JP2835772B2 - Heavy metal removal method for iron chloride waste liquid - Google Patents
Heavy metal removal method for iron chloride waste liquidInfo
- Publication number
- JP2835772B2 JP2835772B2 JP2116388A JP11638890A JP2835772B2 JP 2835772 B2 JP2835772 B2 JP 2835772B2 JP 2116388 A JP2116388 A JP 2116388A JP 11638890 A JP11638890 A JP 11638890A JP 2835772 B2 JP2835772 B2 JP 2835772B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- iron powder
- iron
- nickel
- copper
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、銅、ニッケル等を含む塩化鉄系の廃液（例
えば、エッチング液）から銅、ニッケル等の重金属を除
去する方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for removing heavy metals such as copper and nickel from an iron chloride-based waste liquid (eg, an etching solution) containing copper and nickel.
従来、特公昭61−44814号公報記載の如く、鉄以外の
重金属を含む強酸性塩化第二鉄廃液に塊状の金属鉄を混
入し、加温状態に保持しかつ撹拌することで析出した重
金属を除去する塩化鉄系廃液の重金属除去方法が提案さ
れている。Conventionally, as described in Japanese Patent Publication No. 61-44814, heavy metallic iron was mixed with a strongly acidic ferric chloride waste liquid containing heavy metals other than iron, and the heavy metal precipitated by stirring and maintaining the heated state was stirred. A method for removing heavy metals from the iron chloride waste liquid to be removed has been proposed.
しかしながら、上記従来例に係る方法においては、中
和素材として塊状の金属鉄を用いるため、強酸性でない
塩化鉄系廃液の場合には、中和、分離反応性が悪いとい
う問題点があり、更には、塊状の金属鉄を投入した後
は、撹拌装置の設計が難しく、仮に可能であっても撹拌
装置に多大の費用がかかるという欠点があった。However, in the method according to the above conventional example, since a lump of metallic iron is used as a neutralizing material, in the case of an iron chloride waste liquid that is not strongly acidic, there is a problem that neutralization and separation reactivity are poor, and However, it is difficult to design a stirrer after the lump of metallic iron is charged, and even if possible, the stirrer has a disadvantage that a great deal of cost is required.
上記方法をニッケルを含む塩化鉄系廃液に適応した場
合には、ニッケルの分離性能が悪いという問題点があっ
た。When the above method is applied to an iron chloride waste liquid containing nickel, there is a problem that the nickel separation performance is poor.
本発明はこのような事情に鑑みてなされたもので、装
置全体を比較的安価に製造でき、ニッケルの分離性能も
良い塩化鉄系廃液の重金属除去方法を提供することを目
的とする。The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for removing heavy metals from iron chloride waste liquid, which can manufacture the entire apparatus at relatively low cost and has good nickel separation performance.
上記目的に沿う本発明に係る塩化鉄系廃液の重金属除
去方法は、銅及びニッケルを含む塩化鉄系の廃液に鉄粉
を混入して銅を沈澱させる工程と、上記工程で銅が除去
された廃液に鉄粉と少量の塩化第二鉄を混入することに
よって鉄粉を活性化してニッケルの除去を行う工程とを
有して構成されている。A method for removing heavy metals from an iron chloride waste liquid according to the present invention, which meets the above object, comprises the steps of: mixing iron powder in an iron chloride waste liquid containing copper and nickel to precipitate copper; and removing copper in the above step. A step of activating the iron powder by mixing the iron powder and a small amount of ferric chloride into the waste liquid to remove nickel.
ここで、上記鉄粉は転炉から回収された精製鉄粉（OG
P）を使用することも可能である。Here, the above-mentioned iron powder is refined iron powder (OG
P) can also be used.
エッチング液等の塩化鉄系廃液は、その成分は塩化第
二鉄を主成分とするが、これにエッチング過程で銅ある
いはニッケル等の金属が溶解してイオンとなり、更には
三価の鉄イオンが還元された二価の鉄イオンが混入して
いる。Ferric chloride-based waste liquid such as an etchant contains ferric chloride as a main component, and a metal such as copper or nickel dissolves in the etching process to form ions, and furthermore, trivalent iron ions are formed. Reduced divalent iron ions are mixed.
従って、まず廃液を適当な温度に加温した後、鉄粉あ
るいは転炉から回収された精製鉄粉を加えてORP（酸化
還元電位）の調整を行い、次の反応を生じさせる。Therefore, first, the waste liquid is heated to an appropriate temperature, and iron powder or purified iron powder recovered from the converter is added to adjust the ORP (oxidation-reduction potential), thereby causing the next reaction.
2FeCl3＋Fe→3FeCl2 CuCl2 ＋Fe→ FeCl2＋Cu 上記処理を行うことによってCuが析出沈澱するので、
沈澱物を除去した上澄み液に、鉄粉あるいは転炉から回
収された精製鉄粉と少量の塩化第二鉄を入れて、ORP及
びPHを調整し、次の反応を生じさせる。2FeCl 3 + Fe → 3FeCl 2 CuCl 2 + Fe → FeCl 2 + Cu By performing the above treatment, Cu precipitates and precipitates.
