JPH0714513B2 - Treatment method of cyanide waste liquid containing iron - Google Patents
Treatment method of cyanide waste liquid containing ironInfo
- Publication number
- JPH0714513B2 JPH0714513B2 JP57200852A JP20085282A JPH0714513B2 JP H0714513 B2 JPH0714513 B2 JP H0714513B2 JP 57200852 A JP57200852 A JP 57200852A JP 20085282 A JP20085282 A JP 20085282A JP H0714513 B2 JPH0714513 B2 JP H0714513B2
- Authority
- JP
- Japan
- Prior art keywords
- cyan
- copper
- waste liquid
- complex
- iron
- 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
Links
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- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Description
【発明の詳細な説明】 本発明はシアン廃液を有効に処理する方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for effectively treating cyan waste liquid.
メッキ前処理液などシアンを含む廃液はシアンが猛毒で
あるため、その廃棄にあたっては、シアンを無害な炭酸
ガスと窒素ガスに完全に分解させる処理を行うことが公
害防止上不可欠である。Since cyanide is a highly poisonous waste liquid containing cyanide such as a pre-plating treatment solution, it is essential to completely decompose cyanide into harmless carbon dioxide gas and nitrogen gas in order to prevent pollution.
従来このシアン廃液処理には酸化分解処理法が広く用い
られている。Conventionally, the oxidative decomposition treatment method has been widely used for the treatment of this cyan waste liquid.
例えば最も一般的な方法である次亜塩素酸(HOCl)を用
いる酸化分解法はまず(1)式により、pH10以上でシア
ンをシアン酸に変え、次にpHを7.5〜8に下げてシアン
酸を(2)式のようにCO2とN2とに分解する方法であ
る。For example, the oxidative decomposition method using hypochlorous acid (HOCl), which is the most general method, first converts cyan to cyanic acid at pH 10 or higher by the formula (1), and then lowers the pH to 7.5 to 8 to produce cyanic acid. Is a method of decomposing CO 2 and N 2 as in formula (2).
CN-+HOCl→Cl-+HCNO ……(1) 2CNO-+3OCl-+H2O→2CO2+N2+3Cl-+2OH- ……(2) しかしながらシアン廃液中に鉄が存在する場合は鉄が主
としてフエロシアンイオン〔Fe(CN)▲4- 6▼〕の形と
なっておりこのイオンは酸化剤によっても非常に酸化さ
れ難いためこのような廃液は単なる酸化分解法では処理
できないものとされている。 CN - + HOCl → Cl - + HCNO ...... (1) 2CNO - + 3OCl - + H 2 O → 2CO 2 + N 2 + 3Cl - + 2OH - ...... (2) , however the iron when iron is present in the cyan liquid waste mainly Hue Russian ions [Fe (CN) ▲ 4- 6 ▼] such waste for hard to be very oxidized even has a form the ions by oxidation agents are those which can not be treated just oxidative decomposition method.
このため鉄を含むシアン廃液の処理方法として酸化分解
処理後該液に硫酸第1鉄を加えて(3)式により鉄をフ
エロシアンの第1鉄塩として沈澱させる方法がとられて
いる。For this reason, as a treatment method of a cyan waste liquid containing iron, a method of adding ferrous sulfate to the liquid after oxidative decomposition treatment and precipitating iron as ferrous cyan ferrous salt according to the formula (3) is adopted.
Fe(CN)▲4- 6▼+2Fe2+→Fe2〔Fe(CN)6〕↓……(3) しかし、(3)式によって生ずる沈澱は空気中の酸素よ
って酸化されたり、紫外線の作用によったりして可溶性
の塩に変化しやすい性質があり処理後に再び廃液中のシ
アン濃度が増加する危険を有しこの2段の処理によって
もシアン廃液のシアン濃度を充分に下げることは困難で
ある。Fe (CN) ▲ 4- 6 ▼ + 2 Fe 2+ → Fe 2 [Fe (CN) 6 ] ↓ …… (3) However, the precipitate generated by the formula (3) is oxidized by oxygen in the air, or the action of ultraviolet rays. Therefore, there is a risk that the soluble salt tends to change, and there is a risk that the cyan concentration in the waste liquid will increase again after the treatment. It is difficult to sufficiently reduce the cyan concentration of the cyan waste liquid even by this two-stage treatment. is there.
