JPH0419310B2 - - Google Patents
Info
- Publication number
- JPH0419310B2 JPH0419310B2 JP21803186A JP21803186A JPH0419310B2 JP H0419310 B2 JPH0419310 B2 JP H0419310B2 JP 21803186 A JP21803186 A JP 21803186A JP 21803186 A JP21803186 A JP 21803186A JP H0419310 B2 JPH0419310 B2 JP H0419310B2
- Authority
- JP
- Japan
- Prior art keywords
- chromate treatment
- current
- treatment solution
- cathode
- metal
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/86—Regeneration of coating baths
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はクロメート処理液の再生方法、特にク
ロメート処理液中に含まれる不要な金属イオンを
イオン交換膜を用いた電解除去法において、電極
上に金属を析出させることなく再生せしめる方法
に係るものである。Detailed Description of the Invention (Industrial Application Field) The present invention is directed to a method for regenerating a chromate treatment solution, particularly in an electrolytic removal method using an ion exchange membrane to remove unnecessary metal ions contained in the chromate treatment solution. This relates to a method of regenerating the metal without depositing metal on the metal.
（従来の技術）
従来から鋼材に亜鉛メツキを施こした材料は各
種屋根材料や工業製品材料として広く利用されて
いる。(Prior Art) Galvanized steel materials have been widely used as various roofing materials and industrial product materials.
亜鉛メツキは、そのままでは亜鉛が耐食性に乏
しい為、短時間で白さびと称する亜鉛の腐食生成
物が生じ、これを抑制する目的で亜鉛表面に化成
被膜を設ける方法が提案されている。 When zinc plating is used as it is, zinc has poor corrosion resistance, so a corrosion product of zinc called white rust occurs in a short period of time.In order to suppress this, a method has been proposed in which a chemical conversion film is provided on the zinc surface.
この方法の代表的手段がクロメート処理と言わ
れるものであり、クロム酸及びある種のアニオン
を含む溶液中に亜鉛メツキ表面を浸漬することに
より、メツキ表面に３価のクロムと６価のクロム
の複合体であるクロム酸クロミウムを主成分とす
る化成被膜を形成させるものである。 A typical means of this method is called chromate treatment, in which trivalent chromium and hexavalent chromium are added to the galvanized surface by immersing it in a solution containing chromic acid and certain anions. It forms a chemical conversion coating whose main component is chromium chromate, which is a complex.
かかるクロメート処理液は、被処理体から溶出
してくる一部の金属イオンや亜鉛、３価のクロム
イオン等の金属イオンが蓄積し、これに新らしい
クロメート処理液を追加して使用する場合には、
クロメート液の濃度管理、溶出金属の蓄積、溶出
金属の被処理体への析出等の不都合が生じる。 Such a chromate treatment solution accumulates some metal ions, zinc, trivalent chromium ions, etc. eluted from the object to be treated, and when a new chromate treatment solution is added and used. teeth,
This causes problems such as concentration control of the chromate solution, accumulation of eluted metal, and precipitation of eluted metal onto the object to be treated.
かかる不都合を回避する為、従来においては溶
出金属が一定の値に達すると液の更新を行なう手
段や、隔膜を用いた電解法によつて溶出金属を除
去する手段等が提案され、又実施されていた。 In order to avoid such inconveniences, conventional methods have been proposed and implemented, such as a method of renewing the liquid when the eluted metal reaches a certain value, and a method of removing the eluted metal by an electrolytic method using a diaphragm. was.
（発明が解決しようとする問題点）
しかしながら、かかる従来法のうち前者の手段
は、使い古した液の処理に当り、公害上の問題が
生ずる欠点があり、又後者の手段は陰極室に移動
した金属イオンが陰極上に析出する為、定期的に
逆通電を行なつて析出金属を溶解せねばならず、
この結果、陽極が還元状態となる為、陽極が劣化
し、その寿命に著しい悪影響を与える欠点があつ
た。(Problems to be Solved by the Invention) However, among these conventional methods, the former method has the drawback of causing pollution problems when disposing of the used liquid, and the latter method has the disadvantage of causing pollution problems when disposing of the used liquid. Since metal ions precipitate on the cathode, reverse current must be periodically applied to dissolve the precipitated metal.
