JP2000282271A - Scale adhesion suppression method for continuous pickling equipment for metallic material - Google Patents
Scale adhesion suppression method for continuous pickling equipment for metallic materialInfo
- Publication number
- JP2000282271A JP2000282271A JP11087600A JP8760099A JP2000282271A JP 2000282271 A JP2000282271 A JP 2000282271A JP 11087600 A JP11087600 A JP 11087600A JP 8760099 A JP8760099 A JP 8760099A JP 2000282271 A JP2000282271 A JP 2000282271A
- Authority
- JP
- Japan
- Prior art keywords
- pickling
- diphosphonic acid
- solution
- scale
- continuous
- 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.)
- Pending
Links
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鋼板など金属材料
の連続酸洗設備におけるスケール付着抑制方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for suppressing scale adhesion in a continuous pickling facility for a metal material such as a steel plate.
【０００２】[0002]
【従来の技術】冷間圧延鋼板、珪素鋼板などの金属材料
の製造工程においては、酸洗が行われる。図２に、鋼板
の連続酸洗設備の一例を示す。なお、図２において、１
は酸洗槽、２は酸洗液、３はヘルパーロール、４は間接
熱交換器（：テフロンチューブ式熱交換器）、５は酸洗
液循環配管、６は酸洗液循環ポンプ、７は酸洗原液貯
槽、８は流量調節弁、９は弁、Ｓは鋼帯、f1は鋼帯Ｓの
通板方向、f2は酸洗液の循環方向を示す。2. Description of the Related Art In the process of producing metal materials such as cold-rolled steel sheets and silicon steel sheets, pickling is performed. FIG. 2 shows an example of a continuous pickling facility for steel sheets. In FIG. 2, 1
Is a pickling tank, 2 is a pickling liquid, 3 is a helper roll, 4 is an indirect heat exchanger (Teflon tube type heat exchanger), 5 is a pickling liquid circulation pipe, 6 is a pickling liquid circulation pump, and 7 is a pickling liquid circulation pump. pickling stock tank, 8 flow rate control valve, 9 is a valve, S is the strip, f 1 is the sheet passing direction of the steel strip S, f 2 denotes a circulation direction of the pickling solution.
【０００３】図２に示す連続酸洗設備においては、酸洗
槽１内の酸洗液の液温、酸濃度の均一化を計るために、
酸洗液循環配管５、酸洗液循環ポンプ６によって酸洗液
を循環する。また、酸洗液加温用の間接熱交換器４とし
て、テフロンチューブ式熱交換器など、蒸気などの加熱
媒体を流通する耐酸性の樹脂チューブを用いた間接熱交
換器が使用される。In the continuous pickling equipment shown in FIG. 2, in order to make the temperature and the acid concentration of the pickling liquid in the pickling tank 1 uniform,
The pickling liquid is circulated by the pickling liquid circulation pipe 5 and the pickling liquid circulation pump 6. As the indirect heat exchanger 4 for heating the pickling liquid, an indirect heat exchanger using an acid-resistant resin tube through which a heating medium such as steam flows, such as a Teflon tube heat exchanger, is used.
【０００４】図２に例示した鋼板の連続酸洗設備におい
ては、酸洗槽１において、鋼帯Ｓは所定の液組成、液温
の酸洗液２に浸漬され酸洗が行われるが、従来、酸洗設
備の接液部へのシリカ系スケール（以下Si系スケールと
記す）の付着によって、下記(1) 〜(7) に示す種々の問
題があった。 (1) 酸洗槽１の酸洗液２中に配設された間接熱交換器４
の器壁（管外壁）にSi系スケールが固着し、熱交換器の
能力低下により蒸気原単位が増加する。In the continuous pickling equipment for steel plates illustrated in FIG. 2, in a pickling tank 1, a steel strip S is immersed in a pickling liquid 2 having a predetermined liquid composition and liquid temperature to perform pickling. In addition, the adhesion of silica-based scale (hereinafter referred to as Si-based scale) to the liquid contact portion of the pickling equipment has caused various problems described in the following (1) to (7). (1) Indirect heat exchanger 4 arranged in pickling liquid 2 in pickling tank 1
The Si-based scale adheres to the vessel wall (outer wall of the tube), and the steam intensity increases due to a decrease in the capacity of the heat exchanger.
【０００５】すなわち、Si系スケールの固着による熱交
換器の能力低下によって酸洗液の液温が低下すると酸洗
液の脱スケール力が低下するため、熱交換器への蒸気供
給量を増加する必要があった。 (2) 間接熱交換器として用いるテフロンチューブ式熱交
換器に固着したSi系スケールを除去するためにラインの
停止が必要となり、連続酸洗設備の生産性が低下する。That is, if the temperature of the pickling solution is lowered due to a decrease in the capacity of the heat exchanger due to the sticking of the Si-based scale, the descaling power of the pickling solution is reduced, and the amount of steam supplied to the heat exchanger is increased. Needed. (2) The line must be stopped to remove the Si-based scale adhered to the Teflon tube type heat exchanger used as the indirect heat exchanger, and the productivity of the continuous pickling equipment will decrease.