本発明はこのような状況に鑑み種々検討の結果鉄を含ん
でいる場合でもシアン廃液の処理後のシアン濃度を1mg/
l以下にできる処理方法を開発したもので、鉄を含むシ
アン廃液を酸化分解処理する方法において、該廃液中に
含まれるフリーシアン、フエロシアン錯体及び該フエロ
シアン錯体よりも安定数の小さなシアン錯体を銅シアン
錯体に変えるのに必要な当量以上の銅イオンを添加し
て、フエロシアン錯体を銅シアン錯体に変えた後、酸化
分解処理を行うことを特徴とする 鉄を含むシアン廃液に、可溶性の銅塩類または銅溶液に
よって銅イオンを添加するとフエロシアンイオンとなっ
ている鉄は、(4)式により銅と置換され銅シアンイオ
ン〔Cu(CN)▲2- 4▼〕が生じ、この鉄は水酸基と結合
して水酸化物となって沈澱する。銅シアンイオンは通常
の酸化分解処理によって完全に処理できる。In the present invention, in consideration of such a situation, the cyan concentration after treatment of the cyan waste liquid is 1 mg / m even when it contains iron as a result of various studies.
We have developed a treatment method capable of reducing the amount of iron to less than 1. In the method of oxidative decomposition treatment of a cyan waste liquid containing iron, free cyan contained in the waste liquid, a ferrocyan complex and a cyan complex having a stable number smaller than that of the ferrocyan complex are treated with copper. A copper cyanide containing iron, which is characterized in that ferrocyan complex is converted to a copper cyan complex by adding copper ions in an amount equal to or more than the amount required to convert to a cyan complex, and then oxidative decomposition treatment is performed. or iron that is the addition of copper ions and Hue Russian ions by copper solution (4) copper and substituted copper cyanide ion [Cu (CN) ▲ 2-4 ▼] is produced by expression, the iron and a hydroxyl group They combine to form hydroxides and precipitate. Copper cyanide can be completely treated by a conventional oxidative decomposition treatment.
2Fe(CN)▲4- 6▼+3Cu2+→3Cu(CN)▲2- 4▼+2Fe2+…
…(4) なお、フエリシアンイオン〔Fe(CN)▲3- 6▼〕となっ
ている鉄は、このイオンの安定度定数が銅シアンイオン
のそれよりも大きいため銅と置換されることはないが、
フエリシアンイオンは銅シアンイオンと同様に通常の方
法で酸化分解されるので問題はない。 2Fe (CN) ▲ 4- 6 ▼ + 3Cu 2+ → 3Cu (CN) ▲ 2- 4 ▼ + 2Fe 2+ ...
... (4) In addition, iron has a full collar cyanide ion [Fe (CN) ▲ 3- 6 ▼] can be stability constant of the ion is replaced with larger for copper than copper cyanide ions But not
Since the ferricyan ion is oxidized and decomposed by the usual method like the copper cyan ion, there is no problem.
しかして酸化処理前の銅イオン添加量を上記の如く限定
したのは次の理由による。The reason why the amount of copper ions added before the oxidation treatment is limited as described above is as follows.
フリーシアンやカドミウム、亜鉛、第1鉄など銅シアン
錯体よりも安定度定数の小さなシアン錯体を形成する金
属の含まれているシアン廃液に銅イオンを添加すると銅
イオンは安定度定数の小さなシアン錯体を形成している
金属と順次置換して(5)(6)(7)(8)式により
銅シアン錯体を形成する 4CN-+Cu2+→Cu(CN)▲2- 4▼ ……(5) Cd(CN)▲2- 4▼+Cu2+→Cu(CN)▲2- 4▼ ……(6) Zn(CN)▲2- 4▼+Cu2+→Cu(CN)▲2- 4▼ ……(7) 2Fe(CN)▲4- 6▼+3Cu2+→3Cu(CN)▲2- 4▼ ……
(8) 従って(5)、(6)、(7)式による反応が完結した
後(4)式(又は(8)式)による反応が完了するの
で、第1鉄を銅と完全に置換するにはフリーシアン、フ
エロシアン錯体及び該フエロシアン錯体よりも安定数の
小さなシアン錯体を銅シアン錯体に変えるのに必要な当
量以上の銅イオンを添加しなければならない。シアン廃
液中の鉄は大部分が第1鉄として存在しているから実操
業上は第1鉄、第2鉄の分離分析が困難であることから
全体の鉄に対して当量となるように銅イオンの添加量を
決定しても何等差し支えはない。When copper ions are added to a cyan waste liquid containing a metal that forms a cyan complex having a smaller stability constant than copper cyan complexes such as free cyan, cadmium, zinc, and ferrous iron, copper ions have a small stability constant. sequentially replaced with the metal forming the (5) (6) (7 ) (8) 4CN forming copper cyanide complexes by formula - + Cu 2+ → Cu (CN ) ▲ 2- 4 ▼ ...... (5 ) Cd (CN) ▲ 2- 4 ▼ + Cu 2+ → Cu (CN) ▲ 2- 4 ▼ ...... (6) Zn (CN) ▲ 2- 4 ▼ + Cu 2+ → Cu (CN) ▲ 2- 4 ▼ ...... (7) 2Fe (CN) ▲ 4- 6 ▼ + 3Cu 2+ → 3Cu (CN) ▲ 2- 4 ▼ ......
