JPH09176899A - Method for removing nickel ion and iron ion in galvanizing solution, device therefor and production of electrogalvanized steel sheet by the removed galvanized solution - Google Patents
Method for removing nickel ion and iron ion in galvanizing solution, device therefor and production of electrogalvanized steel sheet by the removed galvanized solutionInfo
- Publication number
- JPH09176899A JPH09176899A JP34126595A JP34126595A JPH09176899A JP H09176899 A JPH09176899 A JP H09176899A JP 34126595 A JP34126595 A JP 34126595A JP 34126595 A JP34126595 A JP 34126595A JP H09176899 A JPH09176899 A JP H09176899A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- plating solution
- solution
- ion
- galvanizing
- 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.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 42
- 239000010959 steel Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005246 galvanizing Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 74
- 229910052742 iron Inorganic materials 0.000 title description 8
- 229910001453 nickel ion Inorganic materials 0.000 title 1
- 239000012535 impurity Substances 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims description 141
- 238000007747 plating Methods 0.000 claims description 97
- 239000011701 zinc Substances 0.000 claims description 37
- 229910052725 zinc Inorganic materials 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 239000013522 chelant Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001429 chelating resin Polymers 0.000 abstract description 8
- -1 iminodiacetyl group Chemical group 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 92
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000009287 sand filtration Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気亜鉛めっき系鋼
板の製造に用いる亜鉛めっき液から不純物としてＮｉイ
オンとＦｅイオンを除去する方法、その除去装置、更に
はそのＮｉイオンおよびＦｅイオンを除去しためっき液
を用いて電気亜鉛めっき鋼板を製造する方法に関する。TECHNICAL FIELD The present invention relates to a method for removing Ni ions and Fe ions as impurities from a galvanizing solution used for producing an electrogalvanized steel sheet, a removal apparatus therefor, and further removal of the Ni ions and Fe ions. The present invention relates to a method for producing an electrogalvanized steel sheet using a plating solution.
【０００２】[0002]
【従来の技術】近年の自動車、家電等の目ざましい普及
に対応して、電気亜鉛めっき系鋼板、すなわち、電気亜
鉛めっき鋼板、電気亜鉛−鉄めっき鋼板、電気亜鉛−ニ
ッケルめっき鋼板等が防錆機能の優れたものとして需要
増大している。また、電気亜鉛めっき系鋼板は特性とし
て防錆機能に加えて、塗装後の耐食性、塗装仕上がり性
の機能も要求され、それらの要求に応じて電気亜鉛めっ
き系鋼板の上記した種々の夕イプのものが用いられてい
る。2. Description of the Related Art In response to the remarkable spread of automobiles, home appliances, etc. in recent years, electrogalvanized steel sheets, namely electrogalvanized steel sheets, electrogalvanized-iron plated steel sheets, electrogalvanized-nickel plated steel sheets, etc., have an anticorrosive function. Demand is increasing as an excellent product. Further, the electrogalvanized steel sheet is required to have not only a rust preventive function as a characteristic but also a function of corrosion resistance after painting and a finish property of coating. Things are used.
【０００３】一方、製造側では種々のタイプの電気亜鉛
めっき系鋼板について専用ラインを設置して製造した場
合、種々のタイプの電気亜鉛めっき系鋼板の需要の相違
から遊休するラインも生じ、生産性が低下するという問
題がある。そのために、一般には一つの電気亜鉛めっき
系鋼板のラインを設置し、種々のタイプの電気亜鉛めっ
き系鋼板の需要に応じて、兼用ラインとして、めっき液
等を替えて、それらの電気亜鉛めっき系鋼板の製造が行
われている。一般にめっき液はめっき液循環タンクで不
純物を除去して調整され、めっき浴に供給されている。On the other hand, on the manufacturing side, when a dedicated line is installed for various types of electrogalvanized steel sheets, some lines are idle due to the difference in demand for various types of electrogalvanized steel sheets, resulting in productivity. There is a problem that Therefore, in general, one electrogalvanized steel sheet line is installed, and according to the demand for various types of electrogalvanized steel sheet, the plating solution or the like is changed as a dual-purpose line and those electrogalvanized steel sheets are used. Steel sheets are manufactured. Generally, the plating solution is prepared by removing impurities in a plating solution circulation tank and supplied to the plating bath.
【０００４】電気亜鉛めっき系鋼板の製造ではめっき液
に不純物が存在すると、成品の外観等に大きく影響を与
えるので、めっき液の不純物の除去について厳密な管理
が要求されている。上記のような兼用ラインでのめっき
液の取替えには、特に厳密な管理が要求されている。例
えば電気亜鉛−ニッケルめっき鋼板の製造から電気亜鉛
めっき鋼板の製造に切換える場合は亜鉛−ニッケルめっ
き液から混入するＮｉイオンおよびＦｅイオンを含む不
純物、また鋼板等から溶損するＦｅイオンの不純物が成
品の外観等に大きく影響を与えるので、それらの不純物
を充分に除去することが必要である。In the production of galvanized steel sheets, the presence of impurities in the plating solution has a great influence on the appearance of the product, so that strict control is required for the removal of impurities from the plating solution. Particularly strict management is required for the replacement of the plating solution in the above-mentioned dual-purpose line. For example, when switching from the production of electrogalvanized nickel-plated steel sheet to the production of electrogalvanized steel sheet, impurities containing Ni ions and Fe ions mixed from the zinc-nickel plating solution, and Fe ion impurities that melt from the steel sheet etc. Since it greatly affects the appearance and the like, it is necessary to sufficiently remove those impurities.