【０００６】(3) 上記(2) における熱交換器に固着した
Si系スケール除去の際に、テフロンチューブが一部破損
し、蒸気漏れおよび該チューブに接続された蒸気供給配
管（鋼製）への酸液侵入による蒸気供給配管の腐食、孔
開きが生じる。 (4) ヘルパーロール３の溝部へSi系スケールであるヘド
ロが固着し、ロール溝部へのヘドロ固着に起因する鋼帯
蛇行が生じ、その際、ラインを停止し、ヘルパーロール
を交換する必要がある。(3) It is fixed to the heat exchanger in (2) above.
At the time of removing the Si-based scale, the Teflon tube is partially damaged, and the steam supply pipe is corroded and perforated by an acid solution entering the steam supply pipe (made of steel) connected to the tube. (4) Sludge, which is a Si-based scale, adheres to the groove of the helper roll 3, and the steel strip meanders due to the adhesion of the sludge to the roll groove. At this time, it is necessary to stop the line and replace the helper roll. .
【０００７】(5) 酸洗槽１内に堆積するSi系スケールで
あるヘドロの吸引、除去および酸洗槽１内の清掃に多数
の工数を必要とする。 (6) 酸洗液循環ポンプ６のメカニカルシールが破損す
る。 (7) 酸洗液循環ポンプ６がSi系スケールによって閉塞
し、酸洗槽内の液温が不均一となる。(5) A large number of man-hours are required for sucking and removing sludge, which is a Si-based scale deposited in the pickling tank 1, and cleaning the inside of the pickling tank 1. (6) The mechanical seal of the pickling liquid circulation pump 6 is broken. (7) The pickling liquid circulation pump 6 is blocked by the Si-based scale, and the liquid temperature in the pickling tank becomes uneven.
【０００８】上記した種々の問題は、特に、珪素鋼板の
酸洗において顕著であった。[0008] The above-mentioned various problems have been particularly remarkable in pickling silicon steel sheets.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、前記した従
来技術の問題点を解決し、鋼板など金属材料の連続酸洗
設備におけるスケールの付着を抑制することが可能な金
属材料の連続酸洗設備におけるスケール付着抑制方法を
提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and enables continuous pickling of a metal material such as a steel sheet, which can suppress the adhesion of scale in a continuous pickling facility. An object of the present invention is to provide a method for suppressing scale adhesion in equipment.
【００１０】[0010]
【課題を解決するための手段】本発明は、金属材料の連
続酸洗設備の酸洗槽の酸洗液に、ヒドロキシアルキリデ
ンジホスホン酸および／またはヒドロキシアルキリデン
ジホスホン酸の水溶性塩を、前記酸洗液中の合計濃度と
して１mg/l以上添加することを特徴とする金属材料の連
続酸洗設備におけるスケール付着抑制方法である。According to the present invention, a pickling solution in a pickling tank of a continuous pickling facility for metal materials is provided with a hydroxyalkylidene diphosphonic acid and / or a water-soluble salt of hydroxyalkylidene diphosphonic acid. A method for suppressing scale adhesion in a continuous pickling facility for metal materials, characterized by adding 1 mg / l or more as a total concentration in a pickling solution.
【００１１】前記した本発明は、好ましくは、前記酸洗
液中のSi（金属シリコン）およびSi化合物のSiの合計量
（：合計濃度）がSiO2換算で50mg/l以上、より好ましく
は、前記酸洗液中のSi（金属シリコン）およびSi化合物
のSiの合計量（：合計濃度）がSiO2換算で100mg/l 以上
である金属材料の連続酸洗設備におけるスケール付着抑
制方法として適用される（本発明の好適態様）。In the present invention, preferably, the total amount of Si (metallic silicon) and Si in the pickling solution (total concentration) is at least 50 mg / l in terms of SiO 2 , more preferably This method is applied as a method for suppressing scale adhesion in a continuous pickling facility for a metal material in which the total amount of Si (metallic silicon) and Si in the pickling solution (Si: the total concentration) is 100 mg / l or more in terms of SiO 2. (Preferred embodiment of the present invention).
【００１２】また、前記した本発明、本発明の好適態様
は、好ましくは、前記金属材料が鋼板である金属材料の
連続酸洗設備におけるスケール付着抑制方法として適用
される。また、前記した本発明、本発明の好適態様は、
さらに好ましくは、前記金属材料が、Siを2.5 wt％以上
含有する珪素鋼板である金属材料の連続酸洗設備におけ
るスケール付着抑制方法として適用される。The above-described present invention and the preferred embodiments of the present invention are preferably applied as a method for suppressing scale adhesion in a continuous pickling facility for a metal material in which the metal material is a steel plate. In addition, the present invention described above, preferred embodiments of the present invention,
More preferably, the method is applied as a method of suppressing scale adhesion in a continuous pickling facility for a metal material in which the metal material is a silicon steel sheet containing 2.5 wt% or more of Si.
【００１３】[0013]
【発明の実施の形態】以下、本発明をさらに詳細に説明
する。前記したように、鋼板などの金属材料、特にSiを
含有する珪素鋼板の連続酸洗設備においては、酸洗槽に
おけるヘドロ状のSi系スケールによる種々の問題が発生
し、その都度、連続酸洗設備の操業を停止し、付設装置
の保守、交換を行い、さらにはこれらの問題に対処する
ために、ヘドロ状のSi系スケールの吸引、除去および酸
洗槽内の清掃を行う必要があった。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As described above, in a continuous pickling facility for a metal material such as a steel plate, particularly a silicon steel plate containing Si, various problems occur due to a sludge-like Si-based scale in a pickling tank. In order to stop the operation of the equipment, maintain and replace the attached equipment, and to address these problems, it was necessary to suction and remove the sludge-like Si scale and clean the pickling tank .