(8) Therefore, after the reaction according to the equations (5), (6) and (7) is completed, the reaction according to the equation (4) (or the equation (8)) is completed, so that the ferrous iron is completely replaced with copper. In order to convert the free cyan, the ferrocyan complex, and the cyan complex having a stable number smaller than that of the ferrocyan complex into the copper cyan complex, copper ions must be added in an amount equal to or more than the equivalent amount. Most of the iron in the cyanogen effluent is present as ferrous iron, so it is difficult to separate and analyze ferrous and ferric iron in actual operation, so copper should be used in an amount equivalent to the total iron. There is no problem in determining the amount of added ions.
またこのようにして決定した最低限の銅イオン添加量以
上の銅イオンを添加すると過剰の銅イオンは緑色の水酸
化銅となり沈澱するのでシアン廃液の組成や添加する銅
溶液の銅濃度が不明の場合には水酸化銅の沈澱が生成す
る点を銅イオン添加の終点とする方法が、実操業上は便
利である。In addition, if the copper ion is added in excess of the minimum amount of copper ion determined in this way, the excess copper ion becomes green copper hydroxide and precipitates.Therefore, the composition of the cyanogen waste solution and the copper concentration of the added copper solution are unknown. In some cases, it is convenient in practical operation to use the point at which copper hydroxide precipitates as the end point of copper ion addition.
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 鉄3g/l、フリーシアン800mg/lを含む廃液5m3に硫酸銅
溶液(Cu25g/l)1.25m3(フリーシアン、鉄に対し銅1.1
1当量)を加えた後次亜塩素酸ナトリウム溶液(10W/V
%)0.7m2を加えた後pHを8に下げて分解処理を行っ
た。この処理後廃液中に含まれているシアン濃度は0.8m
g/lであった。Example 1 Iron 3 g / l, free cyanide 800 mg / l copper sulfate solution to the waste liquid 5 m 3 comprising (Cu25g / l) 1.25m 3 (free cyanide, copper to iron 1.1
After adding 1 equivalent) sodium hypochlorite solution (10W / V
%) 0.7 m 2 was added and then the pH was lowered to 8 for decomposition. Cyan concentration in the waste liquid after this treatment is 0.8m
It was g / l.
実施例2 実施例1と同じ廃液5m3に硫酸銅溶液(Cu25g/l)1.35m
3(フリーシアン、鉄に対し銅1.20当量)を加えた後次
亜塩素酸ナトリウム溶液(10W/V%)0.7m3を加え酸化処
理後pHを8に下げて分解処理した。この処理後廃液中の
シアン濃度は0.5mg/lであった。Example 2 Copper sulphate solution (Cu25g / l) 1.35m in 5m 3 of the same waste liquid as in Example 1
3 (free cyan, 1.20 equivalents of copper relative to iron) was added, and then 0.7 m 3 of sodium hypochlorite solution (10 W / V%) was added, and after the oxidation treatment, the pH was lowered to 8 for decomposition treatment. The cyanide concentration in the waste liquid after this treatment was 0.5 mg / l.
実施例3 鉄5g/l、フリーシアン600mg/lの廃液7m3に銅を含む廃
液(銅濃度不明)を銅の水酸化物が生成するまで加えそ
の後次亜塩素酸ナトリウム溶液(10W/V%)0.7m3を加え
て酸化処理した後pHを8に下げて分解処理した。この処
理後の廃液のシアン濃度は0.4mg/lであった。Example 3 A waste solution containing copper (copper concentration unknown) was added to 7 m 3 of waste solution of iron 5 g / l and free cyan 600 mg / l until copper hydroxide was formed, and then sodium hypochlorite solution (10 W / V% ) 0.7m 3 was added for oxidation and then pH was lowered to 8 for decomposition. The cyanide concentration of the waste liquid after this treatment was 0.4 mg / l.