【０００５】そのために、Ｎｉイオン、Ｆｅイオン等の
金属イオンを含む不純物の除去について種々の対策が行
われている。Ｆｅイオンを含有する不純物の除去方法に
ついては特開昭６３−１３０７９９号公報にアミノカル
ボン酢酸基を有するキレート樹脂を用いて鉄イオンを吸
着することが開示されている。Ｎｉイオンを含有する不
純物の除去方法については特開昭６３−１１７００号公
報に電気めっきにより失われる亜鉛系成分として連続的
または間欠的に亜鉛系めっき液に鱗片状亜鉛または鱗片
状亜鉛合金を補給して、電気めっき中に蓄積するＮｉイ
オン等の不純物を操作を中断することなく除去すること
がてきることが開示されている。Therefore, various measures have been taken to remove impurities containing metal ions such as Ni ions and Fe ions. Regarding the method for removing impurities containing Fe ions, JP-A-63-130799 discloses that iron ions are adsorbed using a chelating resin having an aminocarboxylic acetic acid group. Regarding the method for removing impurities containing Ni ions, Japanese Patent Laid-Open No. 63-11700 discloses a zinc-based plating solution that is continuously or intermittently supplemented with scale-like zinc or scale-like zinc alloy as a zinc-based component lost by electroplating. Then, it is disclosed that impurities such as Ni ions accumulated during electroplating can be removed without interrupting the operation.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上述し
た特開昭６３−１３０７９９号公報、特開昭６３−１１
７００号公報に開示された技術は以下に示すような問題
がある。 （１）特開昭６３−１３０７９９号公報に開示された技
術ではＦｅイオンの除去方法については効果が期待され
るが、Ｎｉイオンの除去を行うことができない。However, the above-mentioned JP-A-63-130799 and JP-A-63-11 are mentioned above.
The technique disclosed in Japanese Patent Publication No. 700 has the following problems. (1) The technique disclosed in Japanese Patent Laid-Open No. 63-130799 is expected to be effective in removing Fe ions, but cannot remove Ni ions.
【０００７】（２）特開昭６３−１１７００号公報に開
示された技術ではＮｉイオンの除去を行うことができる
が、Ｆｅイオンと同時に亜鉛も除去してしまう。 このように、上記２つの除去方法は、不純物としてＮｉ
イオンおよびＦｅイオンを同時に含む亜鉛めっき液から
ＮｉイオンおよびＦｅイオンを除去する場合には適用が
困難であり、また、上記２つの除去方法を組合わせて
も、工程が複雑となり実用上困難である。(2) Although the technique disclosed in Japanese Patent Laid-Open No. 63-11700 can remove Ni ions, it also removes zinc at the same time as Fe ions. As described above, the above two removal methods use Ni as an impurity.
It is difficult to apply Ni ions and Fe ions when removing Ni ions and Fe ions from a zinc plating solution that contains both ions and Fe ions at the same time, and even if the above two removal methods are combined, the process becomes complicated and it is practically difficult. .
【０００８】本発明はかかる事情に鑑みてなされたもの
であって、不純物としてＮｉイオンおよびＦｅイオンを
含有する亜鉛めっき液からＮｉイオンおよびＦｅイオン
を簡単な操作により精度良く除去することの出来る除去
方法、その除去装置、そのＮｉイオンおよびＦｅイオン
を除去した亜鉛めっき液により電気亜鉛めっき鋼板を製
造する方法を提供することを目的とする。The present invention has been made in view of the above circumstances, and can remove Ni ions and Fe ions from a zinc plating solution containing Ni ions and Fe ions as impurities by a simple operation with high accuracy. It is an object of the present invention to provide a method, a removing device therefor, and a method for producing an electrogalvanized steel sheet by a zinc plating solution from which Ni ions and Fe ions are removed.
【０００９】[0009]
【発明が解決しようとする手段】上記課題を解決するた
めに、本発明は、第１に、亜鉛めっき液から不純物とし
てＮｉイオンおよびＦｅイオンを除去するにあたり、は
じめに前記めっき液のＮｉイオンをＮｉ2+イオンとして
アクリル系イミノジ酢酸基を含有するキレート樹脂に吸
着させて設定値まで除去し、その後に該めっき液に酸化
剤を添加してＦｅ2+イオンとして存在するＦｅイオンを
Ｆｅ3+イオンに酸化し、該めっき液のＦｅイオンをＦｅ
3+イオンとしてアクリル系イミノジ酢酸基に吸着させて
除去することを特徴とする亜鉛めっき液のＮｉイオンお
よびＦｅイオンの除去方法を提供する。In order to solve the above problems, the present invention firstly requires that when Ni ions and Fe ions are removed as impurities from a zinc plating solution, the Ni ions in the plating solution are first converted into Ni ions. 2+ ions are adsorbed to a chelate resin containing an acrylic iminodiacetic acid group and removed to a set value, and then an oxidizing agent is added to the plating solution to convert Fe ions existing as Fe 2+ ions into Fe 3+ ions. To the Fe ion of the plating solution.
Disclosed is a method for removing Ni ions and Fe ions from a zinc plating solution, which is characterized by adsorbing 3+ ions on an acrylic iminodiacetic acid group and removing the ions.