【００１４】本発明者らは、上記した問題点を解決する
ために鋭意検討した結果、金属材料の連続酸洗設備の酸
洗槽の酸洗液に、ヒドロキシアルキリデンジホスホン酸
および／またはヒドロキシアルキリデンジホスホン酸の
水溶性塩を、上記酸洗液中の合計濃度として１mg/l以上
添加することによって、連続酸洗設備におけるスケール
の付着を大幅に抑制し、前記した種々の問題のいずれを
も解決することが可能であることを見出した。The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, hydroxyalkylidene diphosphonic acid and / or hydroxyalkylidene was added to the pickling solution in the pickling tank of the continuous pickling equipment for metallic materials. By adding a water-soluble salt of diphosphonic acid at a total concentration of 1 mg / l or more in the above pickling solution, the adhesion of scale in a continuous pickling facility is significantly suppressed, and any of the various problems described above is solved. It was found that it could be solved.
【００１５】本発明におけるヒドロキシアルキリデンジ
ホスホン酸は、下記一般式(1) で示され、該ヒドロキシ
アルキリデンジホスホン酸としては、１−ヒドロキシエ
チリデン−１，１−ジホスホン酸（：１−ヒドロキシエ
タン−１，１−ジホスホン酸）が例示される。The hydroxyalkylidene diphosphonic acid in the present invention is represented by the following general formula (1), and the hydroxyalkylidene diphosphonic acid is 1-hydroxyethylidene-1,1-diphosphonic acid (: 1-hydroxyethane- 1,1-diphosphonic acid).
【００１６】[0016]
【化１】 Embedded image
【００１７】上記一般式(1) 中、Ｒは炭素原子数１〜５
のアルキル基を示す。また、一般式(1) で示されるヒド
ロキシアルキリデンジホスホン酸の水溶性塩としては、
ヒドロキシアルキリデンジホスホン酸のアルカリ金属
塩、アルカリ土類金属塩、アンモニウムアミン塩、アン
モニウム塩および低級アルカノールアミン塩などから選
ばれる１種または２種以上が好ましい。In the above general formula (1), R represents 1 to 5 carbon atoms.
Represents an alkyl group. Further, as the water-soluble salt of hydroxyalkylidene diphosphonic acid represented by the general formula (1),
One or more selected from alkali metal salts, alkaline earth metal salts, ammonium amine salts, ammonium salts and lower alkanolamine salts of hydroxyalkylidene diphosphonic acid are preferred.
【００１８】なお、上記したアルカリ金属塩としては、
Na塩および／またはＫ塩が好ましく、アルカリ土類金属
塩としてはCa塩および／またはMg塩が好ましい。また、
本発明においては、好ましくは、ヒドロキシアルキリデ
ンジホスホン酸および／またはヒドロキシアルキリデン
ジホスホン酸の水溶性塩を、金属材料の連続酸洗設備の
酸洗槽の酸洗液に、該酸洗液中の合計濃度として１mg/l
以上、より好ましくは１〜20mg/lとなるように添加す
る。The above alkali metal salts include:
Na salts and / or K salts are preferred, and alkaline earth metal salts are preferably Ca salts and / or Mg salts. Also,
In the present invention, preferably, a hydroxyalkylidene diphosphonic acid and / or a water-soluble salt of hydroxyalkylidene diphosphonic acid is added to a pickling bath in a pickling tank of a continuous pickling facility for metal materials, 1 mg / l as total concentration
As described above, it is more preferable to add 1 to 20 mg / l.
【００１９】上記添加量が１mg/l未満の場合は、スケー
ル付着抑制効果が低く、逆に20mg/lを超える場合は、ス
ケール付着抑制効果が実用上飽和し、経済的でない。本
発明においては、酸洗槽の酸洗液へのヒドロキシアルキ
リデンジホスホン酸および／またはヒドロキシアルキリ
デンジホスホン酸の水溶性塩の添加は、図２に示す酸洗
液補給のための酸洗液貯槽７への供給、酸洗槽の酸洗液
への直接供給もしくは図１に示すように酸洗液循環配管
５中の酸洗液への供給によって行うことができる。When the amount is less than 1 mg / l, the effect of suppressing scale adhesion is low. On the other hand, when it exceeds 20 mg / l, the effect of suppressing scale adhesion is practically saturated and is not economical. In the present invention, the addition of the hydroxyalkylidene diphosphonic acid and / or the water-soluble salt of hydroxyalkylidene diphosphonic acid to the pickling solution in the pickling tank is performed by adding the pickling solution tank shown in FIG. 7 or by direct supply to the pickling solution in the pickling tank or to the pickling solution in the pickling solution circulation pipe 5 as shown in FIG.