To the supernatant from which the precipitate has been removed, iron powder or purified iron powder recovered from the converter and a small amount of ferric chloride are added to adjust ORP and PH, and the next reaction is caused.
NiCl2＋Fe→FeCl2＋Ni この場合、投入した鉄の表面に不動態の膜を作り反応
の進行を妨げる。そこで、少量の塩化第二鉄を混入する
ことによって、不動態の膜の生成を防止し、鉄粉の表面
を活性化し鉄粉の反応を進行させると共に、析出したニ
ッケルを該鉄粉に付着させて沈澱物を生じさせる。NiCl 2 + Fe → FeCl 2 + Ni In this case, a passive film is formed on the surface of the introduced iron to hinder the progress of the reaction. Therefore, by mixing a small amount of ferric chloride, the formation of a passive film is prevented, the surface of the iron powder is activated and the reaction of the iron powder proceeds, and the precipitated nickel is adhered to the iron powder. To form a precipitate.
これによってニッケルが除去され、上澄み液は少量の
塩化第二鉄を含む塩化第一鉄液となる。This removes the nickel and the supernatant becomes a ferrous chloride solution containing a small amount of ferric chloride.
続いて、添付した図面を参照しつつ、本発明を具体化
した実施例につき説明し、本発明の理解に供する。Next, embodiments of the present invention will be described with reference to the accompanying drawings to provide an understanding of the present invention.
第１図は本発明の一実施例に係る塩化鉄系廃液の重金
属除去方法を示すフロー図である。FIG. 1 is a flow chart showing a method for removing heavy metals from iron chloride waste liquid according to one embodiment of the present invention.
第１図に示すように、塩化鉄系廃液の一例であるエッ
チング液500gを、小型の第１撹拌槽に入れて40〜100℃
程度に加温し、鉄粉の一例である転炉回収精製鉄粉を投
入し、ORP（酸化還元電位）を−300〜−350mVに調整す
る。これによって次の反応が起こり、塩化第二鉄は塩化
第一鉄に代わり、更に含有する銅が溶液中に析出して懸
濁液となる。As shown in FIG. 1, 500 g of an etching solution, which is an example of an iron chloride waste solution, is placed in a small first stirring tank and heated to 40 to 100 ° C.
Then, the purified iron powder recovered from the converter, which is an example of the iron powder, is charged, and the ORP (oxidation-reduction potential) is adjusted to −300 to −350 mV. As a result, the following reaction occurs, and ferric chloride replaces ferrous chloride, and further contained copper precipitates in the solution to form a suspension.
2FeCl3＋Fe→3FeCl2 CuCl2 ＋Fe→ FeCl2＋Cu そこで、この懸濁液を別槽あるいは側部の補助槽に取
込み析出した銅を沈澱させ、その上澄み液を第２撹拌槽
に入れる。なお、上記銅の沈澱物は銅資源として再利用
する。2FeCl 3 + Fe → 3FeCl 2 CuCl 2 + Fe → FeCl 2 + Cu Then, this suspension is taken into another tank or an auxiliary tank on the side to precipitate the precipitated copper, and the supernatant is put into the second stirring tank. The copper precipitate is reused as copper resources.
次に、第２撹拌槽においては、温度を40〜100℃にし
た状態で、まず、少量の塩化第二鉄を入れ、上記転炉回
収精製鉄粉（OGPという）を入れて、ORPを−450mV以
下、PHを３以下に調整する。Next, in the second stirring tank, at a temperature of 40 to 100 ° C., first, a small amount of ferric chloride is added, and the above-mentioned converter recovered purified iron powder (referred to as OGP) is added. Adjust 450mV or less and PH to 3 or less.
これによって、次の反応が生じニッケルが析出する。 As a result, the following reaction occurs and nickel is deposited.
NiCl2＋Fe→FeCl2＋Ni そして、投入した少量の塩化第二鉄液によって上記鉄
粉の表面が活性化され、不動態の膜の発生を阻み、反応
を進め、析出したニッケルを吸着して沈澱する。NiCl 2 + Fe → FeCl 2 + Ni Then, the surface of the iron powder is activated by a small amount of ferric chloride solution added, preventing the formation of a passive film, promoting the reaction, adsorbing the precipitated nickel and precipitating. I do.
上記沈澱物は鉄粉にニッケルが付着した粒として回収
されるので、ニッケルのみを回収する場合には、その後
該沈澱物をニッケル付着鉄粉として回収するかあるい
は、化学反応を利用した処理によってニッケルのみを回
収することになる。Since the precipitate is collected as particles in which nickel has adhered to the iron powder, when only nickel is to be recovered, the precipitate is then recovered as nickel-adhered iron powder or nickel is treated by a chemical reaction. Only will be collected.
上記沈澱物を除いた溶液は少しの塩化第二鉄が混じっ
た塩化第一鉄溶液となる。The solution excluding the precipitate becomes a ferrous chloride solution mixed with a small amount of ferric chloride.
