JP2006316330A - Method and device for maintaining function of nitric acid solution for activating surface of plating stock - Google Patents
Method and device for maintaining function of nitric acid solution for activating surface of plating stock Download PDFInfo
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 70
- 238000007747 plating Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003213 activating effect Effects 0.000 title 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 24
- 238000005342 ion exchange Methods 0.000 claims abstract description 19
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 18
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 24
- 238000012423 maintenance Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims description 7
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 24
- 229910000831 Steel Inorganic materials 0.000 abstract description 10
- 239000010959 steel Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 52
- 239000007788 liquid Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 hydrogen ions Chemical class 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
本発明は、鋼材の亜鉛めっき・クロメート処理におけるめっき素材表面活性化硝酸溶液の機能維持方法と装置に関する。 The present invention relates to a method and an apparatus for maintaining the function of a plating material surface activated nitric acid solution in galvanizing / chromate treatment of steel.
従来、鋼材は腐食しやすいため、広くめっきが行われている。鋼材のめっきとして、亜鉛めっきが広く行われているが、更に表面特性向上のため、亜鉛めっきを施した後、更にクロメート処理が行われている。
この場合、亜鉛めっきと、クロメート処理の連続した工程で行われることが多く、亜鉛めっきに伴う金属イオンが次の工程であるクロメート処理に悪影響を及ぼす可能性がある。
Conventionally, since steel materials are easily corroded, they are widely plated. As plating of steel materials, galvanization is widely performed, but further chromate treatment is performed after galvanization for further improving surface characteristics.
In this case, it is often performed in a continuous process of galvanization and chromate treatment, and metal ions accompanying galvanization may adversely affect the chromate treatment which is the next process.
このような悪影響を除去するため、クロメート処理のためのクロメート処理槽にｐＨ計を設けると共に、該ｐＨ計に制御されて動作する送液ポンプ、及び薬注ポンプを設け、ｐＨ値が一定範囲を超えた場合該送液ポンプを作動させてクロメート処理液をＨ型カチオン交換塔に導き、クロメート処理液に溶解する金属イオンをイオン交換により水素イオンと交換させて処理水として再度クロメート処理槽に返送することにより、金属イオンの発生により消費された量の水素イオンを金属イオンの除去と共に補給し、
ｐＨ値が所定の値まで下がらない場合に該薬注ポンプを作動させて被処理物への付着及び被処理物による液出しなどによるクロメート処理有効成分を補給し、
クロメート被処理槽内のクロメート処理液のｐＨ値、有効成分濃度、金属濃度を調整しつつクロメート処理浴の管理を行うことを特徴とする低濃度クロメート処理浴の管理方法が公知である（特許文献１）
しかし、亜鉛めっき後、クロメート処理を行う場合、なお、クロメート処理層の密着性になお問題を残し改良の余地を残している。
In order to eliminate such adverse effects, a chromate treatment tank for chromate treatment is provided with a pH meter, a liquid feed pump that operates under the control of the pH meter, and a chemical injection pump, and the pH value falls within a certain range. If exceeded, the liquid feed pump is operated to guide the chromate treatment liquid to the H-type cation exchange tower, and the metal ions dissolved in the chromate treatment liquid are exchanged with hydrogen ions by ion exchange and returned to the chromate treatment tank again as treated water. By replenishing the amount of hydrogen ions consumed by the generation of metal ions together with the removal of metal ions,
When the pH value does not drop to a predetermined value, the chemical injection pump is operated to replenish the chromate treatment active ingredient by adhesion to the treatment object and liquid discharge by the treatment object,
A management method for a low-concentration chromate treatment bath is known in which the chromate treatment bath is managed while adjusting the pH value, active ingredient concentration, and metal concentration of the chromate treatment liquid in the chromate treatment tank (Patent Literature). 1)
However, when chromate treatment is performed after galvanization, there is still a problem in the adhesion of the chromate treatment layer, leaving room for improvement.