【００１０】本発明は、第２に、上記方法において、Ｎ
ｉ2+イオンの設定値の範囲が５０ｐｐｍ以下であること
を特徴とする亜鉛めっき液のＮｉイオンおよびＦｅイオ
ンの除去方法を提供する。The present invention is secondly the method described above, wherein N
Provided is a method for removing Ni ions and Fe ions from a galvanizing solution, characterized in that the set value range of i 2+ ions is 50 ppm or less.
【００１１】本発明は、第３に、めっき液循環タンク
と、該循環タンクのめっき液出側から酸化剤供給管を付
設した酸化槽と、キレート塔を順次配設し、めっき液が
循環するように配管させるとともに、前記酸化槽の入側
に金属イオン検出装置とその検出値により酸化剤の添加
を制御する制御装置を設けたことを特徴とする亜鉛めっ
き液のＮｉイオンおよびＦｅイオンの除去装置を提供す
る。Thirdly, according to the present invention, a plating solution circulating tank, an oxidizing tank provided with an oxidizing agent supply pipe from the plating solution outlet side of the circulating tank, and a chelating tower are sequentially arranged to circulate the plating solution. And a control device for controlling the addition of the oxidant according to the detection value of the metal ion detector on the inlet side of the oxidation tank. Provide a device.
【００１２】本発明は、第４に、一つのめっきラインで
電気亜鉛−ニッケルめっき鋼板を製造した後、上記製造
に用いためっき液をラインから分離し、ライン設備を水
洗した後、亜鉛めっき液に切り換え、その際に該亜鉛め
っき液に不純物として混入するＮｉイオンおよびＦｅイ
オンを上記第１および第２の方法により除去した亜鉛め
っき液を用いて、前記めっきラインで電気亜鉛めっき鋼
板を製造することを特徴とするＮｉイオンおよびＦｅイ
オンの除去された亜鉛めっき液による電気亜鉛めっき鋼
板の製造方法を提供する。Fourthly, according to the present invention, after producing an electrogalvanized nickel-plated steel sheet by one plating line, the plating solution used in the above production is separated from the line, the line equipment is washed with water, and then the galvanizing solution is used. The galvanizing solution is produced by removing the Ni ions and Fe ions mixed as impurities in the galvanizing solution by the first and second methods at that time to produce an electrogalvanized steel sheet on the galvanizing line. A method for producing an electrogalvanized steel sheet using a zinc plating solution from which Ni ions and Fe ions are removed is provided.
【００１３】[0013]
【発明の実施の形態】本発明では亜鉛めっき液が一般に
酸性亜鉛めっき液でＮｉイオン、ＦｅイオンはＮｉ2+イ
オン、Ｆｅ2+イオンとして存在しているので、はじめに
亜鉛めっき液のＮｉイオンをアクリル系イミノジ酢酸基
を含有するキレート樹脂にＮｉ2+イオンとして吸着させ
て設定値まで除去し、その後に該めっき液に酸化剤を添
加してめっき液のＦｅイオンをＦｅ2+イオンからＦｅ3+
イオンに酸化し、アクリル系イミノジ酢酸基にＦｅ3+イ
オンとして吸着させて除去するものであり、めっき液の
Ｎｉイオン、Ｆｅイオンは上記キレート樹脂に最適な状
態で吸着除去される。Ｎｉイオンの除去をはじめに行う
のは、Ｎｉイオンの混入は切替え時の場合だけであり、
Ｆｅイオンは切替え時の場合に加えて、その後でも鋼板
等から溶解混入する可能性があることによる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the zinc plating solution is generally an acidic zinc plating solution and Ni ions and Fe ions are present as Ni 2+ ions and Fe 2+ ions. A chelate resin containing an acrylic iminodiacetic acid group is adsorbed as Ni 2+ ions to remove it to a set value, and then an oxidizing agent is added to the plating solution to change the Fe ions of the plating solution from Fe 2+ ions to Fe 3 +. +
It is oxidized to ions and is adsorbed and removed as Fe 3+ ions by the acrylic iminodiacetic acid group, and Ni ions and Fe ions in the plating solution are adsorbed and removed in the optimum state for the chelate resin. The first removal of Ni ions is only when mixing Ni ions when switching,
This is because Fe ions may be dissolved and mixed in from the steel plate or the like after switching, in addition to when switching.
【００１４】本発明において、キレート樹脂をアクリル
系イミノジ酢酸基を含有するキレート樹脂に限定したの
は以下の理由による。亜鉛めっき液からＮｉイオンおよ
びＦｅイオンを除去するためのキレート樹脂の条件とし
て、金属イオンの選択性はＦｅ3+およびＮｉ2+をＺｎ2+
よりも優先的に吸着させるキレート樹脂でなければなら
ない。In the present invention, the reason why the chelate resin is limited to the chelate resin containing an acrylic iminodiacetic acid group is as follows. As a condition of the chelating resin for removing Ni ions and Fe ions from the galvanizing solution, the selectivity of metal ions is such that Fe 3+ and Ni 2+ are Zn 2+.
It must be a chelating resin that is adsorbed preferentially over.
【００１５】上記のような選択性を満足させたキレート
樹脂として、選択性がＦｅ3+＞Ｎｉ2+＞Ｚｎ2+≒Ｆｅ2+
であるアクリル系イミノジ酢酸基を含有するキレート樹
脂が挙げられる。As a chelate resin satisfying the above-mentioned selectivity, the selectivity is Fe 3+ > Ni 2+ > Zn 2+ ≈Fe 2+
And a chelate resin containing an acrylic iminodiacetic acid group.