そこで、塩素ガスを吹き込むことによって、塩化第一
鉄を酸化させて塩化第二鉄とする。これによって、廃液
の再生も完全に行われ、再度該塩化第二鉄液をエッチン
グ液として使用することができる。Therefore, by blowing chlorine gas, ferrous chloride is oxidized to ferric chloride. As a result, the waste liquid is completely regenerated, and the ferric chloride liquid can be used again as an etching liquid.
なお、上記実施例においては鉄粉として転炉回収精製
鉄粉を使用したが、通常の機械処理によって製造される
鉄粉を使用することもできる。In the above embodiment, the converter recovered and purified iron powder was used as the iron powder, but iron powder produced by ordinary mechanical processing may be used.
本発明に係る重金属除去方法は以上の説明からも明ら
かなように、銅及びニッケルを個別に分離しているの
で、それぞれを銅資源及びニッケル資源として有効に活
用することができる。As is clear from the above description, the method for removing heavy metals according to the present invention separates copper and nickel, so that they can be effectively utilized as copper resources and nickel resources, respectively.
しかも、処理された塩化鉄系廃液は不純物が除去され
ているので、例えば、塩素ガスを吹き込んで酸化させる
等の処理を行ってエッチング液として再生することもで
きる。In addition, since the treated iron chloride waste liquid is free of impurities, it can be regenerated as an etching liquid by performing a process such as blowing chlorine gas to oxidize.
特に、鉄粉として転炉回収精製鉄粉を使用することに
よって、製鉄所から発生する副産物を有効に利用でき
る。In particular, by using the converter recovered and purified iron powder as the iron powder, by-products generated from the steelworks can be effectively used.
第１図は本発明の一実施例に係る塩化鉄系廃液の重金属
除去方法を示したフロー図である。FIG. 1 is a flow chart showing a method for removing heavy metals from an iron chloride waste liquid according to one embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ２５Ｆ 7/02 Ｃ２２Ｂ 23/04 (72)発明者 永岡 米治郎 福岡県北九州市戸畑区飛幡町１番１号 新日本製鐵株式會社八幡製鐵所内 (56)参考文献 特開 平１−167235（ＪＰ，Ａ) 特開 昭59−157283（ＪＰ，Ａ) 特開 昭59−229490（ＪＰ，Ａ) 特公 昭61−44814（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.6，ＤＢ名) C02F 1/62 C23F 1/46 C25F 7/02 C22B 15/12 C22B 23/04 C01G 49/10────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification symbol FI C25F 7/02 C22B 23/04 (72) Inventor Yonejiro Nagaoka 1-1-1, Tobata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka Nippon Steel Corporation (56) References JP-A-1-167235 (JP, A) JP-A-59-157283 (JP, A) JP-A-59-229490 (JP, A) JP-B-61-44814 (JP, B2) (58) Fields surveyed (Int. Cl. 6 , DB name) C02F 1/62 C23F 1/46 C25F 7/02 C22B 15/12 C22B 23/04 C01G 49/10
Claims (1)
粉を混入して銅を沈澱させる工程と、上記工程で銅が除
去された廃液に鉄粉と少量の塩化第二鉄を混入すること
によって鉄粉を活性化してニッケルの除去を行う工程と
を有することを特徴とする塩化鉄系廃液の重金属除去方
法1. A step of mixing iron powder into an iron chloride waste liquid containing copper and nickel to precipitate copper, and mixing iron powder and a small amount of ferric chloride into the waste liquid from which copper has been removed in the above step. Removing the nickel by activating the iron powder by removing the iron powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2116388A JP2835772B2 (en) | 1990-05-01 | 1990-05-01 | Heavy metal removal method for iron chloride waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2116388A JP2835772B2 (en) | 1990-05-01 | 1990-05-01 | Heavy metal removal method for iron chloride waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0411989A JPH0411989A (en) | 1992-01-16 |
| JP2835772B2 true JP2835772B2 (en) | 1998-12-14 |
Family
ID=14685789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2116388A Expired - Lifetime JP2835772B2 (en) | 1990-05-01 | 1990-05-01 | Heavy metal removal method for iron chloride waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2835772B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0774404B2 (en) * | 1991-04-12 | 1995-08-09 | 播磨化学工業株式会社 | Method for recovering metallic nickel from ferric chloride waste liquid |
| US5472618A (en) * | 1994-02-07 | 1995-12-05 | Great Western Chemical Company | Method for recovering metals from solutions |
| KR20080027911A (en) * | 2005-07-06 | 2008-03-28 | 가부시키가이샤 신꼬오 간쿄우 솔루션 | Process for recovery of metals and equipment therefor |
| JP2007039788A (en) * | 2005-07-06 | 2007-02-15 | Kobelco Eco-Solutions Co Ltd | Process for recovery of metals and equipment therefor |
-
1990
- 1990-05-01 JP JP2116388A patent/JP2835772B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0411989A (en) | 1992-01-16 |
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