JPH08120472A - Pickling and descaling of wire rod coil and neutralizing and cleaning of coil after pickling - Google Patents
Pickling and descaling of wire rod coil and neutralizing and cleaning of coil after picklingInfo
- Publication number
- JPH08120472A JPH08120472A JP7129867A JP12986795A JPH08120472A JP H08120472 A JPH08120472 A JP H08120472A JP 7129867 A JP7129867 A JP 7129867A JP 12986795 A JP12986795 A JP 12986795A JP H08120472 A JPH08120472 A JP H08120472A
- Authority
- JP
- Japan
- Prior art keywords
- pickling
- scale
- wire
- coil
- acid solution
- 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
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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明はコイル状に巻き取られた
線材の表面に生成したスケールを酸洗により剥離する際
に脱スケールまでの時間短縮と酸洗後のコイル表面の清
浄化を図るための酸洗による脱スケール処理方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention aims to shorten the time until descaling when the scale formed on the surface of a wire wound into a coil is peeled by pickling and to clean the coil surface after pickling. The present invention relates to a method for descaling by pickling.
【0002】[0002]
【従来の技術】熱間圧延により製造された線材あるいは
二次加工工程で熱処理された鋼線の表面にはスケールが
形成されており、線材の二次加工の伸線等に先立ち表面
に形成されたスケールを剥離することが必要である。こ
のスケールを剥離する方法としては機械的方法と化学的
方法あるいは両者を組み合わせた方法がある。また、化
学的方法でも線材を軸芯方向に走行させて酸洗液中を通
過させるストランド方式と線材をコイル状のまま酸洗液
中に浸漬させるバッチ方式とがある。2. Description of the Related Art A scale is formed on the surface of a wire rod manufactured by hot rolling or a steel wire heat-treated in the secondary processing step, and the scale is formed on the surface prior to wire drawing in the secondary processing of the wire rod. It is necessary to peel off the scale. As a method for exfoliating this scale, there are a mechanical method and a chemical method, or a method in which both are combined. Further, also in the chemical method, there are a strand method in which a wire is made to run in the axial direction to pass through the pickling solution, and a batch method in which the wire is immersed in the pickling solution in a coil form.
【0003】近年、公害問題やコスト低減の観点からメ
カニカルデスケーリング法も採用されているが酸洗法は
生産性が高く、各種鋼種への対応が容易であること、さ
らにスケールの剥離とともに、表面肌の制御による後工
程の二次加工での潤滑性の制御もしやすい等の利点を有
していることから酸洗によるスケールの剥離が広く採用
されている。しかし線材コイルの酸洗を行う場合には線
材がリング状に束になって結束されているためにそれぞ
れの線材が重なり合い、コイル内部に酸溶液が浸透し難
く、コイル内部はスケールが残存し易いために後工程で
のトラブルの原因となる問題があった。In recent years, a mechanical descaling method has also been adopted from the viewpoint of pollution problems and cost reduction, but the pickling method has high productivity and is easily applicable to various steel types. Peeling of scale by pickling is widely adopted because it has advantages such as easy control of lubricity in secondary processing in the post-process by controlling skin. However, when pickling the wire rod coil, the wire rods are bundled in a ring shape and bundled together, so the wire rods overlap and the acid solution does not easily permeate into the coil, and the scale easily remains inside the coil. Therefore, there is a problem that causes trouble in the subsequent process.
【0004】このような問題を解決するために設備によ
る改善としては特開昭54−114438号公報には線
材コイルのバッチ酸洗時に線材コイルに振動を加えると
共に線材コイルをフック上で円周方向に回転させ線材全
長を均一に酸洗する方法が、また、特開平3−6878
9号公報には酸洗浴内に超音波振動子を設置し酸洗時に
超音波を付加して線材コイル全体を均一に酸洗する方法
が開示されている。As an improvement by means of equipment to solve such a problem, Japanese Patent Laid-Open No. 54-114438 discloses that a wire coil is vibrated during batch pickling of the wire coil and the wire coil is circumferentially mounted on the hook. The method of uniformly pickling the entire length of the wire rod by rotating the wire rod is also disclosed in JP-A-3-6878
No. 9 discloses a method in which an ultrasonic vibrator is installed in a pickling bath and ultrasonic waves are applied during pickling to uniformly pickle the entire wire coil.
【0005】しかしこれらの従来技術では以下の問題が
あり必ずしも線材コイル重なり部の酸洗性を改善するに
は不十分であった。酸洗中にコイルを振動させる方法は
装置が大がかりで設備コストが大きくなり、設備化が容
易にできないこと。さらに騒音の発生による作業環境の
悪化、および振動がクレーンあるいは酸洗設備の建築物
まで伝わり設備故障の原因となり易い問題がある。この
ように酸洗時に振動を与える方法はスケール剥離性の改
善効果はあっても実用時の課題が多い技術である。However, these conventional techniques have the following problems and are not always sufficient for improving the pickling property of the wire coil overlapping portion. The method of vibrating the coil during pickling requires a large device, which increases equipment costs and makes it difficult to install equipment. Further, there is a problem that the work environment is deteriorated due to the generation of noise, and the vibration is transmitted to the crane or the building of the pickling equipment, which easily causes equipment failure. As described above, the method of giving vibration during pickling has many problems in practical use even though it has an effect of improving scale releasability.
【0006】酸洗中に超音波振動を与える方法は超音波
振動子の設置位置が非常に重要であり、超音波振動子と
線材コイルの距離が変化するとその効果が著しく変化
し、スケール剥離性の改善効果が低下する。従って、ス
ケールの剥離性改善効果を発揮するためには線材コイル
を確実に位置決めする必要があり、微妙な作業が要求さ
れ、作業性の低下を招くため実用性が乏しい技術であ
る。また超音波を発生するための装置が高価であり容易
には実用化されにくい問題がある。In the method of applying ultrasonic vibration during pickling, the installation position of the ultrasonic vibrator is very important, and when the distance between the ultrasonic vibrator and the wire coil changes, the effect remarkably changes, resulting in scale peeling. The improvement effect of is reduced. Therefore, in order to exert the effect of improving the peelability of the scale, it is necessary to reliably position the wire rod coil, delicate work is required, and the workability is deteriorated. Further, there is a problem that an apparatus for generating ultrasonic waves is expensive and is not easily put into practical use.
【0007】一方、酸溶液の酸洗性を改善する方法とし
ては特開昭58−73778号公報および特開昭58−
73779号公報に1塩基系の酸および2塩基系の酸溶
液の2価および3価の鉄イオン濃度を一定範囲に制御し
て酸洗時のスケールの剥離性を改善する方法が開示され
ている。しかし酸洗溶液によるスケールの剥離性を改善
する方法では線材コイルのように重なり合い、きつく結
束されている場合には線材内部まで酸溶液が浸透するこ
とは困難であり、この酸溶液による線材重なり部でのス
ケールの剥離性を改善するにはほとんど効果がないばか
りか線材重なり部および密閉部では鉄イオン濃度が急激
に増加し、短時間で飽和濃度に達し、酸溶液のスケール
の溶解能力が低下し、線材コイルのスケール剥離性を著
しく悪化させるために線材コイルの酸洗には適用できな
いものであった。On the other hand, as a method for improving the pickling property of an acid solution, JP-A-58-73778 and JP-A-58-78 are known.