【００２０】本発明における酸洗液の組成は、酸洗対象
となる金属材料の組成によって異なるが、塩酸水溶液、
硫酸水溶液、硝酸水溶液、塩酸および硫酸を含む水溶
液、硝酸および弗酸を含む水溶液、硝酸および塩酸を含
む水溶液が例示される。また、本発明は、好ましくは、
酸洗液中のSi（金属シリコン）およびSi化合物のSiの合
計Si量（：合計Si濃度）がSiO2換算で50mg/l以上、より
好ましくは、酸洗液中のSiおよびSi化合物のSiの合計Si
量（：合計Si濃度）がSiO2換算で100mg/l 以上である金
属材料の連続酸洗設備におけるスケール付着抑制方法と
して適用される。The composition of the pickling solution in the present invention depends on the composition of the metal material to be pickled.
Examples thereof include an aqueous solution of sulfuric acid, an aqueous solution of nitric acid, an aqueous solution containing hydrochloric acid and sulfuric acid, an aqueous solution containing nitric acid and hydrofluoric acid, and an aqueous solution containing nitric acid and hydrochloric acid. Also, the present invention, preferably,
The total Si content (total Si concentration) of Si (metallic silicon) and Si of the Si compound in the pickling solution (total Si concentration) is 50 mg / l or more in terms of SiO 2 , more preferably, Si in the pickling solution and Si of the Si compound. Total Si
This method is applied as a method for suppressing scale adhesion in a continuous pickling facility for a metal material having an amount (: total Si concentration) of 100 mg / l or more in terms of SiO 2 .
【００２１】これは、酸洗液中のSiおよびSi化合物のSi
の合計Si量（：合計Si濃度）がSiO2換算で50mg/l以上の
場合、さらには100mg/l 以上の場合、金属材料の連続酸
洗設備における前記した種々の問題が生じ、本発明によ
ってこれらの問題を解決できるためである。なお、酸洗
液中のSiおよびSi化合物のSiの合計Si量（：合計Si濃
度）がSiO2換算で1000mg/lを超える場合、スケール付着
を抑制することが困難となるため、本発明においては、
酸洗液中のSiおよびSi化合物のSiの合計Si量（：合計Si
濃度）はSiO2換算で1000mg/l以下であることが望まし
い。This is because Si and Si compound in the pickling solution
When the total Si amount (: the total Si concentration) is 50 mg / l or more in terms of SiO 2 , or even 100 mg / l or more, the above-described various problems occur in the continuous pickling equipment for metal materials. This is because these problems can be solved. When the total Si amount of Si and Si of the Si compound in the pickling solution (: the total Si concentration) exceeds 1000 mg / l in terms of SiO 2 , it becomes difficult to suppress scale adhesion, and therefore, in the present invention, Is
Total Si amount of Si and Si of Si compound in pickling liquid (: Total Si
Concentration) is preferably 1000 mg / l or less in terms of SiO 2 .
【００２２】また、本発明は、特に、Si含有量が2.5wt
％以上の珪素鋼板、さらに好ましくはSi含有量が2.5 〜
4.5wt ％の珪素鋼板の、好ましくは塩酸水溶液による酸
洗もしくは塩酸−硫酸混酸水溶液による酸洗におけるス
ケール付着抑制方法として好適に適用される。これは、
Si含有量が2.5wt ％以上の珪素鋼板の塩酸酸洗もしくは
塩酸−硫酸混酸酸洗において特に前記した種々の問題が
顕在化し、上記珪素鋼板の酸洗に本発明を適用すること
によって前記した種々の問題を全て基本的に大幅に解決
できるためである。In addition, the present invention is particularly applicable to the case where the Si content is 2.5 wt.
% Or more, more preferably a silicon content of 2.5 to
It is suitably applied as a method for suppressing the adhesion of scale in a 4.5 wt% silicon steel sheet, preferably in an acid solution with an aqueous hydrochloric acid solution or in an acid solution with a mixed aqueous solution of hydrochloric acid and sulfuric acid. this is,
The above-mentioned various problems particularly become apparent when pickling hydrochloric acid or pickling with hydrochloric acid-sulfuric acid of a silicon steel sheet having a Si content of 2.5% by weight or more. This is because all of the above problems can basically be largely solved.
【００２３】前記したように、本発明に係る上記した珪
素鋼板のSi含有量の好適上限値は4.5wt ％であり、これ
はSi含有量が4.5wt ％超えの場合、珪素鋼板の加工が困
難となるためである。また、上記した珪素鋼板の塩酸酸
洗もしくは塩酸−硫酸混酸酸洗における酸濃度の好適範
囲は、塩酸酸洗の場合、塩酸濃度が２〜20wt％であり、
塩酸−硫酸混酸酸洗の場合、塩酸および硫酸の合計濃度
が２〜40wt％である。As described above, the preferred upper limit of the Si content of the above-mentioned silicon steel sheet according to the present invention is 4.5 wt%, which means that when the Si content exceeds 4.5 wt%, it is difficult to process the silicon steel sheet. This is because Further, the preferred range of the acid concentration in the above-mentioned silicon steel sheet pickling with hydrochloric acid or pickling with hydrochloric acid-sulfuric acid is 2 to 20% by weight in the case of pickling with hydrochloric acid,
In the case of pickling with a mixed solution of hydrochloric acid and sulfuric acid, the total concentration of hydrochloric acid and sulfuric acid is 2 to 40% by weight.