【００１６】本発明ではめっき液のＮｉイオンをアクリ
ル系イミノジ酢酸基を含有するキレー卜樹脂にＮｉ2+イ
オンとして吸着させて設定値まで除去し、その後に該め
っき液に酸化剤を添加してめっき液のＦｅ2+イオンをＦ
ｅ3+イオンにし、アクリル系イミノジ酢酸基を含有する
キレート樹脂にＦｅ3+イオンとして吸着させて除去す
る。According to the present invention, Ni ions in the plating solution are adsorbed as Ni 2+ ions on a killing resin containing an acrylic iminodiacetic acid group to remove it to a set value, and then an oxidizing agent is added to the plating solution. Fe 2+ ion of plating solution is F
It is converted into e 3+ ion and is adsorbed and removed as Fe 3+ ion on a chelate resin containing an acrylic iminodiacetic acid group.
【００１７】これは以下の理由による。本発明で対象と
する亜鉛めっき液は酸性溶液であり、Ｎｉ、Ｆｅ、Ｚｎ
イオンはＮｉ2+、Ｚｎ2+、Ｆｅ2+としてめっき液に溶解
しているので、はじめに上記アクリル系イミノジ酢酸基
を含有するキレート樹脂にＮｉ2+として吸着させ除去す
る。This is for the following reason. The zinc plating solution targeted by the present invention is an acidic solution, and Ni, Fe, Zn
Since the ions are dissolved in the plating solution as Ni 2+ , Zn 2+ , and Fe 2+ , they are first adsorbed and removed as Ni 2+ to the chelate resin containing the acrylic iminodiacetic acid group.
【００１８】亜鉛めっき液にはΖｎ2+、Ｆｅ2+がそのま
ま存在するので、Ｎｉ2+イオンを吸着させて設定値まで
除去した後に、Ｆｅを除去するために、めっき液に酸化
剤を添加してめっき液のＦｅ2+イオンとをＦｅ3+イオン
にする。Since zinc 2+ and Fe 2+ are present in the zinc plating solution as they are, an oxidizing agent is added to the plating solution in order to remove Fe after the Ni 2+ ions are adsorbed and removed to a set value. Then, the Fe 2+ ions of the plating solution are changed to Fe 3+ ions.
【００１９】本発明では上記キレート樹脂にＮｉ2+イオ
ンとして吸着させて除去する場合に、Ｆｅイオンへの切
換を行うために、Ｎｉ2+イオンの除去濃度設定値を決め
る。Ｎｉ2+イオンの除去濃度設定値の範囲は図２、図３
に示す実験結果により５０ｐｐｍ以下とする。In the present invention in removing by adsorption as Ni 2+ ions to the chelating resin, in order to perform the switching to Fe ions, determine the removal density setting value of Ni 2+ ions. Ni 2+ ion removal concentration setting range is shown in FIGS. 2 and 3.
According to the experimental result shown in, it is set to 50 ppm or less.
【００２０】図２は無処理のＺｎめっき鋼材における亜
鉛めっき液中のＮｉ濃度（ｐｐｍ）と白色度（Ｌ値）と
の関係を示す図である。また、図３はリン酸処理のＺｎ
めっき鋼材における亜鉛めっき液中のＮｉ濃度（ｐｐ
ｍ）と白色度（Ｌ値）との関係を示す図である。白色度
（Ｌ値）は、試料面に一定方向から照明光をあて、その
反射特性により、ＪＩＳＺ８７２２にて規定するスペク
トル三刺激値を測定し、アール．エス．ハンター（Ｒ．
Ｓ．Ηｕｎｔｅｒ）の計算式を用い算出した数値であ
る。FIG. 2 is a graph showing the relationship between the Ni concentration (ppm) in the zinc plating solution and the whiteness (L value) of untreated Zn-plated steel. In addition, FIG. 3 shows phosphoric acid-treated Zn.
Ni concentration in galvanizing solution in galvanized steel (pp
It is a figure which shows the relationship between m) and whiteness (L value). The whiteness (L value) is measured by irradiating the sample surface with illumination light from a certain direction and measuring the spectral tristimulus value defined by JIS Z8722 by its reflection characteristic. S. Hunter (R.
S. Ηterter) is a numerical value calculated using the formula.
【００２１】図２、図３から明らかなように、Ｎｉ2+イ
オンの濃度は低いほどよく、一点鎖線で示すように５０
ｐｐｍ以下にするとその白色度（Ｌ値）が特に向上す
る。なお、Ｎｉ2+イオンの濃度は低いほどよいため、そ
の下限については特に限定していない。実操業上は、５
ｐｐｍ未満では処理費の増大、ライン停止時間の増大に
よる生産性の低下等を生じるので、５〜５０ｐｐｍの範
囲で処理される。このようなＮｉ2+イオン濃度が５０ｐ
ｐｍ以下の亜鉛めっき液を電気亜鉛めっき鋼板の製造に
用いた場合にはＮｉ2+イオンによる成品外観への影響が
少ない。As is clear from FIGS. 2 and 3, the lower the concentration of Ni 2+ ions, the better, and as shown by the chain line, 50
When the content is ppm or less, the whiteness (L value) is particularly improved. Since the lower the concentration of Ni 2+ ions, the better, the lower limit is not particularly limited. 5 in actual operation
If it is less than ppm, the processing cost increases and the productivity is lowered due to the increase in the line stop time. Therefore, the treatment is performed in the range of 5 to 50 ppm. Such Ni 2+ ion concentration is 50p
When a galvanizing solution of pm or less is used for producing an electrogalvanized steel sheet, Ni 2+ ions have little influence on the appearance of the product.