Japanese Patent No. 73779 discloses a method of improving the peelability of scale during pickling by controlling the divalent and trivalent iron ion concentrations of a monobasic acid and dibasic acid solution within a certain range. . However, in the method of improving the peelability of scale by pickling solution, it overlaps like a wire coil, and when tightly bound, it is difficult for the acid solution to penetrate into the inside of the wire. It has almost no effect on improving the scale releasability at the same time, and the iron ion concentration increases sharply in the overlapped part and the closed part of the wire, reaching the saturated concentration in a short time, and the dissolution capacity of the scale of the acid solution decreases. However, it cannot be applied to the pickling of the wire coil because it significantly deteriorates the scale releasability of the wire coil.
【0008】[0008]
【発明が解決しようとする課題】本発明は、上記のよう
な状況を鑑みて線材コイルのバッチ酸洗処理時に簡便な
方法を用いて線材コイルの重なり部でのスケールの剥離
性を改善し、効率よく短時間で線材スケールを全長にわ
たり均一に剥離するための方法を提供するものである。In view of the above situation, the present invention improves the scale releasability at the overlapping portion of the wire coil by using a simple method during the batch pickling treatment of the wire coil, It is intended to provide a method for efficiently and uniformly stripping a wire rod scale over the entire length.
【0009】[0009]
【課題を解決するための手段】このような線材の重なり
部分あるいは密閉部分のスケールの剥離性を改善するた
めに本発明者らは酸洗状況に関して詳細な検討を加えた
結果、本発明を達成するに至ったものでその要旨とする
ところは線材コイルを酸洗浴に浸漬して脱スケール処理
を行う方法において酸洗溶液を強制的に撹拌、流動させ
ながら処理することを特徴とする線材コイルの酸洗脱ス
ケール方法である。In order to improve the scale releasability of the overlapping portion or the closed portion of such wire rods, the present inventors have made a detailed study on the pickling condition, and as a result, achieved the present invention. In the method of performing descaling treatment by immersing the wire coil in a pickling bath, the pickling solution is forcibly stirred and flowed while the wire coil is treated. It is a pickling descaling method.
【0010】酸洗後の水洗処理あるいは中和処理時にお
いて溶液を撹拌、流動させながら処理することを特徴と
する線材コイルの中和、洗浄方法。A method for neutralizing and cleaning a wire coil, characterized in that the solution is treated while being stirred and flowing during the washing or neutralization treatment after pickling.
【0011】酸溶液および中和、洗浄溶液を撹拌する場
合、ガスを吹き付けるノズルを有するパイプを酸洗浴お
よび中和、洗浄浴内に浸漬し、該ノズルを線材コイルに
向かってガスを吹き付け酸溶液および中和、洗浄溶液を
流動化させることを特徴とする線材コイルの酸洗脱スケ
ール方法で、酸洗溶液の撹拌時にノズルから吹き付ける
ガスが酸素を含有することを特徴とする線材コイルの酸
洗脱スケール方法および中和、洗浄方法。When stirring the acid solution and the neutralization / cleaning solution, a pipe having a nozzle for spraying a gas is immersed in the pickling bath and the neutralization / cleaning bath, and the nozzle is blown with a gas to blow the acid solution. And a method of pickling and descaling a wire coil, characterized by fluidizing the cleaning solution, wherein the gas sprayed from the nozzle at the time of stirring the pickling solution contains oxygen. Descaling method, neutralization and washing method.
【0012】さらに、酸洗処理溶液中の3価のFeイオ
ン濃度が10g/l以上、60g/l以下の濃度範囲に
調整した酸洗溶液を用い、該酸溶液を強制的に撹拌、流
動化させることを特徴とする線材コイルの酸洗脱スケー
ル方法。Further, using a pickling solution in which the concentration of trivalent Fe ions in the pickling solution is adjusted to 10 g / l or more and 60 g / l or less, the acid solution is forcibly stirred and fluidized. A method of pickling and descaling a wire coil, which comprises:
【0013】本発明における酸溶液あるいは水洗および
中和液の撹拌、流動させる手段としてはたとえば酸洗槽
の内部にスクリュー等を設置し機械的に撹拌する方法、
酸洗槽の中に一定流速のガスを吹き込んでガスの流れと
共に酸溶液を撹拌する方法またはこれらの方法を組み合
わせ等いずれの方法も適用できる。As means for stirring and flowing the acid solution or the washing and neutralizing solution in the present invention, for example, a method of installing a screw or the like inside the pickling tank and mechanically stirring,
Any method such as a method of blowing a gas at a constant flow rate into the pickling tank and stirring the acid solution together with the gas flow, or a combination of these methods can be applied.
【0014】酸溶液の流動化の程度は酸洗を行う線材表
面に形成されたスケール厚さ、組成、重量、結束強度、
酸溶液の酸濃度、酸溶液温度等により適宜決定すること
ができ、最適条件とすることにより最も効率よく酸洗が
可能となる。The degree of fluidization of the acid solution depends on the scale thickness, composition, weight, binding strength of the scale formed on the surface of the wire to be pickled.
It can be appropriately determined depending on the acid concentration of the acid solution, the temperature of the acid solution, etc., and the optimum conditions enable the most efficient pickling.
【0015】たとえばスケールの剥離性が良好な線材コ
イルをスケールを剥離させる能力が高い酸溶液で酸洗す
る場合には比較的マイルドな撹拌で十分なスケールの剥
離が可能となる。For example, when a wire rod coil having a good scale releasability is pickled with an acid solution having a high ability to remove the scale, it is possible to sufficiently remove the scale with relatively mild stirring.
【0016】逆に線材コイルの結束強度が強く、かつス
ケールの酸洗剥離性が不良な線材コイルをスケール剥離
能力が低い酸溶液で酸洗する場合は、酸溶液の撹拌速度
を高め酸溶液の運動エネルギーを高めてやることにより
線材コイルの内部まで酸溶液を浸透させることができ、
十分なスケールの剥離が可能となる。On the contrary, when a wire coil having a strong binding strength of the wire coil and a poor pickling and peeling property of the scale is pickled with an acid solution having a low scale peeling ability, the stirring speed of the acid solution is increased. By increasing the kinetic energy, the acid solution can penetrate into the inside of the wire coil,
Peeling of sufficient scale is possible.
【0017】一方、過度に酸溶液を流動化した場合には
酸洗槽から酸溶液が飛散する可能性があるために、酸溶
液の撹拌、流動化は必要最低限の条件が好ましい。ま
た、酸洗槽に蓋をかぶせて酸洗を行うことにより酸溶液
の飛散を完全に防止することも可能である。On the other hand, if the acid solution is excessively fluidized, the acid solution may be scattered from the pickling tank. Therefore, it is preferable that the acid solution is stirred and fluidized under the minimum necessary conditions. It is also possible to completely prevent the acid solution from scattering by covering the pickling tank with a lid and performing pickling.