As a result, the anode is brought into a reduced state, resulting in deterioration of the anode, which has the disadvantage of having a significant negative impact on its lifespan.
（問題点を解決する為の手段）
本発明者はかかる欠点を排除し、隔膜を用いた
電解法によるクロメート処理液の再生時に、不要
金属を陰極に析出せしめることなく、確実に液の
再生を行ない得る手段を見出すことを目的として
種々研究、検討を行なつた結果、陰極室に特定量
の酸を存在せしめて通電することにより、前記目
的を達成し得ることを見出した。(Means for Solving the Problems) The present inventor has eliminated such drawbacks and reliably regenerates the chromate treatment liquid without depositing unnecessary metals on the cathode when regenerating the chromate treatment liquid by electrolytic method using a diaphragm. As a result of various studies and examinations aimed at finding possible means for achieving this, it was discovered that the above object could be achieved by making a specific amount of acid exist in the cathode chamber and energizing it.
かくして本発明は、カチオン交換膜により仕切
られた陽極室と陰極室を有する槽の陽極室に、再
生すべきクロメート処理液を、陰極室に少なくと
も５重量％の鉱酸を含む水溶液を夫々導入して直
流電流を通電することを特徴とするクロメート処
理液の再生方法を提供するにある。 Thus, in the present invention, a chromate treatment solution to be regenerated is introduced into the anode chamber of a tank having an anode chamber and a cathode chamber separated by a cation exchange membrane, and an aqueous solution containing at least 5% by weight of mineral acid is introduced into the cathode chamber. The present invention provides a method for regenerating a chromate treatment solution, characterized in that a direct current is applied to the chromate treatment solution.
本発明において、再生すべきクロメート処理液
は、これを繰り返し使用した為に不要イオン、即
ち亜鉛、ニツケル、鉄等の溶出金属がほぼ濃度に
して0.3〜10ｇ／程度蓄積されたものであり、
この様な液はこれにクロメート処理液を新らたに
追加して再生の為の濃度管理を行なつても大量の
廃クロームが発生するような不都合が生じる液で
ある。 In the present invention, the chromate treatment solution to be regenerated is one in which unnecessary ions, that is, eluted metals such as zinc, nickel, iron, etc., have accumulated at a concentration of about 0.3 to 10 g/dimensions due to repeated use.
Such a solution has problems such as a large amount of waste chromium being generated even if a new chromate treatment solution is added to the solution and the concentration is controlled for regeneration.
この様な液は、カチオン交換膜で仕切られた陽
極室に導入され、陰極室には少なくとも５重量％
の鉱酸を含む水溶液が導入される。鉱酸の量が５
重量％に満たない場合には、陰極上に金属が析出
するのを実質的に防止し得ないので不適当であ
る。 Such a liquid is introduced into an anode compartment separated by a cation exchange membrane, and at least 5% by weight is added to the cathode compartment.
An aqueous solution containing a mineral acid is introduced. The amount of mineral acid is 5
If it is less than % by weight, it is not suitable because metal deposition on the cathode cannot be substantially prevented.
用いられる鉱酸の濃度は理論的には上限はない
が、イオン交換膜への悪影響や槽の材質、特にあ
まり高濃度であると浸透圧差による液の移動や溶
解熱の発生等の不都合を来たす虞れがある。この
為用いられる鉱酸の濃度は５〜50重量％、好まし
くは10〜30重量％を採用するのが適当である。 Although there is no theoretical upper limit to the concentration of the mineral acid used, it may have an adverse effect on the ion exchange membrane or the material of the tank, especially if the concentration is too high, it may cause problems such as liquid movement due to osmotic pressure differences and generation of heat of dissolution. There is a risk. For this reason, it is appropriate that the concentration of the mineral acid used is 5 to 50% by weight, preferably 10 to 30% by weight.