【００２４】本発明においては、酸洗槽の酸洗液に、前
記一般式(1) で示されるヒドロキシアルキリデンジホス
ホン酸および／またはヒドロキシアルキリデンジホスホ
ン酸の水溶性塩に加えて、その他のスケール防止剤、ス
ケール分散剤、防食剤を添加してもよい。以上、本発明
について説明したが、本発明によれば、後記の実施例に
示すように、鋼帯などの金属材料、特に珪素鋼板の連続
酸洗設備におけるSi系スケールの生成に伴う(1) 酸洗液
加温用の熱交換器における使用エネルギーの増加、(2)
耐酸性熱交換器に用いられる樹脂製のチューブ保守時の
破損、(3) 金属帯の蛇行に伴うラインの停止、(4) 金属
帯の蛇行に伴うロールの交換、(5) ヘドロの除去作業、
(6) 酸洗液循環ポンプの破損、(7) 酸洗液循環ポンプの
閉塞に伴う酸洗槽内の液温の不均一化などの問題を全て
大幅に解決することが可能となった。In the present invention, in addition to the water-soluble salt of hydroxyalkylidene diphosphonic acid and / or hydroxyalkylidene diphosphonic acid represented by the general formula (1), other scales may be added to the pickling solution in the pickling tank. An inhibitor, a scale dispersant, and an anticorrosive may be added. Although the present invention has been described above, according to the present invention, as shown in Examples below, a metal material such as a steel strip, particularly with the generation of a Si-based scale in a continuous pickling facility for silicon steel sheets (1) Increased energy used in heat exchanger for heating pickling liquid, (2)
Damage during maintenance of resin tubes used in acid-resistant heat exchangers, (3) Shutdown of line due to meandering of metal band, (4) Replacement of rolls due to meandering of metal band, (5) Removal of sludge ,
(6) Problems such as breakage of the pickling liquid circulation pump and (7) non-uniformity of the liquid temperature in the pickling tank due to blockage of the pickling liquid circulation pump can all be largely solved.
【００２５】[0025]
【実施例】以下、本発明を実施例に基づいてさらに具体
的に説明する。 （実施例１）図１に示す連続酸洗設備において、Si含有
量が３wt％の方向性電磁鋼板（珪素鋼板）の塩酸酸洗を
行った。EXAMPLES The present invention will be described below more specifically based on examples. (Example 1) In the continuous pickling equipment shown in Fig. 1, hydrochloric acid pickling of a grain-oriented electrical steel sheet (silicon steel sheet) having a Si content of 3 wt% was performed.
【００２６】本実施例においては、図１に示す薬液貯液
槽10から、１−ヒドロキシエチリデン−１，１−ジホス
ホン酸（：１−ヒドロキシエタン−１，１−ジホスホン
酸）の濃厚水溶液を、定量ポンプ11によって酸洗液循環
配管５中の酸洗液へ供給し、酸洗槽１内の酸洗液中の上
記１−ヒドロキシエチリデン−１，１−ジホスホン酸の
濃度を10mg/lに維持した（本発明例１）。In the present embodiment, a concentrated aqueous solution of 1-hydroxyethylidene-1,1-diphosphonic acid (: 1-hydroxyethane-1,1-diphosphonic acid) is supplied from a drug solution storage tank 10 shown in FIG. It is supplied to the pickling liquid in the pickling liquid circulation pipe 5 by the metering pump 11 to maintain the concentration of 1-hydroxyethylidene-1,1-diphosphonic acid in the pickling liquid in the pickling tank 1 at 10 mg / l. (Example 1 of the present invention).
【００２７】試験期間中の酸洗液の組成の平均値を表１
に示す。なお、酸洗液の液温は、80℃とした。試験結果
を、１−ヒドロキシエチリデン−１，１−ジホスホン酸
無添加時の結果（比較例）と併せて表２に示す。また、
１−ヒドロキシエチリデン−１，１−ジホスホン酸無添
加時に間接熱交換器４のテフロンチューブに固着したス
ケールの分析結果を表３に示す。Table 1 shows the average value of the composition of the pickling solution during the test period.
Shown in The temperature of the pickling solution was set to 80 ° C. The test results are shown in Table 2 together with the results when no 1-hydroxyethylidene-1,1-diphosphonic acid was added (Comparative Example). Also,
Table 3 shows the analysis results of the scale fixed to the Teflon tube of the indirect heat exchanger 4 when 1-hydroxyethylidene-1,1-diphosphonic acid was not added.
【００２８】なお、上記した本発明例においては、板表
面保護性の指標である酸洗減量(Pickling-Loss) は比較
例に対してほとんど変化せず、過酸洗は生ぜず、また製
造された珪素鋼板へホルステライト皮膜を形成せしめた
際の皮膜の目付量も比較例に対してほとんど変化せず、
本発明による酸洗方法を用いても良好な品質の珪素鋼板
が得られることが分かった。In the above-mentioned examples of the present invention, the pickling loss (Pickling-Loss), which is an index of the surface protection of the plate, hardly changes from that of the comparative example, and no peracid washing occurs, and the product is manufactured. When the forsterite film was formed on the silicon steel sheet, the basis weight of the film hardly changed from the comparative example.
It has been found that a silicon steel sheet of good quality can be obtained even by using the pickling method according to the present invention.