【0018】ノズルを有するパイプを酸溶液、中和液お
よび洗浄液に浸漬してノズルからガスを吹き込みこれら
の溶液を撹拌、流動化する本発明の方法において、ノズ
ルは単純な微少な穴をあけたものでもガスが拡散放出さ
れるように構成されたノズル等ガスの吹き込みが行える
ものであれば使用可能である。In the method of the present invention in which a pipe having a nozzle is immersed in an acid solution, a neutralizing solution and a cleaning solution and gas is blown from the nozzle to stir and fluidize these solutions, the nozzle is provided with simple fine holes. Any one can be used as long as it can blow the gas, such as a nozzle configured to diffuse and discharge the gas.
【0019】ガス吹き出しノズルの設置形態は処理浴内
部に事前に浸漬させ、固定しておく方法でも、処理作業
を行うときにのみ浸漬する方法のいずれでも良いが、ノ
ズルの酸液による腐食防止、寿命を考慮すると、作業時
にのみ浸漬させる方法が好ましい。また、酸溶液、水洗
等の各処理液の撹拌、流動のみを目的とした場合には、
酸洗液と反応して有害なガスが発生するものでなければ
特にガスの種類は限定されず、不活性ガス、空気等使用
できる。The gas blowing nozzle may be installed either by preliminarily immersing it in the treatment bath and fixing it, or by immersing it only during the treatment work. To prevent corrosion of the nozzle by the acid solution, Considering the service life, the method of immersing only during working is preferable. Further, when the purpose is only to stir and flow each treatment solution such as an acid solution and water washing,
The type of gas is not particularly limited as long as it does not generate a harmful gas by reacting with the pickling solution, and an inert gas, air or the like can be used.
【0020】本発明の3価の鉄イオンの濃度を制御する
手段としては酸溶液に溶解し、Fe3+となる薬品を添加
しても、酸素を含有するガスを酸洗液中に吹き込んで酸
溶液の中の2価の鉄イオンを酸化して3価の鉄イオンと
するいずれの方法も適用可能である。As a means for controlling the concentration of trivalent iron ions of the present invention, even if a chemical that becomes Fe 3+ is added after being dissolved in an acid solution, a gas containing oxygen is blown into the pickling solution. Any method of oxidizing divalent iron ions in the acid solution to form trivalent iron ions can be applied.
【0021】Fe3+となる試薬を添加する場合は酸洗浴
が比較的大きいために使用する薬品量が多くなること、
酸洗浴中にFe2+とFe3+の両イオンが溶解し、総Fe
イオン濃度が増す為に酸洗溶液の飽和溶解度に達し、比
較的早めにスケールの溶解能力が低下する可能性があ
る。一方、本発明の方法である酸素を含有するガスを酸
溶液内に吹き込んで酸洗浴中のFe2+を酸化してFe3+
とする方法は簡便でコストもかからない方法であり好ま
しい方法である。When a reagent that becomes Fe 3+ is added, the amount of chemicals used is large because the pickling bath is relatively large,
Both Fe 2+ and Fe 3+ ions are dissolved in the pickling bath and total Fe
Since the ion concentration increases, the saturated solubility of the pickling solution may be reached, and the dissolution capacity of the scale may decrease relatively early. On the other hand, according to the method of the present invention, a gas containing oxygen is blown into the acid solution to oxidize Fe 2+ in the pickling bath to produce Fe 3+.
Is a simple and inexpensive method and is a preferable method.
【0022】この吹き込みガスは酸素を含有しているガ
スであればその種類は特に限定されず、酸素含有率が高
いガス、吹き込み流量が多い場合はより短時間でFe2+
をFe3+とすることができ、酸素含有率が低く吹き込み
流量が少ない場合はFe2+の酸化に長時間を有するもの
の、この場合でも十分に酸溶液中の鉄イオンの制御は可
能である。最も簡便かつ低コストのガスとしては工場圧
空、コンプレッサーによる圧空が使用できる。Fe2+の
酸化による酸洗浴中のFeイオン濃度の調整による方法
は酸洗処理を行っていない間に空気を含有するガスを酸
溶液中に吹き込むことにより制御できるために特に酸洗
作業の支障となることはなく、酸溶液の撹拌、流動化処
理用ノズルが併用可能である。The type of the blown gas is not particularly limited as long as it is a gas containing oxygen. If the gas has a high oxygen content and the flow rate of the blown gas is large, Fe 2+ is supplied in a shorter time.
Can be changed to Fe 3+, and if the oxygen content is low and the flow rate of blowing is small, it takes a long time to oxidize Fe 2+ , but even in this case, iron ions in the acid solution can be sufficiently controlled. . The most convenient and low-cost gas can be factory compressed air or compressed air by a compressor. The method of adjusting the Fe ion concentration in the pickling bath by oxidation of Fe 2+ can be controlled by blowing a gas containing air into the acid solution while the pickling treatment is not performed, so that the pickling work is particularly hindered. However, the nozzle for acid solution stirring and fluidization treatment can be used together.
【0023】[0023]
【作用】線材コイルの表面に形成されるスケールは熱間
圧延後の冷却時に酸化され、線材の鉄に近い部分からF
eO、Fe3O4、Fe2O3の層状構造になっている。こ
のスケールの剥離性改善のためにスケールの物性値とし
てスケール厚さ、スケール組成のFeO比率が管理さ
れ、酸洗剥離性を改善するためには薄いスケールで高い
FeO比率を有するスケール組成が有利とされている。
このFeO比率を高めるために一般的には高温で二次ス
ケールを形成する必要があり、この結果スケールも厚く
なる。従って、薄く、高FeO比率のスケールを達成す
ることは困難で、スケール性状のみで酸洗によるスケー
ル剥離性を改善することは実用上不可能であった。[Function] The scale formed on the surface of the wire coil is oxidized during cooling after hot rolling, and the part near the iron of the wire is F
It has a layered structure of eO, Fe 3 O 4 , and Fe 2 O 3 . In order to improve the peelability of the scale, the scale thickness and the FeO ratio of the scale composition are controlled as physical property values of the scale, and in order to improve the pickling peelability, the scale composition having a high FeO ratio in a thin scale is advantageous. Has been done.
In order to increase this FeO ratio, it is generally necessary to form a secondary scale at high temperature, which results in a thicker scale. Therefore, it was difficult to achieve a thin scale with a high FeO ratio, and it was practically impossible to improve the scale releasability by pickling only with the scale properties.
【0024】しかし、鋼材の歩留りを高め、酸洗作業性
を改善するためにより薄く、高い剥離性を有するスケー
ルを有する線材が要求されている。この要求に対応する
ために本発明者らは線材コイルのスケールを酸洗剥離す
る方法について詳細に検討したものである。However, in order to improve the yield of steel materials and improve the pickling workability, there is a demand for thinner wire rods having a scale having a high peeling property. In order to meet this demand, the present inventors have studied in detail a method of pickling and removing the scale of the wire coil.