また、亜鉛めっきとクロメート処理の間に硝酸溶液に浸漬して光沢を増す処理も行われている。硝酸処理液は、亜鉛めっき工程から製品に付着して持ち込まれる金属イオン（鉄、亜鉛）、活性化による素地表面からの溶解金属イオン（鉄、亜鉛）が次第に蓄積して活性化の効果が失われる。素地表面の光沢が失われた時点で、硝酸溶液の全量入れ替えが必要となり、硝酸の調達費用や作業の手間が必要となる。 Further, a treatment for increasing gloss by dipping in a nitric acid solution between galvanization and chromate treatment is also performed. In the nitric acid treatment solution, the metal ions (iron and zinc) that are brought into the product from the galvanizing process and the dissolved metal ions (iron and zinc) from the substrate surface due to activation gradually accumulate and the activation effect is lost. Is called. When the luster of the substrate surface is lost, it is necessary to replace the entire amount of the nitric acid solution, which necessitates a procurement cost of nitric acid and labor.
本発明の目的は、
鋼材のめっきにおいて、従来から広く行われてきた所定時間経過後における全量交換などの方法に代え、硝酸溶液中の金属イオンを除去し、素材表面活性化硝酸溶液の機能維持し、素地の表面の光沢を維持すること、硝酸の廃棄を可能な限り少なくすること
である。
The purpose of the present invention is to
In the plating of steel materials, instead of replacing the entire amount after a predetermined time, which has been widely used in the past, the metal ions in the nitric acid solution are removed, the function of the material surface activated nitric acid solution is maintained, and the surface of the substrate is removed. To maintain gloss and to reduce nitric acid disposal as much as possible.
本発明者らは、前記目的のため、硝酸酸性下においても、イオン交換樹脂を使用するイオン交換により金属イオンが除去可能であることを見出し本発明到達したのである。
すなわち本発明は、
（１）めっき素材表面活性化硝酸溶液の機能維持方法において、
硝酸溶液処理に使用する硝酸溶液に混入した金属イオンを、イオン交換樹脂を使用するイオン交換によって除去し、再び硝酸溶液にして返還する工程を含むことを特徴とする、
（２）めっき素材表面活性化硝酸溶液の機能維持装置おいて、
硝酸溶液処理装置に混入してくる金属イオンをイオン交換樹脂を使用するイオン交換によって除去し、硝酸溶液処理装置に返還するための装置を有することを特徴とする、
（３） （１）のめっき素材表面活性化硝酸溶液の機能維持方法において、硝酸及び金属イオンを含む硝酸溶液は水素イオン濃度が管理され、かつ管理された量の硝酸溶液が、イオン交換され、金属イオンが除去されることを特徴とする、
（４） （２）のめっき素材表面活性化硝酸溶液の機能維持装置において、
硝酸溶液装置には、水素イオン濃度を管理するための装置が付属し、管理された量の硝酸溶液をイオン交換装置に送るための装置を有することを特徴とする、
（５） （１）のめっき素材表面活性化硝酸溶液の機能維持方法において、
使用するイオン交換樹脂が強酸型陽イオン交換樹脂であることを特徴とする、
（６） （２）のめっき素材表面活性化硝酸溶液の機能維持装置において、
使用するイオン交換樹脂が強酸型陽イオン交換樹脂であることを特徴とする。
For the purpose described above, the present inventors have found that metal ions can be removed by ion exchange using an ion exchange resin even under acidic conditions of nitric acid, and have reached the present invention.
That is, the present invention
(1) In the method of maintaining the function of the plating material surface activated nitric acid solution,
The method includes removing the metal ions mixed in the nitric acid solution used for the nitric acid solution treatment by ion exchange using an ion exchange resin, and returning the nitric acid solution again.
(2) In the function maintenance device of the plating material surface activated nitric acid solution,
It has a device for removing metal ions mixed in the nitric acid solution treatment apparatus by ion exchange using an ion exchange resin and returning it to the nitric acid solution treatment apparatus.
(3) In the method for maintaining the function of the plating material surface activated nitric acid solution according to (1), the nitric acid solution containing nitric acid and metal ions is controlled in hydrogen ion concentration, and the controlled amount of nitric acid solution is ion-exchanged, Metal ions are removed,
(4) In the function maintaining device of the plating material surface activated nitric acid solution of (2),
The nitric acid solution device is equipped with a device for managing the hydrogen ion concentration, and has a device for sending a controlled amount of the nitric acid solution to the ion exchange device.