【００２９】（実施例２）図１に示す連続酸洗設備にお
いて、前記した本発明例１において、添加する薬剤を代
えた以外は本発明例１と同様の条件で、Si含有量が３wt
％の方向性電磁鋼板（珪素鋼板）の塩酸酸洗を行った。
すなわち、前記した本発明例１において、１−ヒドロキ
シエチリデン−１，１−ジホスホン酸に代えて、１−ヒ
ドロキシエチリデン−１，１−ジホスホン酸（：１−ヒ
ドロキシエタン−１，１−ジホスホン酸）のNa塩を本発
明例１と同様の方法で、酸洗槽１内の酸洗液中に供給
し、酸洗槽１内の酸洗液中の上記Na塩の濃度を10mg/lに
維持した（本発明例２）。Example 2 In the continuous pickling equipment shown in FIG. 1, the Si content was 3 wt.% Under the same conditions as in Example 1 of the present invention except that the agent to be added was changed.
% Oriented magnetic steel sheet (silicon steel sheet) was pickled with hydrochloric acid.
That is, in Example 1 of the present invention described above, 1-hydroxyethylidene-1,1-diphosphonic acid (: 1-hydroxyethane-1,1-diphosphonic acid) is used instead of 1-hydroxyethylidene-1,1-diphosphonic acid. Is supplied to the pickling solution in the pickling tank 1 in the same manner as in Example 1 of the present invention, and the concentration of the Na salt in the pickling solution in the pickling tank 1 is maintained at 10 mg / l. (Example 2 of the present invention).
【００３０】試験結果を、表４に示す。表２〜表４に示
されるように、本発明によれば、組成が例えばFe2O3 ：
18.7wt％、SiO2：41.0wt％である、硬質で緻密なSi系ス
ケールの酸洗設備の接液部への付着を抑制し、下記の種
々の優れた効果を得ることができ、前記した従来技術の
問題点を全て大幅に解決することが可能となった。The test results are shown in Table 4. As shown in Tables 2 to 4, according to the present invention, the composition is, for example, Fe 2 O 3 :
18.7wt%, SiO 2: a 41.0Wt%, adhesion to the wetted portion of the pickling of dense Si based scale inhibiting a hard, it is possible to obtain various excellent effects described below, and the All the problems of the prior art can be largely solved.
【００３１】(1) 鋼帯の蛇行によるライン停止が皆無と
なり、鋼帯の酸洗設備における生産性の向上を達成する
ことができた。 (2) 鋼帯の蛇行によるライン停止が皆無となり、ロール
交換に要する工数が０となった。 (3) 熱交換器における蒸気などの加熱媒体の使用量を削
減することが可能となり、省エネルギーに寄与すること
ができる。(1) There was no line stoppage due to the meandering of the steel strip, and the productivity of the pickling equipment for the steel strip could be improved. (2) There was no line stoppage due to the meandering of the steel strip, and the man-hour required for the roll change became zero. (3) It is possible to reduce the amount of a heating medium such as steam used in a heat exchanger, which can contribute to energy saving.
【００３２】(4) 熱交換器チューブの交換が不要とな
り、鋼帯の酸洗設備における生産性の向上に寄与するこ
とができ、また熱交換器チューブの交換に要する工数が
０となった。 (5) 循環ポンプの破損、閉塞による循環ポンプの交換頻
度が減少し、循環ポンプの交換に要する工数を削減でき
ると共に、酸洗液循環ポンプの閉塞に伴う酸洗槽内の液
温の不均一化時のトラブルを減少できる。(4) It is not necessary to replace the heat exchanger tube, which can contribute to the improvement of productivity in the pickling equipment for steel strip, and the man-hour required for replacing the heat exchanger tube becomes zero. (5) The frequency of replacing the circulating pump due to breakage or blockage of the circulating pump is reduced, and the man-hour required for replacing the circulating pump can be reduced. Troubles during construction can be reduced.
【００３３】(6) 酸洗設備の酸洗液と接触する各種器壁
に付着、固着するスケールの除去および酸洗槽底部に堆
積するヘドロの清掃に要する時間を短縮することがで
き、鋼帯の酸洗設備における生産性の向上を達成するこ
とができた。(6) It is possible to reduce the time required for removing the scale adhered and fixed to the various walls of the pickling equipment which comes into contact with the pickling liquid and cleaning sludge deposited on the bottom of the pickling tank. The improvement of productivity in the acid pickling equipment was achieved.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【表３】 [Table 3]
【００３７】[0037]
【表４】 [Table 4]
【００３８】[0038]
【発明の効果】本発明によれば、下記(1) 〜(3) に示す
種々の優れた効果が得られ、珪素鋼帯などの金属帯の連
続酸洗設備の生産性が大幅に向上すると共に、省エネル
ギーおよび省力化が達成でき、さらには安全に寄与する
ことができ、本発明は工業上極めて有用である。According to the present invention, various excellent effects shown in the following (1) to (3) are obtained, and the productivity of the continuous pickling equipment for metal strips such as silicon steel strips is greatly improved. At the same time, energy saving and labor saving can be achieved, and furthermore, safety can be contributed, and the present invention is extremely useful industrially.