比較例 実施例1と同じ廃液5m3に硫酸銅溶液(Cu25g/l)1.0m3
(フリーシアン、鉄に対しCu0.89当量)を加えた後、次
亜塩素酸ナトリウム溶液(10W/V%)0.7m3を加えて酸化
処理後、pHを8に下げて分解処理した。この処理後の廃
液のシアン濃度は30.2mg/lであった。Comparative Example Copper sulfate solution (Cu25g / l) 1.0m 3 in the same waste liquid 5m 3 as in Example 1
(Free cyan, Cu 0.89 equivalent to iron) was added, and then sodium hypochlorite solution (10 W / V%) 0.7 m 3 was added for oxidation treatment, and then the pH was lowered to 8 for decomposition treatment. The cyanide concentration of the waste liquid after this treatment was 30.2 mg / l.
従来例 鉄3g/l、フリーシアン800mg/lを含むシアン廃液4m3に
次亜塩素酸ナトリウム溶液(10W/V%)2m3を加えて酸
化処理した後pHを8に下げて分解処理したが、処理後の
廃液のシアン濃度は45mg/lであった。この処理後の廃液
に更に硫酸第1鉄を加えて沈澱を生成させたが、廃液の
シアン濃度は5.3mg/lであった。Conventional example 4m 3 of cyanogen waste solution containing 3g / l of iron and 800mg / l of free cyan was added with 2m 3 of sodium hypochlorite solution (10W / V%), and then the pH was lowered to 8 for decomposition treatment. The cyanide concentration of the waste liquid after the treatment was 45 mg / l. Ferrous sulfate was further added to the waste liquid after this treatment to form a precipitate, and the cyan concentration of the waste liquid was 5.3 mg / l.
以上述べた如く本発明方法は鉄を含むシアン廃液の処理
を従来法に比べて簡単かつ有効に行なえるものであり、
公害防止上顕著な効果を有するものである。As described above, the method of the present invention can treat cyanide waste liquid containing iron more easily and effectively than the conventional method.
It has a remarkable effect on pollution prevention.
Claims (1)
法において、該廃液中に含まれるフリーシアン、フエロ
シアン錯体及び該フエロシアン錯体よりも安定数の小さ
なシアン錯体を銅シアン錯体に変えるのに必要な当量以
上の銅イオンを添加して、フエロシアン錯体を銅シアン
錯体に変えた後、酸化分解処理を行うことを特徴とする
鉄を含むシアン廃液の処理方法。1. In a method for oxidative decomposition treatment of a cyan waste liquid containing iron, it is necessary to convert a free cyan, a ferrocyan complex and a cyan complex having a stable number smaller than the ferrocyan complex contained in the waste liquid into a copper cyan complex. A method for treating a cyan waste liquid containing iron, which comprises adding a copper ion in an equivalent amount or more to convert a ferrocyan complex into a copper cyan complex, and then performing an oxidative decomposition treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57200852A JPH0714513B2 (en) | 1982-11-16 | 1982-11-16 | Treatment method of cyanide waste liquid containing iron |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57200852A JPH0714513B2 (en) | 1982-11-16 | 1982-11-16 | Treatment method of cyanide waste liquid containing iron |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5990692A JPS5990692A (en) | 1984-05-25 |
JPH0714513B2 true JPH0714513B2 (en) | 1995-02-22 |
Family
ID=16431287
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57200852A Expired - Lifetime JPH0714513B2 (en) | 1982-11-16 | 1982-11-16 | Treatment method of cyanide waste liquid containing iron |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0714513B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1241774A (en) * | 1984-05-23 | 1988-09-06 | Bruce R. Conard | Effluent treatment |
JP6145682B2 (en) * | 2015-10-29 | 2017-06-14 | 株式会社片山化学工業研究所 | Method of treating complex cyanide-containing wastewater and treating agent used therefor |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51121957A (en) * | 1975-04-18 | 1976-10-25 | Asahi Chem Ind Co Ltd | Method of treating waste liquid |
-
1982
- 1982-11-16 JP JP57200852A patent/JPH0714513B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS5990692A (en) | 1984-05-25 |
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