【００２２】上記のようなＮｉ2+イオンの除去後、Ｆｅ
イオンをＦｅ2+イオンからＦｅ3+イオンにするための操
作の切換えは金属イオン検出装置によるＮｉ2+イオンの
検出値を制御装置に入力して、Ｎｉ2+イオンが除去濃度
設定値に達した時点で行われる。酸化槽に酸化剤の添加
が行われ、めっき液のＦｅ2+イオンはＦｅ3+イオンに酸
化される。めっき液のＦｅイオンはＦｅ3+イオンとして
アクリル系イミノジ酢酸基を含有するキレート樹脂に吸
着されて除去される。After removing Ni 2+ ions as described above, Fe
To switch the operation for changing the ions from Fe 2+ ions to Fe 3+ ions, the detection value of Ni 2+ ions by the metal ion detection device is input to the control device, and the Ni 2+ ions reach the removal concentration set value. Will be done at the time. An oxidizing agent is added to the oxidizing tank, and Fe 2+ ions in the plating solution are oxidized into Fe 3+ ions. Fe ions in the plating solution are adsorbed and removed as Fe 3+ ions by the chelating resin containing an acrylic iminodiacetic acid group.
【００２３】本発明では一つのめっきラインで電気亜鉛
−ニッケルめっき鋼板を製造した後、上記製造に用いた
めっき液をラインから分離し、ライン設備を水洗した
後、亜鉛めっき液に切り換え、その際に亜鉛めっき液に
不純物として混入するＮｉイオンおよびＦｅイオンを上
記のような方法によって除去し、その不純物の除去され
た亜鉛めっき液を用いて、前記めっきラインで電気亜鉛
めっき鋼板を製造するので、電気亜鉛−ニッケルめっき
鋼板の製造後でも、白色度（Ｌ値）の優れた電気亜鉛め
っき鋼板を製造することができる。In the present invention, after producing an electrogalvanized-nickel plated steel sheet by one plating line, the plating solution used in the above production is separated from the line, the line equipment is washed with water, and then the galvanizing solution is switched to the galvanizing solution. Ni ions and Fe ions mixed as impurities in the zinc plating solution are removed by the method as described above, and the galvanizing solution from which the impurities are removed is used to produce an electrogalvanized steel sheet, Even after the production of the electrogalvanized nickel-plated steel sheet, the electrogalvanized steel sheet having excellent whiteness (L value) can be produced.
【００２４】[0024]
【実施例】以下に本発明の実施例について詳述する。図
１は本発明のめっき液循環装置の一実施例を示す概略図
である。図１において、参照符号１はめっき液循環タン
クで、ここで調整されためっき液は図示しない供給系統
によりめっき浴に供給される。めっき液循環タンク１で
はめっき液が浄化のために、矢印に示すようにポンプΡ
により酸化槽２に送入される。ここではＦｅ２＋イオン
をＦｅ３＋イオンに酸化することができるように、Η2
Ｏ2 の供給管７が付設されている。めっき液は酸化槽２
からポンプＰにより砂濾過塔３に送入される。Embodiments of the present invention will be described below in detail. FIG. 1 is a schematic diagram showing an embodiment of the plating solution circulating apparatus of the present invention. In FIG. 1, reference numeral 1 is a plating solution circulation tank, and the plating solution adjusted here is supplied to a plating bath by a supply system (not shown). In order to purify the plating solution in the plating solution circulation tank 1, the pump Ρ
Is sent to the oxidation tank 2. Here, as can oxidize Fe @ 2 + ions in the Fe @ 3 + ions, Eta 2
An O 2 supply pipe 7 is attached. Plating solution is oxidation tank 2
Is pumped into the sand filtration tower 3 from the pump.
【００２５】砂濾過塔３を出ためっき液は更にキレート
塔４でアクリル系イミノジ酢酸基を有するキレート樹脂
によりＮｉ2+イオンまたはＦｅ3+イオンが除去される。
キレート塔４を出ためっき液はめっき液循環タンク１に
循環される。Ni 2+ ions or Fe 3+ ions in the plating solution leaving the sand filtration tower 3 are further removed by the chelate resin having an acrylic iminodiacetic acid group in the chelate tower 4.
The plating solution leaving the chelate tower 4 is circulated in the plating solution circulation tank 1.
【００２６】この装置は、本発明にしたがって、酸化槽
２の入側にめっき液のＮｉ2+イオンおよびＦｅ3+イオン
を連続的に検出する検出装置５が付設されている。検出
装置５としては蛍光Χ線分析装置等が用いられる。検出
装置５からの検出値は制御装置６に入力されて、めっき
液のＦｅ2+イオンをＦｅ3+イオンに酸化するΗ2 Ｏ2２
の調整弁８を調整できるように構成されている。また、
必要に応じて、制御装置６からはキレート塔４のキレー
ト樹脂の再生の指令等が行われる。According to the present invention, this device is provided with a detector 5 on the inlet side of the oxidation tank 2 for continuously detecting Ni 2+ ions and Fe 3+ ions in the plating solution. As the detection device 5, a fluorescence X-ray analysis device or the like is used. Detection values from the detector 5 is inputted to the control unit 6, the Fe 2+ ion in the plating solution is oxidized to Fe 3+ ions Eta 2 O 2 2
The adjusting valve 8 is adjustable. Also,
If necessary, the controller 6 issues a command to regenerate the chelate resin in the chelate tower 4.