次に、本発明に用いられる陽極の材質として
は、例えば白金、イリジウム等の貴金属が被覆さ
れた金属電極等を、又陰極の材質としては例えば
鉄、ニツケル、ステンレス等を適宜採用すること
が出来る。 Next, as the material of the anode used in the present invention, for example, a metal electrode coated with a noble metal such as platinum or iridium, etc., and as the material of the cathode, for example, iron, nickel, stainless steel, etc. can be appropriately adopted. .
又、用いられるカチオン交換膜としては、イオ
ン交換基が例えばスルホン酸、カルボン酸、リン
酸等を、又母体となる膜としては例えばフツ素樹
脂の如き耐酸化性を有する膜等を適宜採用し得
る。 The cation exchange membrane to be used may have an ion exchange group such as sulfonic acid, carboxylic acid, phosphoric acid, etc., and the base membrane may be a membrane having oxidation resistance such as fluororesin as appropriate. obtain.
かくして本発明において陰陽極間に直流電流が
印加される。 Thus, in the present invention, a direct current is applied between the cathode and anode.
印加される直流電流は、通常５〜50A／ｄm2、
電圧２〜6Vが採用され、かくすることにより、
陰極室中へ不要な金属イオンが容易に移行し、且
陰極上に不要金属の析出は実質的に生じない。 The applied direct current is usually 5 to 50 A/dm 2 ,
A voltage of 2 to 6 V is adopted, and thus,
Unnecessary metal ions easily migrate into the cathode chamber, and substantially no unnecessary metal is deposited on the cathode.
しかしながら、本発明者は、印加される直流電
流に変化を与えることにより、一層確実に陰極上
への金属の析出を抑制し得ることが知見された。
かかる直流電流の印加法としては、交互に大電流
と小電流を通電するものであり、この場合大電流
としては、電流密度が５〜50A／ｄm2の電流を10
〜300分間程度、小電流としては電流密度が0.1〜
4A／ｄm2を１〜60分間程度交互に通電するのが
適当である。 However, the present inventors have discovered that metal deposition on the cathode can be suppressed more reliably by changing the applied direct current.
The method of applying such a direct current is to alternately apply a large current and a small current, and in this case, the large current is a current with a current density of 5 to 50 A/ dm2 .
~300 minutes, current density is 0.1 ~ as a small current
It is appropriate to alternately apply a current of 4 A/dm 2 for about 1 to 60 minutes.
（実施例）
実施例 １
フツ素樹脂製のカチオン交換膜により仕切ら
れ、白金イリジウム製の陽極とSUS316製の陰極
を夫々備えた陽極室と陰極室を有する槽の陽極室
中に、３価のクロムイオン15ｇ／、亜鉛イオン
５ｇ／、ニツケルイオン300ppm、鉄イオン
500ppmを含むクロメート処理液を１／時の割
合で供給しつつ、他方陰極室中には40重量％の硫
酸水溶液を１／時の割合で供給しつつ電流密度
10A／ｄm2、電圧4Vを陰、陽極間に印加してク
ロメート処理液の再生を行なつた。定常状態にな
つたときの再生クロメート処理液中の金属イオン
濃度は、クロムイオン14ｇ／、亜鉛イオン１
ｇ／、ニツケルイオン200ppm、鉄イオン
340ppmと減少しており、十分再使用に耐えるも
のであつた。又、かかる再生処理操作は連続して
時間実施されたが、陰極上への金属の析出は実質
的に認められなかつた。(Example) Example 1 Trivalent Chromium ion 15g/, zinc ion 5g/, nickel ion 300ppm, iron ion
A chromate treatment solution containing 500 ppm was supplied at a rate of 1/hour, while a 40% by weight sulfuric acid aqueous solution was supplied at a rate of 1/hour into the cathode chamber, and the current density was increased.