【００３９】(1) 金属帯の連続酸洗設備の生産性の向
上：金属帯の蛇行によるライン停止、保守および熱交換
器チューブ交換が不要となると共に、酸洗設備における
付着、固着スケール、堆積スケールの除去、清掃に要す
る時間を短縮することができ、金属帯の連続酸洗設備に
おける生産性の向上を達成することができる。(1) Improvement in productivity of continuous pickling equipment for metal strips: line stoppage due to meandering of metal strips, maintenance and replacement of heat exchanger tubes are not required, and adhesion, sticking scale, and deposition in pickling equipment. The time required for scale removal and cleaning can be reduced, and the productivity of the continuous pickling equipment for metal strips can be improved.
【００４０】(2) 省エネルギーへの寄与：熱交換器にお
ける蒸気使用を削減することが可能となり、省エネルギ
ーに寄与することができる。 (3) 省力化の達成、安全への寄与：スケールの除去、清
掃に要する時間の短縮、ロール交換頻度の減少、酸洗液
循環ポンプの交換頻度の減少、熱交換器チューブの交換
の不要化などによって、省力化を達成することができ
る。(2) Contribution to energy saving: It is possible to reduce the use of steam in the heat exchanger, and to contribute to energy saving. (3) Achieving labor saving and contributing to safety: removing scale, shortening the time required for cleaning, reducing the frequency of changing rolls, reducing the frequency of replacing pickling liquid circulation pumps, and eliminating the need to replace heat exchanger tubes. For example, labor saving can be achieved.
【００４１】また、さらには、酸洗液を扱う設備の保守
作業が軽減されるため安全に寄与することができる。Further, since the maintenance work of the equipment for handling the pickling liquid is reduced, it is possible to contribute to safety.
【図１】本発明に係る鋼帯の連続酸洗設備の一例を示す
説明図（側断面図）である。FIG. 1 is an explanatory diagram (side sectional view) showing an example of a continuous pickling facility for steel strip according to the present invention.
【図２】本発明に係る鋼帯の連続酸洗設備の一例を示す
説明図（側断面図）である。FIG. 2 is an explanatory view (side sectional view) showing an example of a continuous pickling equipment for a steel strip according to the present invention.
１ 酸洗槽 ２ 酸洗液 ３ ヘルパーロール ４ 間接熱交換器（：テフロンチューブ式熱交換器） ５ 酸洗液循環配管 ６ 酸洗液循環ポンプ ７ 酸洗液貯液槽 ８ 流量調節弁 ９ 弁 10 薬液貯液槽 11 薬液定量供給ポンプ 12 逆止弁 Ｓ 鋼帯 f1 鋼帯の通板方向 f2 酸洗液の循環方向DESCRIPTION OF SYMBOLS 1 Pickling tank 2 Pickling liquid 3 Helper roll 4 Indirect heat exchanger (: Teflon tube type heat exchanger) 5 Pickling liquid circulation pipe 6 Pickling liquid circulation pump 7 Pickling liquid storage tank 8 Flow control valve 9 Valve 10 Chemical liquid storage tank 11 Chemical liquid supply pump 12 Check valve S Steel strip f 1 Passing direction of steel strip f 2 Direction of pickling liquid circulation
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K053 PA02 PA12 QA01 RA11 RA14 RA15 RA16 RA17 RA19 RA25 RA52 RA63 SA06 TA16 XA14 XA24 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K053 PA02 PA12 QA01 RA11 RA14 RA15 RA16 RA17 RA19 RA25 RA52 RA63 SA06 TA16 XA14 XA24
Claims (3)
液に、ヒドロキシアルキリデンジホスホン酸および／ま
たはヒドロキシアルキリデンジホスホン酸の水溶性塩
を、前記酸洗液中の合計濃度として１mg/l以上添加する
ことを特徴とする金属材料の連続酸洗設備におけるスケ
ール付着抑制方法。1. A pickling solution in a pickling tank of a continuous pickling equipment for metal materials, wherein a hydroxyalkylidene diphosphonic acid and / or a water-soluble salt of hydroxyalkylidene diphosphonic acid are added as a total concentration in the pickling solution. A method for suppressing scale adhesion in a continuous pickling facility for metallic materials, characterized by adding 1 mg / l or more.
合計量がSiO2換算で50mg/l以上であることを特徴とする
請求項１記載の金属材料の連続酸洗設備におけるスケー
ル付着抑制方法。2. The scale according to claim 1, wherein the total amount of Si and Si of the Si compound in the pickling liquid is 50 mg / l or more in terms of SiO 2. Adhesion control method.
する珪素鋼板であることを特徴とする請求項１または２
記載の金属材料の連続酸洗設備におけるスケール付着抑
制方法。3. The method according to claim 1, wherein the metal material is a silicon steel sheet containing 2.5 wt% or more of Si.