【００２７】次に図１に示すめっき液循環装置を用いて
めっき液を浄化する方法を詳述する。不純物としてＮｉ
イオンおよびＦｅイオンを含有しているめっき液がめっ
き液循環タンク１に送入される。使用しためっき液の浄
化前の主な組成を表１に示す。ここでは最終浄化後のめ
っき液の目標値を設定している。また、使用したキレー
ト樹脂の特性を表２に示す。なお、比較例としてフェノ
ール系イミノジ酸によるキレート樹脂を用いた。Next, a method for purifying the plating solution using the plating solution circulating device shown in FIG. 1 will be described in detail. Ni as an impurity
A plating solution containing ions and Fe ions is fed into the plating solution circulating tank 1. Table 1 shows the main composition of the used plating solution before purification. Here, the target value of the plating solution after the final purification is set. Table 2 shows the characteristics of the chelate resin used. As a comparative example, a chelate resin based on phenolic iminodiic acid was used.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】始めにＮｉイオンの除去を行うために、酸
化槽２にはΗ2 Ｏ2 の供給が停止されて、めっき液のＦ
ｅイオンはＦｅ2+イオンとして砂濾過塔３を通過してキ
レート塔４に送入される。キレート塔４でアクリル系イ
ミノジ酢酸基を有するキレート樹脂によりＮｉ2+イオン
が吸着され、めっき液のＮｉ2+イオンの除去が行われ
る。[0030] In order to perform the removal of Ni ions in the beginning, the oxidation tank 2 is stopped the supply of Eta 2 O 2, F of the plating solution
The e ions pass through the sand filtration tower 3 as Fe 2+ ions and are fed into the chelate tower 4. Ni 2+ ions are adsorbed by the chelate tower 4 by a chelate resin having an acrylic iminodiacetic acid group, the removal of the Ni 2+ ions in the plating solution is performed.
【００３１】めっき液のＮｉ2+イオンの濃度は連続的に
検出装置５で検出されており、その値が設定値を超えて
低くなった場合に直ちに酸化槽２のΗ2 Ｏ2 の供給が開
始される。めっき液のＦｅイオンは酸化されてＦｅ3+イ
オンとして砂濾過塔３を通過してキレート塔４に送入さ
れる。キレート塔４でアクリル系イミノジ酢酸基を有す
るキレート樹脂によりＦｅ3+イオンが吸着され除去され
る。The concentration of Ni 2+ ions in the plating solution is continuously detected by the detector 5, and when the value becomes lower than the set value, the supply of Η 2 O 2 in the oxidation tank 2 is immediately stopped. Be started. The Fe ions of the plating solution are oxidized and fed as Fe 3+ ions through the sand filtration tower 3 into the chelate tower 4. In the chelate tower 4, Fe 3+ ions are adsorbed and removed by the chelate resin having an acrylic iminodiacetic acid group.
【００３２】亜鉛めっき液のキレート塔での通液時間と
Ｆｅ、Ｎｉ吸着量との関係を図４、図５に示す。図４は
本発明の除去方法による亜鉛めっき液のキレート塔での
通液時間とＮｉ吸着量との関係を示す図である。図５は
本発明の除去方法による亜鉛めっき液のキレート塔での
通液時間とＦｅ吸着量との関係を示す図である。The relationship between the passage time of the zinc plating solution through the chelate tower and the Fe and Ni adsorption amounts are shown in FIGS. 4 and 5. FIG. 4 is a diagram showing the relationship between the passage time of the zinc plating solution in the chelate tower and the Ni adsorption amount by the removing method of the present invention. FIG. 5 is a graph showing the relationship between the time during which the zinc plating solution is passed through the chelate tower according to the removal method of the present invention and the amount of Fe adsorbed.
【００３３】また、図６はＮｉ、Ｆｅの切換えを行った
場合の亜鉛めっき液のキレート塔での通過時間とＦｅ、
Ｎｉ吸着量との関係を示す図である。ここではＮｉ2+イ
オンが吸着されて、除去濃度設定値に達した時点で酸化
槽２に酸化剤が添加され、Ｆｅ3+イオンの吸着増加が行
われている。Ｆｅ3+イオンの吸着が横這いになった時点
でめっき液の浄化が完了する。その結果を表３に示す。Further, FIG. 6 shows the passage time of the zinc plating solution in the chelate tower and the Fe,
It is a figure which shows the relationship with Ni adsorption amount. Here, when Ni 2+ ions are adsorbed and the removal concentration set value is reached, an oxidizing agent is added to the oxidizing tank 2 to increase the adsorption of Fe 3+ ions. The purification of the plating solution is completed when the adsorption of Fe 3+ ions has leveled off. Table 3 shows the results.
【００３４】[0034]
【表３】 [Table 3]
【００３５】このようにして浄化されためっき液は、表
３から明らかなようにＮｉイオンおよびＦｅイオンが目
標値を達成している。比較例のフェノール系イミノジ酸
によるキレート樹脂での亜鉛めっき液の浄化では、Ｆｅ
の吸着は優れているが、Ｎｉの吸着が困難であって目標
値を達成していない。As is clear from Table 3, in the plating solution thus purified, Ni ions and Fe ions have reached the target values. In cleaning the zinc plating solution with the chelating resin using the phenolic iminodic acid of Comparative Example, Fe
Is excellent, but Ni is difficult to adsorb and the target value is not achieved.