The chromate treatment solution was regenerated by applying 10 A/dm 2 and a voltage of 4 V between the anode and the anode. The metal ion concentration in the regenerated chromate treatment solution when it reaches a steady state is chromium ion 14g/zinc ion 1
g/, Nickel ion 200ppm, Iron ion
The amount was reduced to 340ppm, which was sufficient to withstand reuse. Further, although such regeneration treatment operation was carried out continuously for a period of time, substantially no metal precipitation was observed on the cathode.
実施例 ２
実施例１と同様の槽を用い、同様の被再生クロ
メート処理液を同様に陽極室に２／時の割合で
導入し、他方陰極室中には15重量％のリン酸水溶
液を２／時の割合で連続的に導入した。Example 2 Using the same tank as in Example 1, the same regenerated chromate treatment solution was similarly introduced into the anode chamber at a rate of 2/hour, while a 15% by weight phosphoric acid aqueous solution was introduced into the cathode chamber at a rate of 2/hour. /hour of continuous introduction.
そして先づ電流密度20A／ｄm2、6Vの直流電
流を陰陽極間に100分間印加し、次いで電流密度
1A／ｄm2、2Vの直流電流を陰陽極間に20分間印
加し、これらの電流を交互に24時間印加した。こ
の時得られた再生クロメート処理液中の金属イオ
ン濃度は、クロムイオン14.1ｇ／、亜鉛イオン
1.2ｇ／、ニツケルイオン100ppm、鉄イオン
340ppmと減少しており、十分再使用に耐えるも
のであつた。又、かかる再生処理操作は連続して
24時間実施されたが、陰極上への金属の析出は皆
無であつた。 First, a direct current of 6V at a current density of 20A/dm 2 was applied between the cathode and anode for 100 minutes, and then the current density
A direct current of 1 A/dm 2 and 2 V was applied between the cathode and anode for 20 minutes, and these currents were applied alternately for 24 hours. The metal ion concentration in the regenerated chromate treatment solution obtained at this time was 14.1 g/14.1 g/g of chromium ions, and 14.1 g/g/g of zinc ions.
1.2g/, Nickel ion 100ppm, Iron ion
The amount was reduced to 340ppm, which was sufficient to withstand reuse. In addition, such regeneration processing operations are performed continuously.
Although the test was carried out for 24 hours, no metal was deposited on the cathode.
Claims (1)
極室を有する槽の陽極室に、再生すべきクロメー
ト処理液を、陰極室に少なくとも５重量％の鉱酸
を含む水溶液を夫々導入して直流電流を通電する
ことを特徴とするクロメート処理液の再生方法。 ２ 再生すべきクロメート処理液中に含まれる金
属イオンは、亜鉛、ニツケル、鉄である請求の範
囲１の方法。 ３ 鉱酸の濃度は５〜50重量％である請求の範囲
１の方法。 ４ 直流電流の通電は、大電流と小電流を交互に
通電する請求の範囲１の方法。 ５ 大電流は、10〜50A／ｄm2を10〜300分間通
電する請求の範囲４の方法。 ６ 小電流は、0.1〜4A／ｄm2を１〜60分間通電
する請求の範囲４の方法。[Scope of Claims] 1. A chromate treatment solution to be regenerated is placed in the anode chamber of a tank having an anode chamber and a cathode chamber separated by a cation exchange membrane, and an aqueous solution containing at least 5% by weight of mineral acid is placed in the cathode chamber. A method for regenerating a chromate treatment solution, which comprises introducing a direct current and applying a direct current. 2. The method according to claim 1, wherein the metal ions contained in the chromate treatment solution to be regenerated are zinc, nickel, and iron. 3. The method of claim 1, wherein the concentration of mineral acid is between 5 and 50% by weight. 4. The method according to claim 1, in which the DC current is applied alternately with a large current and a small current. 5. The method according to claim 4, wherein the large current is 10 to 50 A/dm 2 for 10 to 300 minutes. 6. The method according to claim 4, wherein the small current is 0.1 to 4 A/dm 2 for 1 to 60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21803186A JPS6376884A (en) | 1986-09-18 | 1986-09-18 | Method for regenerating chromate treatment liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21803186A JPS6376884A (en) | 1986-09-18 | 1986-09-18 | Method for regenerating chromate treatment liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6376884A JPS6376884A (en) | 1988-04-07 |