【0025】スケールの酸洗剥離は1塩基系の塩酸を主
体とした反応ではFeO,Fe3O4のスケールの溶解反
応および酸洗処理中に酸洗溶液がスケールの亀裂及び欠
陥から進入し、地鉄、酸溶液、スケールの間に形成され
る局部電池による酸洗溶液中の水素イオンがガス化し水
素ガスとなることにより、地鉄の上層部に存在するスケ
ールに内部から圧力を加え機械的にスケールの剥離を行
う機械的な剥離作用による。The pickling and peeling of the scale is carried out by a reaction mainly consisting of monobasic hydrochloric acid, in which the pickling solution enters from scale cracks and defects during the dissolution reaction of FeO, Fe 3 O 4 scale and the pickling treatment. The hydrogen ions in the pickling solution from the local battery formed between the base iron, the acid solution, and the scale are gasified into hydrogen gas, and pressure is applied internally from the inside to the scale existing in the upper layer of the base iron. Due to the mechanical peeling action to perform scale peeling.
【0026】2塩基系の酸である硫酸の場合もほぼ同じ
作用でスケールの剥離が行われるが、溶解能力は塩酸ほ
ど大きくなく、スケール剥離の主体は水素ガス発生によ
る機械的な剥離作用となる。In the case of sulfuric acid which is a dibasic acid, the scale can be peeled off by almost the same action, but the dissolving ability is not so large as that of hydrochloric acid, and the main factor of scale peeling is the mechanical peeling action by hydrogen gas generation. .
【0027】酸洗処理はこのような化学反応が主体の反
応であるために、スケールの剥離能力を改善する方法と
して一般に高濃度、高温度が指向される。しかし、酸濃
度を高める場合には酸洗溶液の原単位の増加、作業環境
の悪化、スケールの溶解に伴う鉄イオンの溶解度の低下
による寿命の低下を引き起こし、酸溶液温度を高める方
法はヒューム等の飛散、加熱装置を有する等の設備対策
が必要であった。Since the pickling treatment is mainly a chemical reaction as described above, a high concentration and a high temperature are generally directed as a method for improving the peeling ability of the scale. However, when the acid concentration is increased, the basic unit of the pickling solution is increased, the working environment is deteriorated, the life of the iron ion is decreased due to the dissolution of scale, and the life is shortened. It was necessary to take measures for the equipment, such as the scattering of water and having a heating device.
【0028】また、スケール剥離能力を高めた酸溶液を
使用する場合には、線材と酸溶液が接触しており常に新
鮮な酸溶液が供給されている部分のスケールは剥離され
やすく、短時間でスケールが剥離するものの線材コイル
内部のスケールは剥離され難いためにスケールが残存
し、スケール剥離部と残存部の差が大きくなる。さらに
残存スケールを少なくするために酸洗時間を長くした場
合には、初期にスケールが剥離した部分はさらに線材の
浸食が進行し、孔食等の欠陥による品質の低下を引き起
こし問題となり、線材コイルの全長にわたるスケールを
短時間で均一に剥離することは困難であった。When an acid solution having an enhanced scale peeling ability is used, the wire rod and the acid solution are in contact with each other, and the scale of the portion to which the fresh acid solution is constantly supplied is easily peeled off, and the scale is easily removed in a short time. Although the scale peels off, the scale inside the wire coil is difficult to peel off, so that the scale remains and the difference between the scale peeling portion and the remaining portion increases. Furthermore, when the pickling time is extended to reduce the remaining scale, the erosion of the wire progresses further in the area where the scale is peeled off in the initial stage, causing a problem of quality deterioration due to defects such as pitting corrosion. It was difficult to uniformly peel off the scale over the entire length in a short time.
【0029】特に、単純な浸漬酸洗方法では線材コイル
の重なり部周辺では酸溶液が滞留し、鉄イオン濃度が短
時間で増加し、新しい酸溶液が供給されないために酸溶
液中の2価の鉄イオンが飽和状態となりスケールの溶解
能力が著しく低下する。このために酸洗時間を長くして
もスケールは酸洗初期に剥離された状態のままで、スケ
ールの剥離性の改善効果は小さい。逆にスケール剥離部
では酸洗初期にスケールが剥離され、酸溶液と鉄部分が
直接接触するために孔食が発生し易く酸洗処理時間が長
くなると、特に激しい孔食が発生する。このようなアン
バランスな酸洗が行われる重なり部あるいは密閉部での
スケール剥離性を改善するためには、酸溶液のスケール
剥離性を高め、短時間で処理を終了する必要があり、新
しい酸溶液を常に供給してやることが有効である。Particularly, in the simple immersion pickling method, the acid solution stays around the overlapping portion of the wire coil, the iron ion concentration increases in a short time, and a new acid solution is not supplied, so that the divalent acid solution in the acid solution is not supplied. Iron ions are saturated and the scale's dissolution capacity is significantly reduced. For this reason, even if the pickling time is lengthened, the scale remains in a peeled state in the initial stage of pickling, and the effect of improving the peelability of the scale is small. On the contrary, in the scale peeling portion, the scale is peeled off at the initial stage of pickling, and the acid solution and the iron portion are in direct contact with each other, so that pitting corrosion easily occurs, and particularly when the pickling treatment time becomes long, particularly severe pitting corrosion occurs. In order to improve the scale releasability at the overlapping part or the closed part where such unbalanced pickling is performed, it is necessary to enhance the scale removability of the acid solution and complete the treatment in a short time. It is effective to constantly supply the solution.
【0030】このような線材重なり部の酸洗性を改善す
る方法の一つとして振動酸洗があるが、本発明者らはよ
り簡便で効率良い酸洗を行う方法として、線材コイルを
酸洗浴に浸漬して脱スケール処理を行う時に、酸溶液を
撹拌し運動エネルギーを与える酸洗処理方法を発明した
ものである。撹拌、流動化することにより酸溶液は運動
エネルギーを得て、線材の重なり部境界および密閉空間
にスケール剥離性の高い酸溶液を強制的かつ連続的に供
給することができるようになりスケールの剥離性を改善
するものである。Vibration pickling is one of the methods for improving the pickling property of the overlapping portion of the wire rods. The present inventors have proposed a simpler and more efficient pickling method as follows: The present invention is an invention of a pickling treatment method in which an acid solution is stirred to give kinetic energy when it is subjected to a descaling treatment by immersing it in. By stirring and fluidizing, the acid solution gains kinetic energy, and it becomes possible to forcibly and continuously supply the acid solution with high scale releasability to the overlapping part boundary of the wire and the closed space. To improve the sex.
【0031】本発明の酸洗処理を行うことにより同一酸
洗時間とした場合には従来の方法に比べ残留スケール量
が半分に低減し、逆に同一の残留スケール量とするため
には処理時間を半分にすることができる。従って本発明
の方法によれば線材の重なり部および密閉部のスケール
剥離性が改善され、酸洗処理時間が短縮されるために、
線材コイルの表面と内部、重なり部においてスケール剥
離性の差が小さくなり均一なスケールの剥離が達成でき
るものである。When the pickling treatment of the present invention is performed at the same pickling time, the amount of residual scale is reduced to half compared to the conventional method, and conversely, the treatment time is required to obtain the same amount of residual scale. Can be halved. Therefore, according to the method of the present invention, the scale releasability of the overlapped portion and the closed portion of the wire is improved, and the pickling treatment time is shortened,
The difference in scale releasability between the surface, the inside, and the overlapping portion of the wire rod coil is reduced, and uniform scale detachment can be achieved.