【００３６】次に一つのめっきラインで電気亜鉛−ニッ
ケルめっき鋼板を製造した後、上記製造に用いためっき
液をラインから分離し、ライン設備を水洗した後、亜鉛
めっき液に切り換え、その際に亜鉛めっき液に不純物と
して混入するＮｉイオンおよびＦｅイオンを本発明によ
る方法で除去し、その不純物の除去された亜鉛めっき液
を用いて、同じめっきラインで電気亜鉛めっき鋼板を製
造した。その結果、無処理で白色度（Ｌ値）が５８であ
り、電気亜鉛−ニッケルめっき鋼板の製造後でも、白色
度（Ｌ値）の優れた電気亜鉛めっき鋼板を製造すること
ができた。Next, after producing an electrogalvanized nickel-plated steel sheet in one plating line, the plating solution used in the above production is separated from the line, the line equipment is washed with water, and then the galvanizing solution is switched to, Ni and Fe ions mixed as impurities in the galvanizing solution were removed by the method according to the present invention, and the galvanizing solution from which the impurities had been removed was used to produce an electrogalvanized steel sheet on the same plating line. As a result, the whiteness (L value) was 58 without any treatment, and the electrogalvanized steel sheet having excellent whiteness (L value) could be produced even after the production of the electrogalvanized nickel-plated steel sheet.
【００３７】比較例としてフェノール系イミノジ酸によ
るキレート樹脂で処理した亜鉛めっき液で同様に上記と
同じめっきラインで電気亜鉛めっき鋼板を製造した場
合、無処理で白色度（Ｌ値）が４０であり、白色度（Ｌ
値）の悪い電気亜鉛めっき鋼板が製造された。As a comparative example, when an electrogalvanized steel sheet was produced in the same plating line as above using a galvanizing solution treated with a chelating resin of phenolic iminodioic acid, the whiteness (L value) was 40 without any treatment. , Whiteness (L
A galvanized steel sheet with a bad value was produced.
【００３８】[0038]
【発明の効果】以上のように、本発明の除去方法および
除去装置によれば、不純物としてＮｉイオンおよびＦｅ
イオンを含有する亜鉛めっき液からＮｉイオンおよびＦ
ｅイオンを簡単な操作により精度良く除去することがで
きる。また、上記ＮｉイオンおよびＦｅイオンを除去し
た亜鉛めっき液で電気亜鉛めっき鋼板を製造した場合、
電気亜鉛−ニッケルめっき鋼板の製造後でも、白色度
（Ｌ値）の優れた電気亜鉛めっき鋼板を得ることができ
る。As described above, according to the removing method and the removing apparatus of the present invention, Ni ions and Fe are used as impurities.
Zinc plating solution containing Ni ions and F
The e-ions can be removed with high precision by a simple operation. Further, when an electrogalvanized steel sheet is manufactured with a zinc plating solution from which the Ni ions and Fe ions are removed,
Even after the production of the electrogalvanized nickel-plated steel sheet, the electrogalvanized steel sheet having excellent whiteness (L value) can be obtained.
【図１】本発明の一実施例を示す概略図。FIG. 1 is a schematic diagram showing one embodiment of the present invention.
【図２】無処理のＺｎめっき鋼材における亜鉛めっき液
中のＮｉ濃度と白色度との関係を示す図。FIG. 2 is a graph showing the relationship between the Ni concentration in a zinc plating solution and whiteness of untreated Zn-plated steel.
【図３】リン酸処理のＺｎめっき鋼材における亜鉛めっ
き液中のＮｉ濃度と白色度との関係を示す図。FIG. 3 is a diagram showing the relationship between the Ni concentration in a zinc plating solution and whiteness in a phosphoric acid-treated Zn-plated steel material.
【図４】本発明の除去方法による亜鉛めっき液のキレー
ト塔での通過時間とＮｉ吸着量との関係を示す図。FIG. 4 is a graph showing the relationship between the passage time of a zinc plating solution through a chelate tower and the amount of Ni adsorbed by the removing method of the present invention.
【図５】本発明の除去方法による亜鉛めっき液のキレー
ト塔での通過時間とＦｅ吸着量との関係を示す図。FIG. 5 is a graph showing the relationship between the time taken for the zinc plating solution to pass through the chelate tower and the amount of Fe adsorbed by the removing method of the present invention.
【図６】本発明の除去方法によるＮｉ、Ｆｅの切換えを
行った場合の亜鉛めっき液のキレート塔での通過時間と
Ｎｉ、Ｆｅ吸着量との関係を示す図。FIG. 6 is a diagram showing the relationship between the passing time of a zinc plating solution through a chelate tower and the amounts of Ni and Fe adsorbed when Ni and Fe are switched by the removing method of the present invention.
１……めっき液循環タンク ２……酸化槽 ３……砂濾過塔、 ４……キレート塔 ５……検出装置 ６……制御装置 ７……酸化剤供給管 ８……調整弁 1 ... Plating solution circulation tank 2 ... Oxidation tank 3 ... Sand filtration tower, 4 ... Chelate tower 5 ... Detection device 6 ... Control device 7 ... Oxidant supply pipe 8 ... Regulator valve
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河野 典生 東京都千代田区丸の内三丁目２番３号 日 本錬水株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Norio Kono 3 2-3 Marunouchi, Chiyoda-ku, Tokyo Nihon Rensei Co., Ltd.