(5) In the function maintaining method of the plating material surface activated nitric acid solution of (1),
The ion exchange resin used is a strong acid cation exchange resin,
(6) In the function maintaining device of the plating material surface activated nitric acid solution of (2),
The ion exchange resin to be used is a strong acid type cation exchange resin.
本発明においては、硝酸溶液処理に使用する硝酸溶液に混入した金属イオンを、イオン交換によって除去する。ここにイオン交換に使用されるイオン交換樹脂としては、スルホン酸型の陽イオン交換樹脂が使用される。すなわち、スチレンとジビニルベンゼンとの共重合物をスルホン化し、更に硫酸などの酸を使用し、Ｈ型とした陽イオン型樹脂をあげることができる。 In the present invention, metal ions mixed in the nitric acid solution used for the nitric acid solution treatment are removed by ion exchange. Here, as the ion exchange resin used for ion exchange, a sulfonic acid type cation exchange resin is used. That is, it is possible to use a cation-type resin which is obtained by sulfonating a copolymer of styrene and divinylbenzene and further using an acid such as sulfuric acid.
ここに使用される陽イオン交換樹脂は、使用によりＨ型から、スルホン酸金属塩である金属塩型に移行するが、硫酸などの酸により、再びＨ型に変化し再生が可能であり、再び硝酸溶液に混入した金属イオンの除去が可能となる。なお、ここで、イオン交換樹脂充填塔に対する硝酸溶液の送液量を計測すれば、所定の送液量となったとき、イオン交換樹脂がＨ型から金属塩型に変化したことを経験的に知ることが可能であり、送液量の計測装置を設置することが好ましい。 The cation exchange resin used here shifts from the H type to the metal salt type which is a sulfonic acid metal salt by use. However, it can be regenerated and regenerated by an acid such as sulfuric acid. Metal ions mixed in the nitric acid solution can be removed. Here, if the amount of nitric acid solution fed to the ion-exchange resin packed tower is measured, it is empirically determined that the ion-exchange resin has changed from the H type to the metal salt type when a predetermined amount of solution is delivered. It is possible to know, and it is preferable to install a measuring device for the amount of liquid delivered.
本発明において、硝酸溶液に混入してくる金属イオンとして、鋼材に基づく、鉄イオン、亜鉛めっきに起因する亜鉛イオンをあげることができる。鉄イオン、亜鉛イオンが硝酸溶液に溶出すれば、水素イオン濃度が変化するので、水素イオン濃度を計測することにより、鉄イオン、亜鉛イオンの溶出状況を計測可能となる。このため、水素イオン濃度計測装置を設置することが好ましい。 In the present invention, examples of the metal ions mixed in the nitric acid solution include iron ions based on steel materials and zinc ions resulting from galvanization. If iron ions and zinc ions are eluted in the nitric acid solution, the hydrogen ion concentration changes. Therefore, by measuring the hydrogen ion concentration, the elution state of iron ions and zinc ions can be measured. For this reason, it is preferable to install a hydrogen ion concentration measuring device.
本発明の前工程において行われる亜鉛めっきとしては、めっき浴にシアン化合物を使用するアルカリシアン浴や、アミン浴・ピロリン酸浴・硫酸浴などの非シアンめっき、溶融亜鉛浴に浸漬する方法など従来公知の方法をあげることができるが、経済性などを考慮するとアルカリシアンめっきが好ましい。 The galvanization performed in the pre-process of the present invention includes conventional methods such as an alkaline cyan bath using a cyanide compound in the plating bath, non-cyan plating such as an amine bath, pyrophosphate bath, and sulfuric acid bath, and a method of immersing in a molten zinc bath. Although known methods can be mentioned, alkali cyan plating is preferable in consideration of economy and the like.
本発明の後工程において行われるクロメート処理としては、６価のクロムイオンを使用する方法、３価のクロムイオンを使用する方法があり、いずれの方法も適用可能である。環境問題のため、近年３価のクロム化合物を使用する方法が注目されているが、なお、問題を残しており、従来から広く使用されてきた６価のクロム化合物を使用する方法が好ましい。 As the chromate treatment performed in the subsequent step of the present invention, there are a method using hexavalent chromium ions and a method using trivalent chromium ions, and any method can be applied. In recent years, due to environmental problems, a method using a trivalent chromium compound has attracted attention. However, a method that uses a hexavalent chromium compound that has been widely used in the past is still preferred.