【0032】また、酸溶液を撹拌、流動させながら酸洗
処理を行った場合には酸洗時間が適正時間よりも長くな
った場合でも線材表面での酸溶液の滞留が抑制され局部
的な孔食の発生が抑制されるために線材全体の表面粗さ
が小さくかつほぼ一定に保たされる傾向がある。この結
果、後工程での二次加工での伸線時のトラブルもなく、
良好な伸線状態が得られるものである。When the pickling treatment is performed while stirring and flowing the acid solution, the acid solution is prevented from staying on the surface of the wire even if the pickling time is longer than an appropriate time, and local holes are formed. Since the occurrence of corrosion is suppressed, the surface roughness of the entire wire tends to be small and kept substantially constant. As a result, there is no trouble during wire drawing in the secondary processing in the post process,
A good wire drawing state can be obtained.
【0033】さらに、酸洗後の水洗あるいは中和処理時
にも処理液を撹拌、流動することにより強制的に線材表
面に付着した酸洗溶液の成分を短時間で内部まで中和お
よび洗浄することができ、酸が原因として起こる錆の発
生を大幅に低減できるものである。Further, even during the washing or neutralization treatment after pickling, the components of the pickling solution adhering to the surface of the wire are forcibly neutralized and washed in a short time by stirring and flowing the treatment liquid. It is possible to significantly reduce the generation of rust caused by acid.
【0034】ガス吹き出しノズルを有するパイプを液の
中に浸漬してノズルから流出するガスのエネルギーで酸
洗溶液、中和液、洗浄液を撹拌する本発明の方法ではノ
ズルから吹き出すガス流速、ノズル形状、ノズルの数等
を調整して撹拌の強さ、液の流れの方向を自由に制御す
ることができる。In the method of the present invention in which a pipe having a gas blowing nozzle is immersed in a liquid and the energy of the gas flowing out from the nozzle is used to stir the pickling solution, the neutralizing liquid, and the cleaning liquid, the gas flow rate blown out from the nozzle, the nozzle shape It is possible to freely control the strength of stirring and the direction of liquid flow by adjusting the number of nozzles and the like.
【0035】たとえば線材コイルの結束力が弱い場合は
ノズルから吹き出すガス流速はあまり速くする必要はな
く、逆に結束強さが強い場合はガス吹きだし速度を高め
かつノズルを数多く配置し、線材に向けてガスを吹き出
すことにより線材コイル内部の線材重なり部にまで酸溶
液、中和液、洗浄液を浸透、供給することによりスケー
ルの剥離性を高めるものである。For example, when the binding force of the wire rod coil is weak, the flow velocity of the gas blown from the nozzle does not need to be too high. On the contrary, when the binding strength is strong, the gas blowing speed is increased and a large number of nozzles are arranged to direct it toward the wire rod. The gas is blown out to infiltrate and supply the acid solution, the neutralizing solution, and the cleaning solution even to the overlapping portion of the wire inside the wire coil, thereby enhancing the peelability of the scale.
【0036】次に鉄イオンの影響であるが酸洗液により
溶解される鉄はほとんどが2価の鉄イオンとして酸溶液
中に存在するが、本発明者らの検討によれば、3価の鉄
イオンがスケールの剥離性を改善し、より短時間処理が
可能であることが明らかになった。しかし、酸溶液を撹
拌、流動化させない従来の酸洗方法では、線材密閉部に
3価の鉄イオンを含有する酸溶液が充填、滞留し、2価
の鉄イオンに短時間で還元され急激に鉄イオン濃度が増
加するためにスケールの剥離性を改善する効果はなくな
る。この結果、2価の鉄イオンの濃度が酸溶液の飽和濃
度に近づくためスケールの剥離性が悪化し、線材の残留
スケール量が多くなる。Next, most of the iron dissolved by the pickling solution due to the influence of iron ions exists in the acid solution as divalent iron ions, but according to the study by the present inventors, trivalent iron ions are present. It was clarified that iron ions improve the peelability of the scale, and the treatment for shorter time is possible. However, according to the conventional pickling method in which the acid solution is not stirred and fluidized, the wire seal portion is filled with and retained by the acid solution containing trivalent iron ions, and is rapidly reduced to divalent iron ions in a short time. Since the iron ion concentration increases, the effect of improving the peelability of the scale disappears. As a result, the concentration of the divalent iron ion approaches the saturation concentration of the acid solution, so the scale releasability deteriorates, and the amount of residual scale on the wire increases.
【0037】一方、3価の鉄イオンを有する酸溶液を撹
拌流動させ線材コイルの密閉部分に新鮮な酸溶液を連続
的に供給した場合は、スケールの剥離性が改善された酸
溶液が供給されるために、酸洗浴中の3価の鉄イオン濃
度を制御しなかった場合に比べさらに短時間でスケール
の剥離が終了する。このようなことから本発明では酸溶
液中の3価の鉄イオン濃度を規定した。On the other hand, when an acid solution having trivalent iron ions is agitated and flown to continuously supply a fresh acid solution to the closed portion of the wire coil, an acid solution having improved scale releasability is supplied. Therefore, the scale peeling is completed in a shorter time than in the case where the trivalent iron ion concentration in the pickling bath is not controlled. Therefore, in the present invention, the concentration of trivalent iron ions in the acid solution is specified.
【0038】酸洗浴中への鉄イオンの供給によりスケー
ルの剥離時間が短縮される理由は以下のように考えられ
る。線材スケール表面での局部電池形成反応に基づいて
考えると以下の式に示すようにアノード、カソード反応
は示される。以下に局部電池反応を示す。 (アノード反応) Fe→Fe2++2e (カソード反応) Fe2O3+6H++2e→2Fe2++3H2O Fe3O4+8H++2e→3Fe2++4H2O 2H++2e→H2 The reason why the stripping time of the scale is shortened by supplying iron ions into the pickling bath is considered as follows. Considering the local cell formation reaction on the surface of the wire scale, the anode and cathode reactions are shown as shown in the following equations. The local battery reaction is shown below. (Anode reaction) Fe → Fe 2+ + 2e (Cathode reaction) Fe 2 O 3 + 6H + + 2e → 2Fe 2+ + 3H 2 O Fe 3 O 4 + 8H + + 2e → 3Fe 2+ + 4H 2 O 2H + + 2e → H 2
【0039】この局部電池形成によるスケールの剥離時
に3価の鉄イオンが存在することにより地鉄の溶解反応
にアノード反応と対の以下の反応が起こリ、3価のイオ
ンは酸溶液中ではより安定な2価のイオンへの還元が行
われこの時に酸溶液中の電子を消費する。 Fe3++e→Fe2+ Due to the presence of trivalent iron ions during the exfoliation of the scale due to the formation of the local battery, the following reaction paired with the anodic reaction occurs in the dissolution reaction of base iron, and the trivalent ions are more likely to exist in the acid solution. Reduction to a stable divalent ion takes place, at which time the electrons in the acid solution are consumed. Fe 3+ + e → Fe 2+
【0040】この還元反応に関与する電子は鉄、あるい
はスケールの溶解により供給されるもので進行により相
手極であるFe(地鉄)は以下の溶解反応が促進され
る。 Fe→Fe2++2e この総括反応として以下の反応となり、 Fe+Fe3+→3Fe2+ 見かけ上3価の鉄イオンが鉄の溶解を促進する反応とな
る。この溶解反応が促進されるために3価の鉄イオンの
存在により局部電池反応が進み、スケールの剥離が改善
されるものと推定される。The electrons involved in this reduction reaction are supplied by the dissolution of iron or scale, and the proceeding dissolution reaction of Fe (base iron), which is the other electrode, is promoted as the electrons progress. Fe → Fe 2+ + 2e The overall reaction is as follows, and Fe + Fe 3+ → 3Fe 2+ apparently trivalent iron ions promote the dissolution of iron. It is presumed that since the dissolution reaction is promoted, the presence of trivalent iron ions promotes the local cell reaction and the scale peeling is improved.