Claims (4)
ンおよびＦｅイオンを除去するにあたり、はじめに前記
めっき液のＮｉイオンをＮｉ2+イオンとしてアクリル系
イミノジ酢酸基を含有するキレート樹脂に吸着させて設
定値まで除去し、その後に該めっき液に酸化剤を添加し
てＦｅ2+イオンとして存在するＦｅイオンをＦｅ3+イオ
ンに酸化し、該めっき液のＦｅイオンをＦｅ3+イオンと
してアクリル系イミノジ酢酸基に吸着させて除去するこ
とを特徴とする亜鉛めっき液のＮｉイオンおよびＦｅイ
オンの除去方法。1. When removing Ni ions and Fe ions as impurities from a zinc plating solution, first, Ni ions of the plating solution are adsorbed as Ni 2+ ions to a chelate resin containing an acrylic iminodiacetic acid group to set values. And then add an oxidizing agent to the plating solution to oxidize Fe ions present as Fe 2+ ions to Fe 3+ ions, and use the Fe ions of the plating solution as Fe 3+ ions as acrylic iminodiacetic acid. A method for removing Ni ions and Fe ions from a zinc plating solution, which is characterized in that it is adsorbed to a base and removed.
ｍ以下であることを特徴とする請求項１記載の亜鉛めっ
き液のＮｉイオンおよびＦｅイオンの除去方法。2. The set value range of Ni 2+ ions is 50 pp.
The method for removing Ni ions and Fe ions from the zinc plating solution according to claim 1, wherein the method is less than or equal to m.
めっき液出側から酸化剤供給管を付設した酸化槽と、キ
レート塔を順次配設し、めっき液が循環するように配管
させるとともに、前記酸化槽の入側に金属イオン検出装
置とその検出値により酸化剤の添加を制御する制御装置
を設けたことを特徴とする亜鉛めっき液のＮｉイオンお
よびＦｅイオンの除去装置。3. A plating solution circulation tank, an oxidation tank provided with an oxidizer supply pipe from the plating solution outlet side of the circulation tank, and a chelate tower are sequentially arranged, and the plating solution is circulated so that the plating solution circulates. A device for removing Ni ions and Fe ions from a galvanizing solution, characterized in that a metal ion detection device and a control device for controlling the addition of an oxidizer according to the detected value are provided on the inlet side of the oxidation tank.
ルめっき鋼板を製造した後、上記製造に用いためっき液
をラインから分離し、ライン設備を水洗した後、亜鉛め
っき液に切り換え、その際に該亜鉛めっき液に不純物と
して混入するＮｉイオンおよびＦｅイオンを請求項１ま
たは請求項２により除去した亜鉛めっき液を用いて、前
記めっきラインで電気亜鉛めっき鋼板を製造することを
特徴とするＮｉイオンおよびＦｅイオンの除去された亜
鉛めっき液による電気亜鉛めっき鋼板の製造方法。4. After producing an electrogalvanized nickel-plated steel sheet by one plating line, the plating solution used in the above production is separated from the line, the line equipment is washed with water, and then the galvanizing solution is switched to, Ni ions and Fe ions mixed as impurities in the galvanizing solution are removed by the galvanizing solution according to claim 1 or 2 to produce an electrogalvanized steel sheet on the galvanizing line. And a method for producing an electrogalvanized steel sheet using a zinc plating solution from which Fe ions have been removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34126595A JP3209674B2 (en) | 1995-12-27 | 1995-12-27 | Method for removing Ni ions and Fe ions from galvanizing solution, apparatus for removing the same, and method for producing electrogalvanized steel sheet by using the removed galvanizing solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34126595A JP3209674B2 (en) | 1995-12-27 | 1995-12-27 | Method for removing Ni ions and Fe ions from galvanizing solution, apparatus for removing the same, and method for producing electrogalvanized steel sheet by using the removed galvanizing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09176899A true JPH09176899A (en) | 1997-07-08 |
| JP3209674B2 JP3209674B2 (en) | 2001-09-17 |
Family
ID=18344712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34126595A Expired - Lifetime JP3209674B2 (en) | 1995-12-27 | 1995-12-27 | Method for removing Ni ions and Fe ions from galvanizing solution, apparatus for removing the same, and method for producing electrogalvanized steel sheet by using the removed galvanizing solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3209674B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013185190A (en) * | 2012-03-07 | 2013-09-19 | Jfe Steel Corp | Method for manufacturing electrogalvanized steel sheet |
| JP5980677B2 (en) * | 2010-05-28 | 2016-08-31 | 東洋製罐株式会社 | Surface treatment bath, method for producing surface-treated steel plate using this surface treatment bath, and surface-treated steel plate comprising this production method |
-
1995
- 1995-12-27 JP JP34126595A patent/JP3209674B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5980677B2 (en) * | 2010-05-28 | 2016-08-31 | 東洋製罐株式会社 | Surface treatment bath, method for producing surface-treated steel plate using this surface treatment bath, and surface-treated steel plate comprising this production method |
| US10000858B2 (en) | 2010-05-28 | 2018-06-19 | Toyo Seikan Group Holdings, Ltd. | Bath for surface treatment, method of producing surface-treated steel plate by using the bath for surface treatment, and surface treated steel plate produced by the same method |
| JP2013185190A (en) * | 2012-03-07 | 2013-09-19 | Jfe Steel Corp | Method for manufacturing electrogalvanized steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3209674B2 (en) | 2001-09-17 |
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