| JPH0419310B2 true JPH0419310B2 (en) | 1992-03-30 |
Family
ID=16713552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21803186A Granted JPS6376884A (en) | 1986-09-18 | 1986-09-18 | Method for regenerating chromate treatment liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6376884A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2481424C2 (en) * | 2011-07-28 | 2013-05-10 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Method of regenerating solution from black chromating of zinc coats |
| US11879172B2 (en) * | 2017-11-24 | 2024-01-23 | Nippon Steel Corporation | Method for producing chemically treated alloy material, and chemical treatment solution regeneration apparatus used in method for producing chemically treated alloy material |
| RU2691791C1 (en) * | 2018-09-07 | 2019-06-18 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of regenerating chromate solutions of passivating |
| RU2685840C1 (en) * | 2018-10-08 | 2019-04-23 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of regenerating chromate zinc passivation solution |
| RU2723177C1 (en) * | 2019-11-26 | 2020-06-09 | Дмитрий Юрьевич Тураев | Regeneration of acidic chromate solutions by membrane electrolysis |
-
1986
- 1986-09-18 JP JP21803186A patent/JPS6376884A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6376884A (en) | 1988-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4306952A (en) | Electrolytic process and apparatus | |
| US3764503A (en) | Electrodialysis regeneration of metal containing acid solutions | |
| Golub et al. | Removal of chromium from aqueous solutions by treatment with porous carbon electrodes: electrochemical principles | |
| KR950011405B1 (en) | Cathode for electrolysis and process for producing the same | |
| US5785833A (en) | Process for removing iron from tin-plating electrolytes | |
| JP3188361B2 (en) | Chrome plating method | |
| CA1079681A (en) | Electrolytically oxidizing organic materials and trivalent chromium in chromic acid solution | |
| US5478448A (en) | Process and apparatus for regenerating an aqueous solution containing metal ions and sulfuric acid | |
| US4105534A (en) | Apparatus for removing impurities from electrolyte solutions | |
| US4011151A (en) | Process for purifying waste water by electrolysis | |
| RU2181150C2 (en) | Method of pickling steel | |
| CN106164340A (en) | Continuous Process for Trivalent Chromate Plating | |
| US3933605A (en) | Non-polluting pickling method | |
| JP2002322593A (en) | Electrolytic phosphate chemical treatment method | |
| JPH0419310B2 (en) | ||
| Guddati et al. | The use of a porous ceramic diaphragm for the removal of metallic impurities from chromium plating baths | |
| JPH06256999A (en) | Method for recovering and regenerating tin plating liquid | |
| JPH04244221A (en) | Method for cleaning filter | |
| US3969207A (en) | Method for the cyclic electrochemical processing of sulfuric acid-containing pickle waste liquors | |
| JPH06158397A (en) | Metal electroplating method | |
| CA1126630A (en) | Method of treating electrodes | |
| US3425920A (en) | Electrolytic method of regenerating organic acid cleaning solution for ferrous metals | |
| JPH0699178A (en) | Electrolytical treating method for waste chemical plating liquid | |
| US2241585A (en) | Process for removing metallic coatings from metallic parts | |
| US4310395A (en) | Process for electrolytic recovery of nickel from solution |