【0041】しかし、逆にFe3+の濃度が高い酸溶液を
線材で密閉された空間に供給し、酸溶液が滞留、保持さ
れた場合は、線材の鉄部の溶解が促進され急激な鉄イオ
ン濃度の増加となり酸溶液の剥離能力が低下する。この
ような作用により3価の鉄イオンを酸溶液に添加するこ
とによりスケールの剥離が促進されるが、Fe3+の濃度
が10g/lより少ない場合は明確なスケールの剥離性
の改善効果は認められず、スケールの剥離を促進する作
用を行わせるためには少なくとも10g/l以上の3価
の鉄イオン濃度が必要である。一方、60g/l以上の
3価の鉄イオン濃度はスケールの溶解性を損なうこと、
地鉄の局部的溶解が促進され孔食状の欠陥が多くなるた
めに酸溶液中のFe3+濃度を60g/l以下とした。However, conversely, when an acid solution having a high Fe 3+ concentration is supplied to the space closed by the wire and the acid solution is retained and held, the dissolution of the iron portion of the wire is accelerated and the iron content is rapidly increased. The ion concentration increases and the stripping ability of the acid solution decreases. By such an action, the exfoliation of the scale is promoted by adding trivalent iron ions to the acid solution, but when the Fe 3+ concentration is less than 10 g / l, the definite improvement effect of the exfoliation property of the scale is not obtained. It is not recognized, and a trivalent iron ion concentration of at least 10 g / l or more is necessary in order to perform the action of promoting scale peeling. On the other hand, a trivalent iron ion concentration of 60 g / l or more impairs the solubility of the scale,
The Fe 3+ concentration in the acid solution was set to 60 g / l or less because local dissolution of the base iron is promoted and pitting-like defects are increased.
【0042】しかし、脱スケール反応で生成する鉄イオ
ンはFe2+の2価の鉄イオンであり、2価の鉄イオンは
酸洗を継続していくことにより必然的に酸洗浴中に生成
し自然に3価の鉄イオンとはならないために、本発明の
目的を達成するために外部から3価の鉄イオンを制御す
る手段を講ずる必要がある。しかし、薬品を添加して鉄
イオン濃度を制御する場合には制御性は高いがランニン
グコストがかさむことと総鉄イオン濃度が増加するため
に比較的早く酸溶液の飽和濃度に達して酸溶液の溶解能
力が低下する。However, the iron ions produced by the descaling reaction are divalent iron ions of Fe 2+ , and the divalent iron ions are inevitably produced in the pickling bath by continuing pickling. In order to achieve the object of the present invention, it is necessary to take measures to externally control the trivalent iron ion in order not to naturally become trivalent iron ion. However, when controlling the iron ion concentration by adding chemicals, the controllability is high, but the running cost is high and the total iron ion concentration increases, so the saturated concentration of the acid solution is reached relatively quickly and Dissolution capacity is reduced.
【0043】これに対して本発明の酸溶液中に存在する
Fe2+イオンを酸素を含有するガスを酸溶液中に吹き込
むことにより酸化してFe3+化する方法は吹き込む酸素
の濃度、ガス量、時間によりFe2+の酸化比率が決定さ
れる。この条件を適宜選択することによりFe3+濃度の
制御ができると共に酸溶液中の総鉄イオン濃度は一定に
保たれることにより酸溶液の溶解能力の低下を防止し、
酸洗溶液の寿命を長く維持できるため、より好ましい方
法である。On the other hand, the method of oxidizing Fe 2+ ions present in the acid solution of the present invention by blowing a gas containing oxygen into the acid solution to form Fe 3+ is as follows. The oxidation ratio of Fe 2+ is determined by the amount and time. By properly selecting this condition, the Fe 3+ concentration can be controlled and the total iron ion concentration in the acid solution can be kept constant to prevent a decrease in the dissolving ability of the acid solution,
This is a more preferable method since the life of the pickling solution can be maintained for a long time.
【0044】[0044]
(実施例1)SWRH82Aの5.5φ線材1トンを結
束した線材コイルを用いて酸洗処理を行った。この線材
のスケール性状は厚さ10.3μm,組成はスケールを
剥離後X線回折による強度ピーク比から求め、FeO
64.4%,Fe3O4 34.2%,Fe2O3 1.4
%であり、地鉄側からFeO,Fe3O4,Fe2O3が層
状に形成されているものである。酸洗浴は塩酸濃度が2
0%,温度が20℃,Fe2+濃度が22g/l,Fe3+
濃度が4.3g/lのものを使用した。この酸洗液でカ
ットサンプルの重なり部が存在しないスケールの剥離時
間は3分であった。(Example 1) A pickling treatment was performed using a wire rod coil formed by binding 1 ton of 5.5φ wire rod of SWRH82A. The scale property of this wire rod is 10.3 μm in thickness, and the composition is obtained from the intensity peak ratio by X-ray diffraction after peeling off the scale.
64.4%, Fe 3 O 4 34.2%, Fe 2 O 3 1.4
%, And FeO, Fe 3 O 4 , and Fe 2 O 3 are formed in layers from the base iron side. The pickling bath has a hydrochloric acid concentration of 2
0%, temperature 20 ° C, Fe 2+ concentration 22g / l, Fe 3+
A concentration of 4.3 g / l was used. With this pickling solution, the peeling time of the scale where the cut sample did not overlap was 3 minutes.
【0045】本発明の方法による酸溶液の撹拌、流動化
する方法として酸洗槽の底に、上側に1.2mm径のノ
ズルを50mmピッチで設けた管状のエンビ管を浸漬
し、ノズルからガス吹き出すことにより行った。線材コ
イルはフックでつり下げて、クレーンで移動して酸洗槽
に浸漬後に圧力4kgf/cm2 の圧縮空気1Nm3 /
minを流して酸溶液を酸浴の撹拌、流動させて処理時
間を変えて線材コイルの残留スケール量を測定した。As a method of stirring and fluidizing the acid solution according to the method of the present invention, a tubular ENVI pipe having nozzles with a diameter of 1.2 mm at a pitch of 50 mm is immersed in the bottom of the pickling tank, and gas is discharged from the nozzle. It was done by blowing out. The wire rod coil is hung by a hook, moved by a crane and immersed in a pickling tank, and then compressed air of 1 Nm 3 / with a pressure of 4 kgf / cm 2.
The amount of residual scale of the wire rod coil was measured by changing the treatment time by flowing min and stirring and flowing the acid solution in the acid bath.