本発明において、イオン交換は、カラムに充填したイオン交換樹脂の層に、硝酸溶液を流す方法によって行われる。硝酸溶液は、上部から落下させて流す方法、下部から流す方法のいずれによっても行うことができる。そして、硝酸溶液は、硝酸処理装置からポンプを利用して送られる。イオン交換によって金属イオンが除去され、再び硝酸溶液槽に戻される。このような方法によれば、金属イオンの増加により、硝酸溶液処理の効果は失われないので、硝酸溶液は繰り返し使用可能となる。 In the present invention, ion exchange is performed by a method in which a nitric acid solution is passed through an ion exchange resin layer packed in a column. The nitric acid solution can be produced by either dropping from the top and flowing, or flowing from the bottom. And nitric acid solution is sent using a pump from a nitric acid processing apparatus. Metal ions are removed by ion exchange and returned to the nitric acid solution tank. According to such a method, since the effect of the nitric acid solution treatment is not lost due to the increase of metal ions, the nitric acid solution can be used repeatedly.
本発明において、使用される硝酸溶液の濃度は０．５〜１．０重量％程度の濃度である。
この範囲で光沢の維持がなされるからである。
In the present invention, the concentration of the nitric acid solution used is about 0.5 to 1.0% by weight.
This is because the gloss is maintained within this range.
図１は、本発明の、めっき素材表面活性化硝酸溶液の機能維持方法を含む鋼材のめっき方法の工程図である。鋼材は、Ｚｎめっき浴１でＺｎめっきが行われ、第一水洗浴２で水洗が行われる。
Ｚｎめっき浴は、アルカリめっき浴であり
Ｚｎ： ７．５〜３７．５ｇ／Ｌ
ＮａＣＮ： ７．５〜１０５ｇ／Ｌ
ＮａＯＨ： ７５〜９０ｇ／Ｌ
の範囲の浴が使用された。
FIG. 1 is a process diagram of a steel plating method including a method for maintaining the function of a plating material surface activated nitric acid solution according to the present invention. The steel material is subjected to Zn plating in the Zn plating
The Zn plating bath is an alkaline plating bath and Zn: 7.5 to 37.5 g / L
NaCN: 7.5-105 g / L
NaOH: 75-90 g / L
A range of baths was used.
亜鉛めっきされた鋼材は、第一水洗槽で水洗され、次に硝酸溶液処理槽３に移行する。ここに硝酸濃度は０．５〜１．０重量％の範囲である。次に第二水洗槽４で水洗され、クロメート処理槽に移行する。硝酸溶液は、挿入されているｐＨメータセンサ８により管理される。また硝酸溶液は、ポンプ６によりイオン交換塔７に送られ、イオン交換により陽イオンが除去された後、硝酸溶液処理槽３に返送される。なお、処理された液量は、流量計９により計測される。
クロメート処理槽の組成としては、
ＣｒＯ3 ：１〜４０ｇ／Ｌ
硫酸 ：３ｇ／Ｌ
硝酸 ：４．９ｇ／Ｌ
が使用された。
The galvanized steel material is washed with water in the first water washing tank and then moves to the nitric acid
As a composition of chromate treatment tank,
CrO 3 : 1 to 40 g / L
Sulfuric acid: 3 g / L
Nitric acid: 4.9 g / L
Was used.
表１は、運転中における硝酸溶液の測定結果である。
註２：Ｆ−ＨＮＯ3 は、ｐＨ＝４までの中和滴定から、ＨＮＯ3 濃度に換算
図２は、本発明の、めっき素材表面活性化硝酸溶液の機能維持装置であるポンプ別置き装置（ポンプとイオン交換樹脂充填塔を別の位置に設置している）の略図である。
硝酸溶液槽３から硝酸溶液は、ポンプ６により、イオン吸着塔７に送られる。硝酸溶液は、イオン吸着塔７の上部から入り、下部から取り出され、硝酸溶液槽７に戻る。
Table 1 shows the measurement results of the nitric acid solution during operation.