A method of suppressing scale adhesion in a continuous pickling facility for a metal material as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11087600A JP2000282271A (en) | 1999-03-30 | 1999-03-30 | Scale adhesion suppression method for continuous pickling equipment for metallic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11087600A JP2000282271A (en) | 1999-03-30 | 1999-03-30 | Scale adhesion suppression method for continuous pickling equipment for metallic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000282271A true JP2000282271A (en) | 2000-10-10 |
Family
ID=13919487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11087600A Pending JP2000282271A (en) | 1999-03-30 | 1999-03-30 | Scale adhesion suppression method for continuous pickling equipment for metallic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000282271A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011141080A (en) * | 2010-01-07 | 2011-07-21 | Kansetsu Sangyo Kk | Method of preventing build-up of scale to heat exchanger |
| US8128754B2 (en) | 2008-11-14 | 2012-03-06 | Ak Steel Properties, Inc. | Ferric pickling of silicon steel |
| JP2016534229A (en) * | 2013-08-29 | 2016-11-04 | ツェーエムイー ウーファオカー ゲーエムベーハー | Processing method of pickling solution for pickling process |
| JP2017197808A (en) * | 2016-04-27 | 2017-11-02 | Ｐｒｉｍｅｔａｌｓ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｊａｐａｎ株式会社 | Acid-pickling apparatus and operation method during suspension of said acid-pickling |
| JP7510078B2 (en) | 2020-06-24 | 2024-07-03 | 日本製鉄株式会社 | Manufacturing method of grain-oriented electrical steel sheet |
| JP7529978B2 (en) | 2020-06-24 | 2024-08-07 | 日本製鉄株式会社 | Manufacturing method of grain-oriented electrical steel sheet |
| JP7568948B2 (en) | 2020-06-24 | 2024-10-17 | 日本製鉄株式会社 | Manufacturing method of electrical steel sheet |
-
1999
- 1999-03-30 JP JP11087600A patent/JP2000282271A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8128754B2 (en) | 2008-11-14 | 2012-03-06 | Ak Steel Properties, Inc. | Ferric pickling of silicon steel |
| JP2011141080A (en) * | 2010-01-07 | 2011-07-21 | Kansetsu Sangyo Kk | Method of preventing build-up of scale to heat exchanger |
| JP2016534229A (en) * | 2013-08-29 | 2016-11-04 | ツェーエムイー ウーファオカー ゲーエムベーハー | Processing method of pickling solution for pickling process |
| JP2017197808A (en) * | 2016-04-27 | 2017-11-02 | Ｐｒｉｍｅｔａｌｓ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｊａｐａｎ株式会社 | Acid-pickling apparatus and operation method during suspension of said acid-pickling |
| WO2017187737A1 (en) * | 2016-04-27 | 2017-11-02 | Ｐｒｉｍｅｔａｌｓ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｊａｐａｎ株式会社 | Pickling device and paused pickling operation method |
| US10711353B2 (en) | 2016-04-27 | 2020-07-14 | Primetals Technologies Japan, Ltd. | Pickling device and pickling pause operation method |
| JP7510078B2 (en) | 2020-06-24 | 2024-07-03 | 日本製鉄株式会社 | Manufacturing method of grain-oriented electrical steel sheet |
| JP7529978B2 (en) | 2020-06-24 | 2024-08-07 | 日本製鉄株式会社 | Manufacturing method of grain-oriented electrical steel sheet |
| JP7568948B2 (en) | 2020-06-24 | 2024-10-17 | 日本製鉄株式会社 | Manufacturing method of electrical steel sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20120273013A1 (en) | Process for the demulsifying cleaning of metallic surfaces | |
| JP4366462B2 (en) | How to wash the circulating water system | |
| US5417819A (en) | Method for desmutting aluminum alloys having a highly reflective surface | |
| JP2000282271A (en) | Scale adhesion suppression method for continuous pickling equipment for metallic material | |
| JP2015150484A (en) | Scale removal method and scale remover for steam generating apparatus | |
| JP2018104752A (en) | Detergent composition for steel plates | |
| CN111322904A (en) | Optimization method for heat exchanger pickling process | |
| EP3134559A1 (en) | Method and formulations for removing rust and scale from steel and for regenerating pickling liquor in hot-dip galvanization process | |
| JP2023093710A (en) | Ultrasound degreasing equipment | |
| CN108342256A (en) | A kind of heat transmission equipment water system cleaning agent and preparation method thereof | |
| WO2012150719A1 (en) | Process and device for producing glass substrate for cover glass for use in electronic appliance, and method and device for removing alkali fluoroaluminate | |
| CN115491681B (en) | Chemical cleaning liquid and cleaning process for boiler with oxygenation working condition | |
| CN112853364A (en) | Condenser manganese scale chemical cleaning agent | |
| JP2008248329A (en) | Method for pickling ferritic stainless steel sheet | |
| US3188292A (en) | Pickling inhibiting compositions | |
| FI83545B (en) | FOERFARANDE FOER KEMISK POLERING AV YTOR AV ROSTFRITT STAOL SAMT VID FOERFARANDET ANVAENT BAD. | |
| JP2002177988A (en) | Water treatment method for circulation type cooling water system | |
| JPH0975950A (en) | Water treatment | |
| JPS638757Y2 (en) | ||
| JP2003286593A (en) | Facility for pickling stainless steel and process for controlling pickling solution in the facility | |
| JP3319398B2 (en) | Horizontal pickling equipment | |
| JPH10265986A (en) | Method for continuously annealing and pickling cold rolled stainless steel strip and device therefor | |
| JP2004342822A (en) | Device and method for treating liquid | |
| JPH0892888A (en) | Scale preventing agent and prevention of scale in deinking process of wastepaper | |
| JP3620373B2 (en) | Continuous annealing method and continuous annealing apparatus for steel strip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040528 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050519 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050607 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050802 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20050830 |