合に比べてアンチモンの除去率が高
く、特にアンチモンを酸化した場合、ならびに有機物を
除去した場合にはアンチモン除去率がさらに高くなるこ
とがわかる。From the above results, when the pH is adjusted to 4 to 7 in the presence of ferric salt, the removal rate of antimony is higher than that in other cases, and in particular, when antimony is oxidized and when organic matter is removed, antimony is removed. It can be seen that the removal rate becomes higher.
〔発明の効果〕 以上の通り、本発明によれば、アンチモン含有水を第
二鉄塩の存在下にpH4〜７に調整して固液分離するよう
にしたので、簡単な操作によりアンチモンを高度かつ能
率的に除去することができる。[Effects of the Invention] As described above, according to the present invention, since the antimony-containing water is adjusted to pH 4 to 7 in the presence of ferric salt to perform solid-liquid separation, antimony is highly advanced by a simple operation. And it can be removed efficiently.
第１図ないし第４図は実施例の結果を示すグラフであ
る。1 to 4 are graphs showing the results of the examples.
Claims (3)
かつpH4〜７に調整して不溶性の沈殿物を生成させ、固
液分離することを特徴とするアンチモン含有水の処理方
法。1. Antimony-containing water in the presence of a ferric salt,
A method for treating antimony-containing water, which comprises adjusting the pH to 4 to 7 to form an insoluble precipitate, and performing solid-liquid separation.
チモンを５価にしたものである特許請求の範囲第１項記
載の処理方法。2. The treatment method according to claim 1, wherein the antimony-containing water is obtained by aeration of trivalent antimony into pentavalent water.
を除去したものである特許請求の範囲第１項または第２
項記載の処理方法。3. An antimony-containing water obtained by removing organic matter by biological treatment, according to claim 1 or 2.
The processing method described in the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62070255A JP2504039B2 (en) | 1987-03-26 | 1987-03-26 | Treatment method of water containing antimony |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62070255A JP2504039B2 (en) | 1987-03-26 | 1987-03-26 | Treatment method of water containing antimony |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63236592A JPS63236592A (en) | 1988-10-03 |
| JP2504039B2 true JP2504039B2 (en) | 1996-06-05 |
Family
ID=13426263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62070255A Expired - Lifetime JP2504039B2 (en) | 1987-03-26 | 1987-03-26 | Treatment method of water containing antimony |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2504039B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8614280B2 (en) | 2008-04-15 | 2013-12-24 | Basf Se | Method for the continuous production of biodegradable polyesters |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4868411B2 (en) * | 2007-09-19 | 2012-02-01 | 日鉄鉱業株式会社 | Purification method for wastewater containing antimony |
| CN103011461A (en) * | 2012-12-28 | 2013-04-03 | 哈尔滨工业大学 | Method of removing antimony (III) in source water by combining ferric salt coagulation pretreatment and ultrafiltration short flow process |
| JP7134658B2 (en) * | 2017-05-30 | 2022-09-12 | Ｊｘ金属株式会社 | Sb removal method and valuable metal recovery method |
| CN107601718B (en) * | 2017-10-25 | 2020-04-21 | 北京中持净水材料技术有限公司 | Method for removing organic antimony in industrial wastewater of typical industry |
| JP7199685B2 (en) * | 2018-05-22 | 2023-01-06 | 壽環境機材株式会社 | Wastewater treatment equipment and wastewater treatment method |
| CN111362385A (en) * | 2020-03-11 | 2020-07-03 | 江苏南大华兴环保科技股份公司 | Method for treating river water polluted by antimony |
| CN114105409A (en) * | 2021-11-19 | 2022-03-01 | 苏州中晟环境修复有限公司 | Method for treating antimony in underground water polluted by printing and dyeing wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61291095A (en) * | 1985-06-18 | 1986-12-20 | Kurita Water Ind Ltd | Treatment of water containing antimony |
-
1987
- 1987-03-26 JP JP62070255A patent/JP2504039B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61291095A (en) * | 1985-06-18 | 1986-12-20 | Kurita Water Ind Ltd | Treatment of water containing antimony |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8614280B2 (en) | 2008-04-15 | 2013-12-24 | Basf Se | Method for the continuous production of biodegradable polyesters |
| US9040639B2 (en) | 2008-04-15 | 2015-05-26 | Basf Se | Method for the continuous production of biodegradable polyesters |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63236592A (en) | 1988-10-03 |
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