The nitric acid solution from the nitric
イオン交換塔の設備概況及び運転条件は下記の通りである。
使用イオン交換樹脂： 強酸性陽イオン交換樹脂 Ｈ型
樹脂量 ： ２００ｍ／Ｌ
使用容器 ： φ２０×５６０ｍｍ（充填層高）
通液速度 ： ＳＶ＝１．５〜２．５（平均２）
上記条件で通液し、一定量毎の成分分析を行った結果を表２に示す。
Used ion exchange resin: Strongly acidic cation exchange resin H-type resin amount: 200 m / L
Container used: φ20 × 560mm (filled bed height)
Flow rate: SV = 1.5 to 2.5 (average 2)
Table 2 shows the results of the component analysis conducted for each fixed amount under the above conditions.
通液終了後に得られた再生液の濃度の一例を表３に示す。吸着量から換算すると亜鉛の再生効率は、約９６％、鉄は約４６％である。
本発明によれば、クロメート処理の前に、管理された硝酸溶液処理がなされ、硝酸溶液に溶出する金属はイオン交換により除去される。このため
（１） クロメート処理槽の密着性が優れ、品質が一定している
（２） 溶出した金属による悪影響が除去されるため、繰り返し使用でき、硝酸の廃棄が実質的にゼロとなり、廃棄硝酸の処理コストが不要となる。
（３） 設備も簡単で比較的少ない費用で可能である。
According to the present invention, a controlled nitric acid solution treatment is performed before the chromate treatment, and the metal eluted in the nitric acid solution is removed by ion exchange. For this reason, (1) the chromate treatment tank has excellent adhesion and the quality is constant. (2) Since the adverse effects of the eluted metal are removed, it can be used repeatedly, and the disposal of nitric acid becomes virtually zero. The processing cost becomes unnecessary.
(3) The equipment is simple and can be produced at relatively low cost.
１ Ｚｎめっき槽
２ 第１水洗槽
３ 硝酸処理槽
４ 第２水洗槽
５ クロメート処理槽
６ 送液ポンプ
７ イオン吸着塔
８ ｐＨメータセンサ
９ 積算流量計
１０ 循環用配管
DESCRIPTION OF
Claims (6)
硝酸溶液処理に使用する硝酸溶液に混入した金属イオンを、イオン交換樹脂を使用するイオン交換によって除去し、再び硝酸溶液にして返還する工程を含むことを特徴とするめっき素材表面活性化硝酸溶液の機能維持方法。 In the method of maintaining the function of the plating material surface activated nitric acid solution,
A plating material surface activated nitric acid solution comprising a step of removing metal ions mixed in a nitric acid solution used for nitric acid solution treatment by ion exchange using an ion exchange resin and returning it to a nitric acid solution again. Function maintenance method.
硝酸溶液処理装置に混入してくる金属イオンをイオン交換樹脂を使用するイオン交換によって除去し、硝酸溶液処理装置に返還するための装置を有することを特徴とするめっき素材表面活性化硝酸溶液の機能維持装置。 In the function maintenance device of plating material surface activated nitric acid solution,
The function of the plating material surface activated nitric acid solution, which has a device for removing metal ions mixed in the nitric acid solution treatment device by ion exchange using an ion exchange resin and returning it to the nitric acid solution treatment device Maintenance device.
硝酸及び金属イオンを含む硝酸溶液は水素イオン濃度が管理され、かつ管理された量の硝酸溶液が、イオン交換され、金属イオンが除去されることを特徴とするめっき素材表面活性化硝酸溶液の機能維持方法。 In the method of maintaining the function of the plating material surface activated nitric acid solution according to claim 1,
Nitric acid solution containing nitric acid and metal ions is controlled in hydrogen ion concentration, and a controlled amount of nitric acid solution is ion-exchanged to remove metal ions. Maintenance method.