【0046】比較例として空気を吹き込まない場合の従
来法の残留スケール量も同様の処理時間毎に測定した。
残留スケール量の測定は酸洗後、水洗槽で水洗処理を行
った後に乾燥してから求めた。このときの水洗処理槽で
も本発明の場合は空気を吹き込み、水を撹拌、流動させ
て処理を行った。残留スケール量の測定は線材コイルの
結束をはずした後に100リング間隔に2リング連続し
て1リング8等分に切断して重量を測定しW1とし、こ
の切断サンプルを地鉄の溶解を抑制するためにインヒビ
ターを添加した塩酸溶液に浸漬して、乾燥後再度重量を
測定しW2とし、 残留スケール(重量%)=(W1−W2)/W1×10
0 の計算式により残留スケール量を求めた。このときスケ
ールの完全剥離時にインヒビ夕ーは添加しているものの
地鉄が溶解して重量減が大きくなるためにダミーとして
スケールの付着していないサンプルと同長さに切断した
線材をダミーとして酸洗してこの重量変化を地鉄溶解重
量として補正を行った。As a comparative example, the residual scale amount of the conventional method when air was not blown was also measured for each similar treatment time.
The amount of residual scale was measured after pickling, followed by washing with a washing tank and drying. In the case of the present invention, air was blown into the washing treatment tank at this time as well, and the treatment was performed by stirring and flowing water. To measure the residual scale amount, after removing the binding of the wire rod coil, cut two rings at 100-ring intervals in succession into 1 ring and divide it into 8 equal parts, and weigh it to W1. For this purpose, it is immersed in a hydrochloric acid solution to which an inhibitor has been added, dried and then weighed again as W2, and the residual scale (% by weight) = (W1−W2) / W1 × 10
The residual scale amount was obtained by the calculation formula of 0. At this time, although the inhibitor was added when the scale was completely peeled off, the ground iron dissolved and the weight loss increased, so a wire rod cut to the same length as the sample with no scale attached was used as a dummy. After washing, this weight change was corrected as the dissolved weight of base iron.
【0047】その結果を図1に示す。酸洗時に空気を吹
き込んだ本発明の方法は同じ酸洗時間で比較すると、従
来の方法で酸洗した線材の残留スケール量に比べ約半分
に低減しており、従来法と同等の残留スケール量とする
場合には酸洗処理時間は約半分に短縮された。The results are shown in FIG. When compared with the same pickling time, the method of the present invention in which air is blown during pickling has been reduced to about half the residual scale amount of the wire rod pickled by the conventional method, and the residual scale amount equivalent to that of the conventional method. In that case, the pickling time was reduced to about half.
【0048】また、酸洗後の線材の表面粗さは図2に示
すように本発明による方法で酸洗した線材の表面粗さは
従来法より小さく、酸洗時間が長くなっても大幅な表面
粗さの悪化はない。Further, as shown in FIG. 2, the surface roughness of the wire after pickling is smaller than that of the conventional method by pickling by the method according to the present invention, and it is large even if the pickling time is long. There is no deterioration in surface roughness.
【0049】さらに本発明の方法でスケールの剥離を行
った線材は、大気環境で保管しても錆の発生が従来の方
法で酸洗した線材コイルに比べ少なく、水洗が十分に行
われ、酸溶液の除去効果も十分であることがわかった。Furthermore, the wire rod from which the scale has been peeled off according to the method of the present invention has less rust even when stored in an atmospheric environment as compared with the wire rod coil pickled by the conventional method, and is sufficiently washed with water to remove the acid. It was found that the removal effect of the solution was also sufficient.
【0050】(実施例2)実施例1と同様の条件で酸洗
液のFe3+の鉄イオン濃度を変えて線材コイルの酸洗処
理を行った。酸溶液は酸洗前に薬品を添加しFe3+を溶
解させた状態および空気を吹き込んで、Fe2+をFe3+
に酸化させた酸溶液を用いて酸溶液を撹拌、流動させ、
線材コイルを酸洗時間10分の酸洗処理を行い残留スケ
ール量を測定した。(Example 2) Under the same conditions as in Example 1, the pickling treatment of the wire coil was performed by changing the iron ion concentration of Fe 3+ in the pickling solution. For the acid solution, before the pickling, chemicals are added to dissolve Fe 3+ and air is blown in to remove Fe 2+ from Fe 3+.
Stir and fluidize the acid solution with the acid solution oxidized to
The wire rod coil was pickled for 10 minutes for pickling, and the amount of residual scale was measured.
【0051】初期のFe2+が約60g/lの酸溶液に空
気を吹き込んだ場合の吹き込み時間とFe2+、Fe3+の
濃度の変化を図3に示した。空気を長時間吹き込むこと
により、Fe2+がFe3+に酸化され、ほぼ全てのFe2+
がFe3+に酸化されることがわかる。また、総鉄イオン
濃度はほぼ一定の値であり、鉄イオン濃度の増加はな
い。FIG. 3 shows changes in the blowing time and the concentrations of Fe 2+ and Fe 3+ when air is blown into the acid solution in which initial Fe 2+ is about 60 g / l. By blowing air for a long time, Fe 2+ is oxidized to Fe 3+ , and almost all Fe 2+ is
It can be seen that is oxidized to Fe 3+ . Further, the total iron ion concentration has a substantially constant value, and the iron ion concentration does not increase.
【0052】本発明の方法と従来の単純に浸漬酸洗した
場合の残留スケール量と酸溶液中のFe3+の鉄イオン濃
度の関係を図4に示す。これより従来の単純浸漬による
酸洗法ではFe3+が25g/lまではFe3+添加による
残留スケール量の改善効果は無く、Fe3+が25g/l
以上では残留スケール量が増加し、スケールの剥離性が
悪化した。これに対して本発明の方法ではFe3+の量が
10g/l以上で残留スケール量が低減し、Fe3+が増
すにつれ残留スケール量はさらに低下する。しかし、6
0g/l以上ではスケールの剥離性改善効果は認められ
ず、改善効果が小さくなった。また、薬品添加の場合と
Fe2+の酸化によるFe3+の制御による残留スケール量
低減効果に明瞭な差はなく、共にFe3+の制御を行わな
かった場合に比べ明らかに残留スケール量の低減効果が
認められた。しかし、Fe3+濃度が60g/l以上にな
ると線材表面に孔食状の欠陥が多発し、表面性状の悪化
となった。FIG. 4 shows the relationship between the residual scale amount and the iron ion concentration of Fe 3+ in the acid solution when the method of the present invention and conventional simple immersion pickling are used. From this rather the effect of improving the residual amount of scale due to the Fe 3+ added Fe 3+ until 25 g / l in the conventional pickling process according to simple immersion, Fe 3+ is 25 g / l
Above, the amount of residual scale increased and the peelability of the scale deteriorated. On the other hand, in the method of the present invention, the amount of residual scale decreases when the amount of Fe 3+ is 10 g / l or more, and the amount of residual scale further decreases as the amount of Fe 3+ increases. But 6
At 0 g / l or more, the effect of improving scale releasability was not recognized, and the effect of improvement was small. Also, no clear difference in the residual amount of scale reduction effect by the control of the Fe 3+ by oxidation in the case of chemicals added and Fe 2+, apparently residual amount of scale compared to the case you did not control the Fe 3+ together A reduction effect was recognized. However, when the Fe 3+ concentration was 60 g / l or more, pitting-like defects frequently occurred on the surface of the wire and the surface quality deteriorated.