硝酸溶液装置には、水素イオン濃度を管理するための装置が付属し、管理された量の硝酸溶液をイオン交換装置に送るための装置を有することを特徴とする鋼材のめっき装置。 In the function maintenance apparatus of the plating raw material surface activation nitric acid solution of Claim 2,
An apparatus for managing the hydrogen ion concentration is attached to the nitric acid solution apparatus, and the apparatus for sending a controlled amount of nitric acid solution to the ion exchange apparatus is provided.
使用するイオン交換樹脂が強酸型陽イオン交換樹脂であることを特徴とするめっき素材表面活性化硝酸溶液の機能維持方法。 In the method of maintaining the function of the plating material surface activated nitric acid solution according to claim 1,
A method for maintaining the function of a plating material surface-activated nitric acid solution, wherein the ion exchange resin used is a strong acid cation exchange resin.
使用するイオン交換樹脂が強酸型陽イオン交換樹脂であることを特徴とするめっき素材表面活性化硝酸溶液の機能維持装置。
In the function maintenance apparatus of the plating raw material surface activation nitric acid solution of Claim 2,
A function maintaining device for a plating material surface activated nitric acid solution, wherein the ion exchange resin used is a strong acid cation exchange resin.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013168799A1 (en) * | 2012-05-10 | 2013-11-14 | ディップソール株式会社 | Method for regenerating solution for nitric acid activation treatment of zinc-plated metal member surface, and regeneration treatment apparatus using same |
| JP2017045031A (en) * | 2015-08-28 | 2017-03-02 | 住華科技股▲フン▼有限公司Ｓｕｍｉｋａ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ | Method of manufacturing polarizing film |
| JP2017145503A (en) * | 2016-02-18 | 2017-08-24 | Ｊｆｅスチール株式会社 | Zn-Al-Mg-BASED PLATED STEEL SHEET WITH COATING FILM AND MANUFACTURING METHOD OF THE SAME |
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- 2005-05-16 JP JP2005142142A patent/JP2006316330A/en active Pending
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| WO2013168799A1 (en) * | 2012-05-10 | 2013-11-14 | ディップソール株式会社 | Method for regenerating solution for nitric acid activation treatment of zinc-plated metal member surface, and regeneration treatment apparatus using same |
| JP2013234371A (en) * | 2012-05-10 | 2013-11-21 | Dipsol Chemicals Co Ltd | Regeneration method of nitric acid activation treatment solution for zinc plating metal member surface, and regeneration apparatus using the same |
| KR20150008084A (en) | 2012-05-10 | 2015-01-21 | 딥솔 가부시키가이샤 | Method for regenerating solution for nitric acid activation treatment of zinc-plated metal member surface, and regeneration treatment apparatus using same |
| CN104321466A (en) * | 2012-05-10 | 2015-01-28 | 迪普索尔化学株式会社 | Method for regenerating solution for nitric acid activation treatment of zinc-plated metal member surface, and regeneration treatment apparatus using same |
| US9249509B2 (en) | 2012-05-10 | 2016-02-02 | Dipsol Chemicals Co., Ltd. | Method for regenerating solution for nitric acid activation treatment of zinc-plated metal member surface, and regeneration treatment apparatus using the same |
| EP2848713A4 (en) * | 2012-05-10 | 2016-02-10 | Dipsol Chem | Method for regenerating solution for nitric acid activation treatment of zinc-plated metal member surface, and regeneration treatment apparatus using same |
| TWI558852B (en) * | 2012-05-10 | 2016-11-21 | 迪普索股份有限公司 | Regeneration method of nitric acid active treatment solution for zinc-plated metal member surface and regeneration treatment apparatus using the same method |
| KR102088542B1 (en) | 2012-05-10 | 2020-03-12 | 딥솔 가부시키가이샤 | Method for regenerating solution for nitric acid activation treatment of zinc-plated metal member surface, and regeneration treatment apparatus using the same |
| JP2017045031A (en) * | 2015-08-28 | 2017-03-02 | 住華科技股▲フン▼有限公司Ｓｕｍｉｋａ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ | Method of manufacturing polarizing film |
| JP2017145503A (en) * | 2016-02-18 | 2017-08-24 | Ｊｆｅスチール株式会社 | Zn-Al-Mg-BASED PLATED STEEL SHEET WITH COATING FILM AND MANUFACTURING METHOD OF THE SAME |
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