【0053】酸溶液中のFe3+は酸洗処理時に還元さ
れ、Fe2+となるために酸洗後は再度空気を吹き込んで
Fe2+をFe3+に還元しておけば、常に適正範囲のFe
3+に調整することができ、コスト的に有利でかつ簡便に
鉄イオンの制御が可能となる。Since Fe 3+ in the acid solution is reduced during the pickling process and becomes Fe 2+ , it is always appropriate to blow air again after the pickling to reduce Fe 2+ to Fe 3+. Fe in the range
It can be adjusted to 3+ , which is advantageous in terms of cost and allows easy control of iron ions.
【0054】[0054]
【発明の効果】線材コイルの浸漬酸洗において本発明の
方法による酸洗槽内の酸洗溶液を撹拌、流動することに
より、線材コイルの重なり部あるいは密閉部分に新鮮な
酸溶液を連続的に供給でき、線材コイルの重なり部ある
いは密閉された部分での残留スケールが半減できるため
に酸洗時間を半分に短縮可能である。また酸溶液中にノ
ズルからガスを吹き込む簡単な装置で酸溶液を撹拌、流
動化することが出来る。酸洗浴中の3価の鉄イオン濃度
を制御することにより酸洗溶液のスケールの剥離性をさ
らに改善することができ、酸洗浴を撹拌、流動させる酸
洗方法と併用することにより効率良い酸洗が可能であ
る。本発明はガスを吹き込むことができるパイプとノズ
ルおよび圧縮空気さえあれば容易に実行可能であり、ま
た、吹き込みガスとして酸素を含有するガスを用いるこ
とにより2価の鉄イオンの酸化により容易に3価の鉄イ
オン濃度の制御が可能となり簡便な装置で大きな効果が
得られ工業的に非常に有用な発明である。EFFECTS OF THE INVENTION In the immersion pickling of the wire coil, the pickling solution in the pickling tank according to the method of the present invention is agitated and allowed to flow, whereby a fresh acid solution is continuously applied to the overlapping portion or the closed portion of the wire coil. It can be supplied, and the residual scale at the overlapped portion or the closed portion of the wire rod coil can be halved, so that the pickling time can be reduced to half. Further, the acid solution can be agitated and fluidized by a simple device in which gas is blown into the acid solution from a nozzle. By controlling the concentration of trivalent iron ions in the pickling bath, scale releasability of the pickling solution can be further improved, and efficient pickling can be achieved by using the pickling method in which the pickling bath is stirred and fluidized. Is possible. The present invention can be easily carried out with a pipe and a nozzle capable of blowing gas and compressed air, and by using a gas containing oxygen as the blowing gas, it can be easily carried out by oxidation of divalent iron ions. This is an industrially very useful invention because it is possible to control the concentration of valent iron ions and a great effect can be obtained with a simple device.
【図1】本発明と従来の酸洗法の酸洗時間と残留スケー
ル量の関係を示す図。FIG. 1 is a diagram showing the relationship between the pickling time and the residual scale amount of the present invention and a conventional pickling method.
【図2】本発明の方法と従来の酸洗法の線材の表面粗さ
の変化を示す図。FIG. 2 is a diagram showing changes in surface roughness of a wire according to the method of the present invention and a conventional pickling method.
【図3】酸溶液中に酸素を吹き込んだ場合の鉄イオン濃
度の変化を示す図。FIG. 3 is a diagram showing changes in iron ion concentration when oxygen is blown into an acid solution.
【図4】Feイオン濃度と残留スケール量の関係を示す
図。FIG. 4 is a diagram showing a relationship between Fe ion concentration and residual scale amount.
Claims (6)
ル処理を行う方法において酸洗溶液を強制的に撹拌、流
動させながら処理することを特徴とする線材コイルの酸
洗脱スケール方法。1. A method of pickling and descaling a wire coil, which comprises performing a descaling treatment by immersing the wire coil in a pickling bath while forcibly stirring and flowing the pickling solution.
おいて溶液を強制的に撹拌、流動させながら処理するこ
とを特徴とする線材コイルの中和、洗浄方法。2. A method for neutralizing and cleaning a wire coil, which comprises treating the solution while forcibly stirring and flowing the solution at the time of water washing or neutralization after pickling.
を酸洗浴内に浸漬し、該ノズルを線材コイルに向けてガ
スを吹き付け、酸溶液を流動化させることを特徴とする
線材コイルの酸洗脱スケール方法。3. A pickling descaler for a wire rod coil, characterized in that a pipe having a nozzle for blowing gas is immersed in a pickling bath, and the gas is blown toward the wire rod coil to fluidize the acid solution. Method.
を水洗および中和処理液内に浸漬し、該ノズルを線材コ
イルに向けてガスを吹き付け、水洗および中和溶液を流
動化させることを特徴とする線材コイルの中和、洗浄方
法。4. A pipe having a nozzle for blowing gas is immersed in a washing and neutralizing treatment liquid, and the gas is blown toward the wire coil so that the washing and neutralizing solution is fluidized. How to neutralize and clean the wire coil.
することを特徴とする請求項3記載の線材コイルの酸洗
脱スケール方法。5. The pickling and descaling method for a wire rod coil according to claim 3, wherein the gas sprayed from the nozzle contains oxygen.
が10g/l以上、60g/l以下の濃度範囲に調整し
た酸洗溶液を用いたことを特徴とする請求項1又は3記
載の線材コイルの酸洗脱スケール方法。6. The pickling solution in which the concentration of trivalent Fe ions in the pickling solution is adjusted to a concentration range of 10 g / l or more and 60 g / l or less is used. Method for pickling and descaling of wire coil of.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP07129867A JP3140328B2 (en) | 1994-08-23 | 1995-04-03 | Pickling and descaling method of wire rod coil and neutralizing and cleaning method of coil after pickling |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21964394 | 1994-08-23 | ||
JP6-219643 | 1994-08-23 | ||
JP07129867A JP3140328B2 (en) | 1994-08-23 | 1995-04-03 | Pickling and descaling method of wire rod coil and neutralizing and cleaning method of coil after pickling |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH08120472A true JPH08120472A (en) | 1996-05-14 |
JP3140328B2 JP3140328B2 (en) | 2001-03-05 |
Family
ID=26465137
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Application Number | Title | Priority Date | Filing Date |
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JP07129867A Expired - Fee Related JP3140328B2 (en) | 1994-08-23 | 1995-04-03 | Pickling and descaling method of wire rod coil and neutralizing and cleaning method of coil after pickling |
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Country | Link |
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JP (1) | JP3140328B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007318170A (en) * | 2007-08-06 | 2007-12-06 | Sanyo Electric Co Ltd | Manufacture and manufacturing apparatus of solid-state electrolytic capacitor |
-
1995
- 1995-04-03 JP JP07129867A patent/JP3140328B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007318170A (en) * | 2007-08-06 | 2007-12-06 | Sanyo Electric Co Ltd | Manufacture and manufacturing apparatus of solid-state electrolytic capacitor |
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Publication number | Publication date |
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JP3140328B2 (en) | 2001-03-05 |
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